JPH08160614A - Positive type photo-resist composition - Google Patents

Abstract

PURPOSE: To provide a positive photo-resist composition having a wide development latitude and high heat resistance with no sensitivity loss while maintaining high resolution and a wide defocus latitude by containing a specific alkali-soluble novolak resin, a photosensitive agent, and a low-molecule compound respectively. CONSTITUTION: Phenols of formula I, phenols and aldehydes selected from formulas II, III, and m-cresol are condensed to obtain an alkali-soluble novolak resin. This positive photo-resist composition contains the alkali-soluble novolak resin having the ratio of 1.5-4.0 between the weight average molecular weight and the number average molecular weight, a 1,2-naphthoquinone diazide-5-(and/or -4-)sulfonic acid ester photosensitive agent, and a low-molecule compound having the total carbon number of 12-50 in one molecule and 2-8 phenol hydroxyl groups in one molecule. In the formulas, R1 and R2 indicate the hydrogen atom or ethoxy group, R3 -R5 indicate the methyl group or hydrogen atom, R6 indicates the hydrogen atom or methyl group, R7 indicates the methyl group or methoxy group, and R8 and R9 indicate the hydrogen atom or hydroxymethyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an ultraviolet ray, a deep ultraviolet ray, containing a specific alkali-soluble novolac resin, a 1,2-quinonediazide compound, and a specific low-molecular component additive.
The present invention relates to a positive photoresist composition sensitive to radiation such as X-rays, electron beams, molecular beams, γ-rays and synchrotron radiation. More specifically, it is excellent in development latitude,
The present invention relates to a positive photoresist composition for fine processing, which has high sensitivity, resolution, defocus latitude, and heat resistance. Typical fields of use include semiconductor manufacturing processes such as ICs, liquid crystal, circuit boards such as thermal heads,
Still another photofabrication process.

[0002]

2. Description of the Related Art As a positive photoresist composition,
Generally, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. For example, "Novolac resin phenol resin / naphthoquinone diazide-substituted compound" is disclosed in US Pat. No. 3,666,473.
No. 4,115,128 and No. 4,173,470, etc., and the most typical composition is "Novolak resin consisting of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazide sulfonic acid ester" as an example of Thompson " Introduction toe microlithography (LFThompson "Intr
oduction to Microlithography ") (ACS Publishing, N
o. 219, P112-121).
Novolak resin as a binder is particularly useful in this application because it can be dissolved in an aqueous alkaline solution without swelling, and when it is used as a mask for etching, it has high resistance to plasma etching. Is. Further, the naphthoquinonediazide compound used as a photosensitive material acts as a dissolution inhibitor which lowers the alkali solubility of the novolak resin itself, but when decomposed by light irradiation, an alkali-soluble substance is produced and rather the alkali solubility of the novolak resin is reduced. It is unique in that it acts to enhance it and is particularly useful as a photosensitive material for a positive photoresist because of its large property change with respect to light. From this point of view, many positive photoresists containing a novolac resin and a naphthoquinonediazide-based photosensitive material have been developed and put into practical use, and sufficient results have been obtained in line width processing up to about 1 μm.

However, the degree of integration of integrated circuits is increasing, and in the manufacture of semiconductor substrates such as VLSI,
It has become necessary to fabricate an ultrafine pattern having a line width of 1 μm or less, further 0.5 μm or less. In such applications, particularly, high resolution, defocus latitude, high pattern shape reproducibility that accurately copies the shape of the exposure mask, and a photoresist having a wide development latitude in order to always secure a constant processing line width are required. There is. Higher sensitivity of the resist is also a necessary condition for obtaining higher productivity. In addition, the etching method has been changed from the conventional wet etching method to the dry etching method in order to increase the degree of integration of the integrated circuit. However, since the temperature of the resist increases during the dry etching, thermal deformation does not occur. As described above, the resist is required to have high heat resistance.

Conventionally, it has been considered advantageous to use a resist having a high γ value in order to enhance the resolution and obtain an image having a good pattern shape, and technical development of a resist composition which meets such a purpose has been carried out. There are a great number of patents and reports disclosing such technology, and many patent applications have been made regarding the monomer composition, molecular weight distribution, synthetic method, etc., of the technology of the novolak resin, which is the main component of the positive photoresist. We have achieved certain results. However, such a high resolution resist often has a drawback that the sensitivity is low. On the other hand, in order to increase the sensitivity, a technique of adding a low molecular weight compound having an alkali-soluble group as a dissolution accelerator is disclosed, but on the other hand, the development latitude is narrowed and the heat resistance is lowered. Problems often occurred. In addition, there are many new defects such as impairing the pattern shape. Therefore, it has been desired to develop a resist having a wide development latitude, high sensitivity, resolution, defocus latitude, and heat resistance. Here, the development latitude can be expressed by the development time dependency or the temperature dependency of the resist line width obtained by development. The defocus latitude can be represented by the change of the resist line width with respect to the focus change or the width of the focus that is separated without film loss.

[0005]

Therefore, an object of the present invention is to provide a positive photoresist composition having a particularly high development latitude and high heat resistance while maintaining a high resolution and a wide defocus latitude and without loss of sensitivity. Is to get.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made an intensive study by paying attention to the above various characteristics, and as a result, have found that the degree of dispersion of a novolak resin containing a specific monomer species (phenols), that is, the weight average molecular weight. The ratio of (Mw) to the number average molecular weight (Mn) (hereinafter referred to as dispersity) is important, and it is important to mix the novolak resin with a specific phenolic compound and a photosensitizer in a predetermined range. I found something.

That is, the object of the present invention is (A) an alkali-soluble novolak resin obtained by condensing a phenol compound comprising the following (a), (b) and (c) with an aldehyde, Alkali-soluble novolac resin having a ratio of average molecular weight to number average molecular weight of 1.5 to 4.0, (a) m-cresol 30 to 90 mol% (b) phenols represented by the following general formula (I) 5 -40 mol% (c) Phenols selected from the following general formulas (II) and (III) 0-40 mol%

[Chemical 4]

Embedded image

[Chemical 6]

(B) 1,2-naphthoquinonediazide-5
-(And / or -4-) sulfonic acid ester photosensitizer (more than 30 parts by weight based on 100 parts by weight of novolac resin 10
(Less than 0 part by weight) (C) A low molecular weight compound having a total carbon number of 12 to 50 in one molecule and having 2 to 8 phenolic hydroxyl groups in one molecule (20 parts by weight with respect to 100 parts by weight of novolak resin). And more than 60 parts by weight). However, the molecular weight of the novolac resin refers to a value obtained by gel permeation chromatography (hereinafter, referred to as GPC) defined using standard polystyrene as a reference value.

Here, the relationship between the known technology and the present invention will be described. As a monomer species of novolac resin,
For example, JP-A-58-17112 and JP-A-60-573.
39, JP-A-62-14148, JP-A-62-35
Novolak resins using cresol have been disclosed so far and many of them have been put into practical use, as exemplified in JP-A-347-35, JP-A-62-35349 and the like. In addition, many novolaks using monomer species other than cresol have been proposed in order to improve resolution, heat resistance, profile and the like. For example, a novolac resin containing xylenol and trimethylphenol is disclosed in JP-A-60-176.
034, JP-A-60-164740, JP-A-64-
Novolak resins containing ethylphenol are disclosed in JP-A-62-260145, and novolak resins containing methoxyphenol and dimethoxyphenol have already been proposed by the present inventors (Japanese Patent Application Laid-Open No. Hei 5-206145). 2-93651). Further, many proposals have been made so far regarding novolak resins using monomer species other than the above.

On the other hand, an attempt to improve the characteristics of the resist by giving the novolak resin a specific molecular weight distribution is already known. For example, JP-A-1-105
No. 243 has a molecular weight in the range of 500 to 5000 of 30.
It is described that a novolac resin having a distribution of not more than% is preferable. In addition, JP-A-62-2271
No. 44 and JP-A No. 63-2044 show that the ratio of the specific molecular weight region in the molecular weight distribution has a preferable range. Further, JP-A-60-97347 and JP-A-60-189739 disclose novolac resins in which low-molecular weight components are fractionally removed, and especially JP-A-60-4523.
No. 8, JP-A-3-208054, JP-A-5-1427.
70, JP-A-60-140235 and the like describe the use of a resin having a dispersity of 3 or less as used in the present invention. Further, the low molecular weight compound having an aromatic hydroxyl group that can be used in the present invention is usually as a dissolution accelerator,
It is used for the purpose of improving sensitivity, and many examples of addition to a resist composition are disclosed. For example, JP-A-61-141441 discloses a positive photoresist composition containing trihydroxybenzophenone. The positive photoresist containing trihydroxybenzophenone has improved sensitivity and developability, but has a problem that heat resistance and profile are deteriorated.

Further, JP-A-64-44439, JP-A-1-177032, JP-A-1-280748, JP-A-2-10350, JP-A-3-200251, JP-A-3-191351, and JP-A-3-191351. No. 3-200255, JP-A-4-299348, and JP-A-5-204144 show a method of adding an aromatic polyhydroxy compound other than trihydroxybenzophenone to improve sensitivity without deteriorating heat resistance. ing. However, when such a compound is added, the film loss in the unexposed area increases, and as a result, the shape of the resist is usually deteriorated. In addition, the development latitude is generally lowered because the development speed is increased. Therefore, structural selection of preferred compounds has been carried out in a manner that minimizes these. Therefore, the effect of the present invention is a specific effect which is exhibited only when a certain specific novolac resin is used, the novolac resin has a specific degree of dispersion, and the low molecular weight compound is added in a predetermined amount thereto. . That is, when such a low molecular weight compound is combined with the novolak resin defined in the present invention, the sensitivity of the resist is improved by the action of promoting the dissolution of the low molecular weight compound as expected, while, surprisingly, it is wider than either one alone. It gives the development latitude. Moreover, a composition proposed by the present inventors in which a conventionally known novolak resin containing cresol, xylenol, and methoxyphenol and having a narrow molecular weight distribution is combined with the above-mentioned dissolution accelerator (Japanese Patent Application Laid-Open No. 2-9365).
1, JP-A-4-296755, JP-A-4-2512.
No. 57, JP-A-4-122938), the resolution, defocus latitude and heat resistance were found to be more excellent, and the present invention was completed. It is not clear why such a peculiar effect occurs, but a novolak resin having a narrow molecular weight distribution introduced with a monomer species represented by the formula (I), that is, a monomer species having an ethoxy group at the o-position or the p-position. The effect is considered to be the largest, but in any case, the resolution, defocus latitude, development latitude, and heat resistance obtained by the combination of the novolak resin of the present invention and the photosensitizer in the predetermined range and the dissolution accelerator are The present invention is based on the discovery of this peculiar combination effect, which cannot be expected from the effect alone or in addition.

The embodiments of the present invention will be described in more detail below. First, preferable combinations of phenols for sufficiently exhibiting the effects of the present invention will be described below. In the present invention, the m-cresol component is essential, and the phenol represented by the general formula (I) and the general formula (I
It is an alkali-soluble novolac resin obtained by condensing a phenol selected from I) or (III) and an aldehyde. The first component of the novolak resin of the present invention, m-cresol, is 30 to 90% of all monomer components.
It is required to be mol%, preferably 40 to 80 mol%. In the combination of phenols used in the present invention, if m-cresol is less than 30 mol%, the sensitivity and heat resistance are insufficient, which is not preferable. On the other hand, if it exceeds 90 mol%, the resolving power, the developing latitude and the defocus latitude become insufficient, which is not preferable.

The second component of the novolak resin of the present invention, which is the phenol represented by the general formula (I), that is, the phenol having an ethoxy group at the o-position and / or the p-position, is 5 out of all monomer components. ˜40 mol% is necessary, and preferably 10 to 35 mol%. If the amount of the phenols represented by the general formula (I) is less than 5 mol%, the effect of the present invention, that is, the resolution, the development latitude and the defocus latitude will be insufficient, and if it exceeds 40 mol%,
It is not preferable because the resist profile tends to deteriorate.

The third component of the novolak resin of the present invention, that is, the phenols selected from the above general formula (II) or (III), is in the range of 0 to 40 mol% in all monomers, preferably 0 to 40 mol%. It is in the range of 35 mol%. If the amount of the phenol represented by the general formula (II) or (III) exceeds 40 mol%, the sensitivity and the development latitude are lowered, which is not preferable.

In the present invention, in addition to the above-mentioned phenols, other phenols other than those described in the present invention are added within a range not impairing the effect of the present invention, that is, 5 out of all monomers.
It can also be used at a mol% or less. Examples of the monomer that can be used here include o-cresol, o-methoxyphenol, m-methoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, m-ethoxyphenol, and 3,5-dimethoxyphenol. , 2-methoxy-4-methylphenol, o-propoxyphenol, m-propoxyphenol, p-
Propoxyphenol, o-butoxyphenol, m-
Butoxyphenol, p-butoxyphenol, 3,
4,5-trimethylphenol, 2,3,6-trimethylphenol, o-vinylphenol, m-vinylphenol, p-vinylphenol, o-allylphenol, m-allylphenol, p-allylphenol, o
-Phenylphenol, m-phenylphenol, p-
Phenylphenol, o-benzylphenol, m-benzylphenol, p-benzylphenol, o-methoxycarbonylphenol, m-methoxycarbonylphenol, p-methoxycarbonylphenol, o-benzoyloxyphenol, m-benzoyloxyphenol, p- Benzoyloxyphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, catechol, resorcinol, hydroquinone, phloroglucinol, pyrogallol, o-cyclohexylphenol, p-cyclohexylphenol, 3-methyl-6-cyclohexylphenol, etc. Polyhydroxybenzenes and the like can be shown.

Next, the molecular weight distribution for exerting the effect of the present invention will be described below. The novolak resin used in the composition must have a relatively narrow molecular weight distribution. It is known that such broadening of the molecular weight distribution of a polymer can be generally represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn), that is, the Mw / Mn value (dispersion degree). The wider the distribution is, the larger the numerical value becomes, and the value of the ratio is 1 when there is no distribution. The novolak resin used for a typical positive photoresist has a relatively wide molecular weight distribution, and is disclosed in, for example, JP-A-62-1723.
Many typically have polydispersities between 5 and 10, as typically shown in No. 41. Also, SPIE Proceedings "Advances in Resist Technology and Processing V"
Volume 920, page 349, suggests that values of 4.55 to 6.75 give higher γ values than those of 3.0. In order for the novolac resin according to the present invention to exert such effects, the dispersity is different from these, and it is 1.5 to 4.0, more preferably 2.0 to
Must be in the 3.5 range. If the dispersity is too large, the effects of the present invention such as high resolution, wide defocus latitude, and wide development latitude cannot be obtained. Also, if this value is too small, it requires a high-level purification step in synthesizing the novolac resin, and is not suitable for practical use. The novolak resin of the present invention has an average molecular weight defined by Mw value of 2000 to
Those in the range of 20,000 are preferable, and further 3000
Those in the range of ˜15000 are particularly preferable. If the Mw value is too large, the effects of the present invention for obtaining a high resolving power, a wide defocus latitude, and a wide development latitude cannot be obtained similarly to the above.

Various methods are conceivable for producing a novolac resin having a small degree of dispersion as in the present invention. For example, JP-A-60-189739 and JP-A-60-14
No. 0235, JP-A 64-14229, JP-A 1-1.
No. 05243, Japanese Patent Application Laid-Open No. 2-60915, Japanese Patent Application Laid-Open No. 4-1
No. 22938, JP-A-4-101147, and JP-A-4-101147.
No. 251257, JP-A-4-296755, US Pat. Nos. 4,795,829, and 5,151,339, etc., that is, selection of a specific phenolic monomer, selection of condensation reaction conditions, and further dispersion degree This can be obtained by fractional precipitation of a large conventional novolak resin. In order to obtain the effects of the present invention, those manufactured by using any of these methods may be used. The novolak resin used in the present invention is obtained by polycondensing a mixture of the above phenols with aldehydes.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde. , Vanillin, o-vanillin, is
o-vanillin, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o
-Nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn
-Butylbenzaldehyde, furfural, chloroacetaldehyde and acetals thereof such as chloroacetaldehyde diethyl acetal can be used, but among these, formaldehyde is preferably used mainly. These aldehydes may be used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, methanesulfonic acid, malonic acid, mercaptoacetic acid, oxalic acid and the like can be used, and two or more kinds may be used in combination.

Examples of the photosensitizer used in the present invention include the following esterified products of polyhydroxy compounds with 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonyl chloride.

Examples of polyhydroxy compounds include bis (2,4-dihydroxyphenyl) methane and bis (2,2
3,4-trihydroxyphenyl) methane, bis (2,2
4-dihydroxyphenyl) propane-1, bis (2,2
Bis ((poly) hydroxyphenyl) alkanes such as 3,4-trihydroxyphenyl) propane-1, nordihydroguaiaretic acid, and 1,1-bis (4-hydroxyphenyl) cyclohexane,

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

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

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

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

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

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

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

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

Tris (4-hydroxyphenyl) methane, 4,4 ', 4 "-trihydroxy-3,5,3',
5'-tetramethyltriphenylmethane, 4,4 ',
3 ", 4'-tetrahydroxy-3,5,3 ', 5'-
Tetramethyltriphenylmethane, 4- [bis (3,5
-Dimethyl-4-hydroxyphenyl) methyl] -2-
Methoxy-phenol, 4,4 '-(3,4-diol-benzylidene) bis [2,6-dimethylphenol], 4,4'-[(2-hydroxyphenyl) methylene] bis [2-cyclohexyl-5- Methylphenol], 4,4 ', 2 ", 3", 4 "-pentahydroxy-3,5,3', 5'-tetramethyltriphenylmethane, 2,3,4,2 ', 3', 4 ′ -Hexahydroxy-5,5′-diacetyltriphenylmethane, 2,3,
4,2 ', 3', 4 ', 3 ", 4"-octahydroxy-5,5'-diacetyltriphenylmethane, 2,4
6,2 ', 4', 6'-Hexahydroxy-5,5'-
Polyhydroxytriphenylmethanes such as dipropionyltriphenylmethane,

Polyhydroxy such as 4,4 '-(phenylmethylene) bisphenol, 4,4'-(1-phenyl-ethylidene) bis [2-methylphenol], 4,4 ', 4 "-ethylidene-trisphenol Triphenylethanes,

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

2,4,4-trimethyl-2 ', 4',
Polyhydroxyflavans such as 7'-trihydroxyflavan,

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 dyes such as morin, quercetin and rutin,

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

Polyhydroxy compounds described in JP-A-5-224410, such as α, α, α ', α', α ", α" -hexakis- (4-hydroxyphenyl) -1,3,5-triethylbenzene. , 1,2,2,3-tetra (p-
Hydroxyphenyl) propane, 1,3,3,5-tetra (p-hydroxyphenyl) pentane, etc.
303200, poly (hydroxyphenyl) alkanes described in EP 530148,

P-bis (2,3,4-trihydroxybenzoyl) benzene, p-bis (2,4,6-trihydroxybenzoyl) benzene, m-bis (2,3,4-)
Trihydroxybenzoyl) benzene, m-bis (2,2
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 (2,3,3)
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- (2,4,6-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-dimethylbenzyl) -pyrogallol, 2,6-bis- (4-hydroxy-3,5-dimethylbenzyl) -1,3,4-trihydroxy-phenol, 4,6-bis- (2,4,6-trihydroxybenzyl) -2,4-dimethyl-phenol, 4,6-bis- (2,3,4-trihydroxybenzyl) -2,5-dimethyl- Phenol, 2,6-bis- (4-hydroxybenzyl) -p-gresol, 2,
6-bis (4-hydroxybenzyl) -4-cyclohexylphenol, 2,6-bis (4-hydroxy-3-)
Methylbenzyl) -p-cresol, 2,6-bis (4
-Hydroxy-3,5-dimethylbenzyl) -p-cresol, 2,6-bis (4-hydroxy-2,5-dimethylbenzyl) -p-cresol, 2,6-bis (4-
Hydroxy-3-methylbenzyl) -4-phenyl-phenol, 2,2 ', 6,6'-tetrakis [(4-hydroxyphenyl) methyl] -4,4'-methylenediphenol, 2,2', 6 , 6'-Tetrakis [(4-hydroxy-3-dimethylphenyl) methyl] -4,4 '
-Methylenediphenol, 2,2 ', 6,6'-tetrakis [(4-hydroxy-3-methylphenyl) methyl] -4,4'-methylenediphenol, 2,2'-bis [(4-hydroxy Examples include -3,5-dimethylphenyl) methyl] 6,6'-dimethyl-4,4'-methylenediphenol.

Further, novolac resin, polyhydroxystyrene resin, acetone-pyrogallol resin and the like can also be used.

In the esterification reaction of the photosensitive material, a predetermined amount of polyhydroxy compound and 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonyl chloride are mixed with dioxane, acetone, tetrahydrofuran, methyl ethyl ketone, N. -Dissolved in a solvent such as methylpyrrolidone, chloroform, trichloroethane, trichloroethylene or dichloroethane, a basic catalyst such as sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethylamine, N-methylmorpholine, N-methylpiperazine, 4-dimethylaminopyridine Etc. are added dropwise to condense. The obtained product is washed with water, purified, and dried.

In the usual esterification reaction, a mixture having different esterification numbers and esterification positions can be obtained. However, by selecting the synthesis conditions or the structure of the polyhydroxy compound, only a specific isomer can be selectively selected. Can also be esterified. The esterification rate in the present invention is defined as the average value of this mixture.

The esterification rate thus defined can be controlled by the mixing ratio of the raw material polyhydroxy compound and 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonyl chloride. That is, the added 1,
2-naphthoquinonediazide-5- (and / or -4-)
Substantially all of the sulfonyl chloride undergoes an esterification reaction, so the molar ratio of the raw materials may be adjusted in order to obtain a mixture having a desired esterification rate. In the present invention,
The preferred esterification rate is 30 to 90%, more preferably 40 to 80%. When the esterification rate is less than 30%, the resolution, defocus latitude and profile deteriorate, and when it is 90% or more, the sensitivity decreases. If necessary, 1,2-naphthoquinonediazide-5-sulfonyl chloride and 1,2-naphthoquinonediazide-4-sulfonyl chloride can be used in combination. The reaction temperature in the above method is usually -20 to 60 ° C, preferably 0.
４０40 ° C.

When the photosensitive compound synthesized by the above-mentioned method is used as a resin composition, it is used alone or as a mixture of two or more kinds thereof, and is blended with an alkali-soluble resin. Is more than 30 parts by weight and less than 100 parts by weight with respect to 100 parts by weight of the novolac resin. It is preferably 35 to 90 parts by weight. If the usage ratio is 30 parts by weight or less, the effect of the present invention, that is, the sensitivity, resolution, defocus latitude, and development latitude cannot be sufficiently increased, and if it exceeds 100 parts by weight, the sensitivity and profile deteriorate. Is not preferred.

The low molecular weight compound having a phenolic hydroxyl group constituting the present invention has a total number of carbon atoms in the molecule of 1
2 to 50 and a total number of phenolic hydroxyl groups of 2 to 8 are used. Of these compounds, compounds that increase the alkali dissolution rate of the novolak resin when added to the novolak resin used in the present invention are particularly desirable. If the compound has 51 or more carbon atoms, the effect of the present invention is significantly reduced. On the other hand, if it is 11 or less, new defects such as deterioration of heat resistance occur. In order to exert the effect of the present invention, it is necessary to have at least two hydroxyl groups in the molecule, but if it is 9 or more, the improvement effects of resolution, defocus latitude and development latitude are lost. The preferable addition amount of this low molecular weight compound is more than 20 parts by weight and less than 60 parts by weight, more preferably 30 parts by weight to 100 parts by weight of the novolak resin.
It is in the range of 55 parts by weight. So far, the present inventors have proposed a positive photoresist composition in which 30 parts by weight of a low molecular weight phenol compound is mixed with 100 parts by weight of a novolak resin having a dispersity of 1.5 to 4.0 (special feature: Kaihei 4-1
22938). In the combination with the novolak resin as disclosed herein, when the amount of the dissolution accelerator added exceeds 30 parts by weight, the pattern is deformed during development. Curiously, however, it was found that when the novolac resin of the present invention was used, the effect of the present invention was sufficiently exerted and no pattern deformation was observed when the addition amount exceeded 20 parts by weight. That is, 2
When the amount is 0 parts by weight or less, the effect of the present invention cannot be sufficiently obtained, and when the amount is more than 60 parts by weight, the heat resistance is deteriorated. As the low molecular weight compound used in the present invention, any compound can be used so long as it satisfies the above structural requirements.

Preferred polyhydroxy compounds are:
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,
4,2 ', 4'-tetrahydroxydiphenyl ether, 2,4,2', 4'-tetrahydroxydiphenyl sulfoxide, 2,4,2 ', 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, 1,1,2,2
-Tetrakis (4-hydroxyphenyl) ethane, 1,
1,3-tris (hydroxyphenyl) butane, para [α, α, α ', α'-tetrakis (4-hydroxyphenyl)]-xylene and the like can be mentioned. Furthermore, a polyhydroxy compound that can be used as an intermediate raw material (skeleton) of the photosensitizer can also be used.

The alkali-soluble novolak resin of the present invention,
As the solvent for dissolving the photosensitizer and the dissolution accelerator, 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, propylene glycol monomethyl ether propionate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Methyl hydroxy-3-methylbutanoate, 3
-Methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl β-methoxyisobutyrate, methyl α-hydroxyisobutyrate, methyl pyruvate, ethyl pyruvate, ethyl acetate , Butyl acetate, etc. can be used. These organic solvents may be used alone or in 2
Used in combination with more than one species.

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

The positive photoresist composition of the present invention may contain a surfactant in order to further improve the coating properties such as striation. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene 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.)
Manufactured by), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Florard FC430, 431 (manufactured by 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 Oil and Fat Chemical Co., Ltd.) 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 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, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, ethylamine,
Primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetra An aqueous solution of alkali such as methylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium salt such as choline, cyclic amines such as pyrrole and piperidine, and the like can be used. 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.

The positive photoresist composition of the present invention may contain a light absorber, a cross-linking agent and an adhesion aid, if necessary. The light absorber is added as necessary for the purpose of preventing halation from the substrate and for improving the visibility when applied to the 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,
117, 137, 143, 199 and 210, CI Disperse Violet 4
3, CI Disperse Blue 96, CI Fluorescent Brighte
ning Agent 112, 135 and 163, CI Solvent Yellow 14,
16, 33 and 56, CI Solvent Orange 2 and 45, CI S
olvent Red 1, 3, 8, 23, 24, 25, 27 and 49, CI Pig
ment Green 10, CI Pigment Brown 2 and the like can be preferably used. Light absorber is usually alkali-soluble resin 1
100 parts by weight or less, preferably 50 parts by weight, relative to 00 parts by weight
It is added in an amount of not more than 30 parts by weight, more preferably not more than 30 parts by weight.

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, and improvement of dry etching resistance. 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 cross-linking agents can be added 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 photosensitizer. When the amount of the crosslinking agent is more than 10 parts by weight, the sensitivity is lowered and scum (development residue) is generated, which is not preferable.

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 particularly 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 and 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 adhesive aids are usually used in an amount of 10 parts by weight per 100 parts by weight of the alkali-soluble resin.
The amount is less than 5 parts by weight, preferably less than 5 parts by weight.

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.) which is used for the production of precision integrated circuit devices, Roll coating method, flow coating method, dip coating method, spray coating method,
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.

[0054]

【Example】

[Example] Synthesis example (1) Synthesis of novolak resin A m-cresol 70 g, o-ethoxyphenol 38
g, 37% formalin aqueous solution 53 g and oxalic acid 0.1
Charge 5 g into a 3-neck flask and stir at 100 ° C.
The temperature was raised to and reacted for 14 hours. Then the temperature is 200 ℃
Then, the pressure was gradually reduced to 1 mmHg, and water, unreacted monomers, formaldehyde, oxalic acid, etc. were distilled off. Next, the molten novolac resin was returned to room temperature and collected.
The obtained novolak resin a has a weight average molecular weight of 4,700.
(Polystyrene equivalent). Then, after completely dissolving 20 g of this novolak resin a in 60 g of methanol,
30 g of water was gradually added to this with stirring to precipitate the resin component. The upper layer was removed by decantation, and the precipitated resin component was recovered and heated to 40 ° C.
It was dried for an hour to obtain an alkali-soluble novolak resin A. The obtained novolac resin A has a weight average molecular weight of 11
It is 600 (polystyrene conversion) and the degree of dispersion is 3.10.
Met. The contents of the monomer, dimer and trimer were 0%, 2.8% and 3.6%, respectively, and 54% of the low molecular weight components were removed by the fractional reprecipitation operation.

Synthesis Example (2) Synthesis of Novolac Resin B 70 g of m-cresol, 32 of o-ethoxyphenol
g, 2,3-xylenol 6 g, 37% aqueous formalin solution 56 g, and oxalic acid 0.16 g were charged into a three-necked flask, heated to 100 ° C. with stirring, and reacted 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 novolac resin was returned to room temperature and collected. The obtained novolak resin b had a weight average molecular weight of 3800 (in terms of polystyrene). Next, 20 g of this novolak resin b was completely dissolved in 60 g of acetone, and 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, and the precipitated resin component was recovered. Four
It was heated to 0 ° C. and dried under reduced pressure for 24 hours to obtain an alkali-soluble novolac resin B. The obtained novolak resin B has a weight average molecular weight of 10700 (in terms of polystyrene).
And the dispersity was 3.0. The contents of the monomer, dimer and trimer are 0%, 2.4% and 2.
9%, 68% of low molecular weight components due to fractional reprecipitation operation
Had been removed.

Synthetic Examples (3) to (13) Synthesis of Novolac Resins cm In the same manner as in Synthetic Example (2), the monomers shown in Table 1 were charged in a predetermined mol%, and the novolac was condensed with formaldehyde. Resins cm were obtained.

Synthesis Examples (14) to (24) Synthesis of Novolak Resins C to M After dissolving 20 g of each of the novolak resins c to m obtained in the above Synthesis Examples (3) to (13) in 80 g of acetone,
Hexane (80 g) was gradually added to this with stirring, and the mixture was allowed to stand for 2 hours, the upper layer was removed by decantation, and the precipitated resin was collected and heated to 40 ° C.
It was dried for an hour to obtain alkali-soluble novolak resins CM. Table 2 shows the low molecular weight component removal rates (%), Mw, Mw / Mn, monomers, dimers, and trimer contents of the obtained fractionated novolak resins C to M.

Comparative Example Synthesis Example (25) Synthesis of Novolac Resin n 43 g of m-cresol, 57 g of p-cresol, 37%
Formalin aqueous solution (49 g) and oxalic acid (0.13 g) were charged into a three-necked flask, and the temperature was raised to 100 ° C. with stirring and reacted for 16 hours. Then raise the temperature to 200 ° C,
The pressure was gradually reduced to 5 mmHg to remove water, unreacted monomers, formaldehyde, oxalic acid and the like. Then, the molten alkali-soluble novolac resin was returned to room temperature and recovered. The obtained novolak resin n has a weight average molecular weight of 780.
It was 0 (polystyrene conversion) and the dispersity was 6.20. The contents of monomer, dimer and trimer were 0.2%, 13.1% and 7.2%, respectively.

Synthesis Example (26) Synthesis of novolac resin o m-cresol 50 g, p-cresol 25 g, 2,5
-Xylenol 28 g, 37% formalin aqueous solution 53 g
Further, 0.15 g of oxalic acid was charged into a three-necked flask, the temperature was raised to 100 ° C. with stirring, and the reaction was carried out for 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 novolac resin was returned to room temperature and collected. The resulting novolak resin o had a weight average molecular weight of 4,800 (in terms of polystyrene) and a dispersity of 5.7. The contents of the monomer, dimer and trimer were 0.1%, 14.0% and 6.9%, respectively.

Synthesis Examples (27) and (28) Synthesis of Novolac Resins p and q In the same manner as in Synthesis Example (26), a predetermined mol% of the monomer shown in Table 3 was charged and condensed with formaldehyde. Thus, novolak resins p and q were obtained. Table 3 shows the weight average molecular weights (in terms of polystyrene) of the obtained novolak resins p and q.

Synthesis Example (29) Synthesis of Novolac Resin R 60 g of m-cresol, 40 g of p-cresol, 37%
56 g of an aqueous formalin solution and 0.16 g of oxalic acid were charged into a three-necked flask, the temperature was raised to 100 ° C. with stirring, and the reaction was carried out for 16 hours. Then raise the temperature to 200 ° C,
The pressure was gradually reduced to 1 mmHg, and water, unreacted monomers, formaldehyde, oxalic acid, etc. were distilled off. Next, the molten novolac resin was returned to room temperature and collected. The obtained novolak resin r had a weight average molecular weight of 4,300 (in terms of polystyrene). Then this novolac resin r20g
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, and the precipitated resin component was recovered and heated to 40 ° C., It was dried under reduced pressure for 24 hours to obtain an alkali-soluble novolak resin R. The obtained novolak resin R had a weight average molecular weight of 8900 (in terms of polystyrene) and a dispersity of 3.40. The contents of the monomer, dimer and trimer are 0% and 2.
9% and 3.8%, and 61% of low molecular weight components were removed by the fractional reprecipitation operation.

Synthesis Example (30) Synthesis of Novolac Resin S m-cresol 50 g, p-cresol 25 g, 2,5
-Xylenol 28 g, 37% formalin aqueous solution 53 g
Further, 0.15 g of oxalic acid was charged into a three-necked flask, the temperature was raised to 100 ° C. with stirring, and the reaction was carried out for 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 novolac resin was returned to room temperature and collected. The obtained novolak resin s had a weight average molecular weight of 4,700 (in terms of polystyrene). Next, 20 g of this novolak resin S was completely dissolved in 60 g of methanol, and then 30 g of water was gradually added thereto 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 novolac resin S. The obtained novolak resin S had a weight average molecular weight of 9920 (in terms of polystyrene) and a dispersity of 3.50. Also, monomers, dimers,
The trimer contents were 0%, 2.5% and 3.7%, respectively, and 54% of low molecular weight components were removed by the fractional reprecipitation operation.

Synthesis Examples (31) to (35) Synthesis of Novolac Resins T to X In the same manner as in Synthesis Example (30), the monomers shown in Table 3 were charged in a predetermined mol% and condensed with formaldehyde to give novolak. Resins tx were obtained. 20 g of each of the novolak resins t to x obtained here was mixed with acetone 80
After being dissolved in 80 g of hexane, 80 g of hexane was gradually added thereto with stirring, and the mixture was allowed to stand for 2 hours, the upper layer was removed by decantation, and the precipitated resin component was recovered and heated to 40 ° C. Alkali-soluble resin T after drying for an hour
~ X was obtained. Removal rate (%) Mw, Mw / Mn of low molecular components of the obtained fractionated novolak resin, monomer, dimer,
The trimer content is shown in Table-4.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4]

Synthesis Example (36) Synthesis of Photosensitive Material A 2,3,4,4'-Tetrahydroxybenzophenone 1
2.3 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 40.3 g and 300 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then, a mixed solution of triethylamine / acetone = 15.2 g / 50 ml was gradually added dropwise, and the mixture was reacted at 25 ° C. for 3 hours. 1 reaction mixture
% 1500 mL hydrochloric acid aqueous solution, the precipitate formed is filtered off, washed with water and dried (40 ° C.) to give 2,3,4,4′-
1,2-naphthoquinonediazide-5-sulfonic acid ester of tetrahydroxybenzophenone (photosensitive material A) 3
9.7 g was obtained.

Synthesis Example (37) Synthesis of Photosensitive Material B 3,3,3 ′, 3′-Tetramethyl-1,1′-spirobiindane-5,6,7,5 ′, 6 ′, 7′-hexol 10 g 1,2,2-naphthoquinonediazide-5-sulfonyl chloride (32.0 g) and acetone (500 ml) were charged into a three-necked flask and uniformly dissolved. Then, a mixed solution of triethylamine / acetone = 13.7 g / 50 ml was gradually added dropwise and reacted at 25 ° C. for 3 hours. 1% of reaction mixture
It was poured into 1500 ml of an aqueous hydrochloric acid solution, the precipitate formed was filtered off, washed with water and methanol, and dried (40 ° C).
1,2-naphthoquinonediazide-5-sulfonic acid ester of 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane-5,6,7,5', 6 ', 7'-hexol ( 27.8 g of Photosensitive Material B) was recovered. The product is H
Analysis by PLC revealed that the hexaester content was 83%,
The balance was a mixture of other low-substituted compounds.

Synthesis Example (38) Synthesis of Photosensitive Material C α, α ′, α ″ -tris (4-hydroxyphenyl)-
35.3 g of 1-ethyl-4-isopropylbenzene,
53.7 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 800 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then triethylamine 2
1.2 g was gradually added dropwise and reacted at 25 ° C. for 3 hours.
The reaction mixture was poured into 3000 ml of a 1% aqueous hydrochloric acid solution, the precipitate formed was filtered off, washed with water and dried to obtain α, α ′, α ″ -tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene. 1,2-naphthoquinonediazide-
75.0 g of 5-sulfonic acid ester (photosensitive material C) was obtained.

Synthesis Example (39) Synthesis of Photosensitive Material D 2,6-bis (4-hydroxy-2,5-dimethylbenzyl) -p-cresol 37.6 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 53 0.7 g and 750 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then, 21.2 g of triethylamine was gradually added dropwise and reacted at 25 ° C. for 3 hours. 1 reaction mixture
% Aqueous hydrochloric acid solution (2,500 ml), the precipitate formed is filtered off, washed with water and dried (40 ° C.) to give 2,6-bis (4-
72.1 g of 1,2-naphthoquinonediazide-5-sulfonic acid ester of hydroxy-2,5-dimethylbenzyl) -p-cresol (photosensitive material D) was obtained.

Synthesis Example (40) Synthesis of Photosensitive Material E 4,4 ′, 4 ″ -trihydroxy-3,5,3 ′, 5 ′
-Tetramethyltriphenylmethane 39.3g, 1,2
-Naphthoquinonediazide-5-sulfonyl chloride 5
3.7 g and 750 ml of chloroform were charged into a three-necked flask and uniformly dissolved. Then, 21.2 g of triethylamine was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was concentrated and redissolved in acetone. The obtained mixed solution was poured into 2500 ml of a 1% hydrochloric acid aqueous solution, the precipitate formed was filtered off, washed with water and dried (40 ° C.).
72,4 ', 4 "-trihydroxy-3,5,3', 5'-tetramethyltriphenylmethane 1,2-naphthoquinonediazide-5-sulfonic acid ester (photosensitive material E) 72.
1 g was obtained.

Synthesis Example (41) Synthesis of Photosensitive Material F 4 equipped with a stirrer, reflux condenser, thermometer, dropping device
A three-necked flask was charged with 107.1 g of 3,3'-dimethyl-4,4'-dihydroxybiphenyl, 455.8 g of a 25% aqueous TMAH solution and 500 ml of distilled water, and heated to 40 ° C to obtain 3,3'-dimethyl-4,3. 4'-dihydroxybiphenyl was dissolved. To the mixed solution, 243.5 g of 37% aqueous formalin solution was added dropwise over 30 minutes, and the mixture was heated with stirring at 40 ° C. for 12 hours. Add 500 ml of distilled water and 1 hydrochloric acid to the reaction mixture.
25 ml was added to give a brown solid. The obtained brown solid was purified by column chromatography to obtain 95.9 g of the following compound (a) as a white powder. Next, 82.2 g of the compound (a) obtained above and phenol 282.3 were placed in a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer.
g and 1000 ml of methanol were charged and heated to 60 ° C. to dissolve the compound C. When completely dissolved, 3 g of concentrated sulfuric acid was added, heated to reflux, and stirred for 5 hours. The reaction mixture was crystallized in 10 liters of distilled water, and the yellow solid obtained after filtration was purified by column chromatography to obtain the compound (b) 63.9 as a white powder. Compound (b) 39.8
g, 1,2-naphthoquinonediazide-5-sulfonyl chloride (73.9 g) and chloroform (750 ml) were charged into a three-necked flask and uniformly dissolved. Then, 30.6 g of triethylamine was gradually added dropwise and reacted at 25 ° C. for 4 hours. The reaction mixture was concentrated and redissolved in acetone. The obtained mixed liquid was poured into 3000 ml of a 1% hydrochloric acid aqueous solution, and the resulting precipitate was filtered off, washed with water and dried (40 ° C.) to obtain a light-sensitive material F (79.5 g).

[0074]

[Chemical 7]

Synthesis Example (42) Synthesis of Photosensitive Material G 4 equipped with a stirrer, reflux condenser, thermometer and dropping device
A 2-necked flask was charged with 1141.7 g of 2-cyclohexyl-5-methylphenol, 60.0 g of sodium hydroxide and 300 g of distilled water, and stirred, and 2-cyclohexyl-
When the 5-methylphenol is dissolved, heat to 50 ° C. A 37% aqueous formalin solution was added dropwise to this aqueous solution over 3 hours, and the mixture was heated and stirred as it was for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, neutralized with concentrated hydrochloric acid, and the precipitated brown solid was collected by filtration. The obtained solid was completely dissolved in a 25% tetramethylammonium hydroxide aqueous solution, and neutralized with a 5% ammonium hydrogencarbonate aqueous solution, whereby a light brown powder was deposited and collected by filtration. This powder was washed with distilled water, diluted hydrochloric acid water and distilled water in this order to obtain 409.2 g of the following compound (c). The obtained compound (c) 227.
3g, phenol 941.1g and methanol 1000
ml was charged, and the mixture was heated with stirring at 40 ° C., and when the compound (c) and phenol were completely dissolved, 5 g of concentrated sulfuric acid was added dropwise over 10 minutes, and the mixture was stirred with heating under reflux for 6 hours. After completion of the reaction, the mixed solution was crystallized in 10 liters of distilled water, and the obtained brown solid was purified by column chromatography to obtain 150.0 g of the following compound (d). Compound (d) 57.6
g, 1,2-naphthoquinonediazide-5-sulfonyl chloride (53.7 g) and chloroform (750 ml) were charged into a three-necked flask and uniformly dissolved. Then, 22.3 g of triethylamine was gradually added dropwise and reacted at 25 ° C. for 4 hours. The reaction mixture was concentrated and redissolved in acetone. The obtained mixed liquid was poured into 3000 ml of a 1% hydrochloric acid aqueous solution, and the resulting precipitate was filtered off, washed with water and dried (40 ° C.) to obtain 80.1 g of a photosensitive material G.

[0076]

Embedded image

Synthesis Example (43) Synthesis of Photosensitive Material H The following compound (e) was obtained according to the synthesis method described in JP-A-6-167805. Compound (e) 14.0 g, 1,
2-naphthoquinonediazide-5-sulfonyl chloride 1
7.3 g of triethylamine was gradually added dropwise to a mixture of 6.1 g and 150 g of dioxane, and after completion of the addition, 6 at 30 ° C.
Allowed to react for hours. The reaction mixture is 750 ml of 1% hydrochloric acid aqueous solution.
The resulting precipitate was filtered, washed with water and dried (40 ° C).
Then, 21.1 g of Photosensitive Material H was obtained.

[0078]

[Chemical 9]

Preparation and Evaluation of Positive Photoresist Composition Photosensitive Material A obtained in Synthesis Examples (36) to (43) above
H, the synthesis examples (1) and (2) and the synthesis examples (14) to
(24), and the novolac resins A to M, the novolac resins n to q, the novolac resins R to X obtained in Synthesis Examples (25) to (35), the solvents shown in Table-5, and the polyhydroxy compounds shown in Table-6. The compounds were mixed at the ratios shown in Tables 7 and 8, respectively, to form a uniform solution, which was then filtered using a Teflon microfilter having a pore size of 0.10 μm to prepare a photoresist composition. This photoresist composition was coated on a silicon wafer using a spinner while changing the rotation speed, and dried at 90 ° C. for 60 seconds on a vacuum adsorption hot plate to obtain a resist film having a thickness of 0.97 μm. A reduction projection exposure device (reduction projection exposure device NSR manufactured by Nikon Corp.)
-2005i9C) and then exposed at 110 ° C. for 60
PEB was carried out for 2 seconds, followed by development with a 2.38% tetramethylammonium hydroxide aqueous solution for 1 minute, washing with water for 30 seconds and drying. The resist pattern on the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist. The results are shown in Tables 9 and 10. The sensitivity is
It was defined as the reciprocal of the exposure dose for reproducing a mask pattern of 0.50 μm, and shown as a relative value to the sensitivity of the resist of Comparative Example 1. The resolving power represents a limiting resolving power at an exposure amount for reproducing a mask pattern of 0.50 μm.
For heat resistance, a resist-patterned silicon wafer is baked on a vacuum adsorption hot plate for 4 minutes,
The temperature at which the deformation of the pattern does not occur is shown. 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 0.50 μm resist pattern cross section. The scum is indicated by the residual state of the development residue in the resist pattern of 0.05 μm, the case where the residue is not observed is indicated by ◯, the case where the residue is slightly observed is indicated by Δ, and the considerably remaining one is indicated by x.

[0080]

[Table 5]

[0081]

[Table 6]

[0082]

[Table 7]

[0083]

[Table 8]

[0084]

[Table 9]

[0085]

[Table 10]

[0086]

As described above, according to the present invention, a positive photoresist composition having a particularly high development latitude and high heat resistance while maintaining a high resolution and a wide defocus latitude and without loss of sensitivity. Is obtained.

Claims (1)

[Claims] 1. (A) An alkali-soluble novolac resin obtained by condensing a phenol with the following (a), (b) and (c) and an aldehyde, wherein the weight average molecular weight and the number average molecular weight are: -Soluble novolak resin having a ratio of 1.5 to 4.0 (a) m-cresol 30 to 90 mol% (b) phenols represented by the following general formula (I) 5 to 40 mol% (c) Phenols selected from the following general formulas (II) and (III): 0 to 40 mol% Embedded image Embedded image (B) 1,2-naphthoquinonediazide-5- (and / or -4-) sulfonic acid ester photosensitizer (more than 30 parts by weight and less than 100 parts by weight with respect to 100 parts by weight of novolac resin) (C) in one molecule Containing a low molecular weight compound having a total carbon number of 12 to 50 and having 2 to 8 phenolic hydroxyl groups in one molecule (more than 20 parts by weight and less than 60 parts by weight with respect to 100 parts by weight of novolak resin). A positive photoresist composition characterized by the following: