JPH08202031A - Positive photoresist composition - Google Patents

Abstract

PURPOSE: To provide a photoresist composition superior in independency of film thickness and development latitude and high in resolution and further, superior in the balance of other resist performances by using the ester form of the quinonediazido compound of a polyhydroxy compound specified in structure and specified in the number and arrangement of intramolecular hydroxyl groups as a photosensitive material. CONSTITUTION: The photoresist composition comprises an alkali-soluble resin, and at least one kind of 1,2-naphthoquinonediazido-sulfonic acid ester of the polyhydroxy compound represented by formulae I and II in which each of R1 -R4 is, independently, an H or halogen atom or an alkyl group; R5 is, independently, same as R1 or the like; each of R and R' is, independently, an H atom or an alkyl group, but when both are H atoms at the same time, each of R1 and R4 is not an H atom: and each of (m) and (n) is 0-3.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION 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. The present invention relates to a line-sensitive positive photoresist composition, more specifically, a positive photoresist for microfabrication, which is excellent in film thickness dependence, development latitude, exhibits high resolution, and is excellent in other resist performance balance. It relates to photoresists.

[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. After that, it is heated and dried, and a circuit pattern or the like is baked through an exposure mask by irradiation of ultraviolet rays or the like, and if necessary, post-exposure baking is performed and then development is performed to form a positive image. Further, etching is performed using this positive image as a mask, whereby patterned processing can be performed on the substrate. Typical fields of application include manufacturing processes for semiconductors such as ICs, manufacturing circuit boards such as liquid crystals and thermal heads, and other photo-ablation processes.
These integrated circuits are becoming more and more integrated,
0.5 μm for manufacturing semiconductor substrates such as VLSI
Alternatively, it has become necessary to process an ultrafine pattern having a line width smaller than that. In such applications, there is a demand for a photoresist having a wide development latitude in which a stable and high resolution can be obtained and a constant processing line width is always ensured. Further, it is required that no resist residue is generated in the resist pattern after development in order to prevent circuit processing defects. Furthermore, since there is a step of baking after exposure, a resist having high heat resistance is desired.

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 resolving power changes greatly even if the film thickness changes by only a few hundredths 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. 1925, p. 626 (1993).
The existence thereof is 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 when the contrast of the resist is increased so as to obtain a pattern having a high resolution and a rectangular cross-sectional shape, the film thickness dependency is often increased. 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 carrying out fine processing close to the limit of its resolution using a positive photoresist. Therefore, the resist is required to have high performance with respect to various performances as described above.

Japanese Unexamined Patent Publication (Kokai) No. 2-296249 discloses a quinonediazide ester compound of a polyhydroxy compound having a specific structure such as the following [formula XVI]. However, the film thickness dependence, the development latitude, and the resolution are disclosed. However, it was still unsatisfactory in terms of balance of resist performance.

[0006]

Embedded image

[0007]

As described above, the composition of the resist material is used in order to produce a film having excellent film thickness dependency, development latitude, high resolution, and other excellent resist performance balance. Until now, it was completely unknown how to design the. Therefore, an object of the present invention is to provide a positive photoresist composition for ultrafine processing, which is excellent in film thickness dependency, development latitude, exhibits high resolution, and is excellent in other resist performance balance. . In the present invention, “thickness dependence” means that the resist film thickness before exposure is λ / 4.
It refers to the fluctuation of the resolution of the resist obtained by exposure and (if necessary, baking) development when the value changes in the range of n.

[0008]

Means for Solving the Problems As a result of intensive investigations by the present inventors, the quinonediazide compound of a polyhydroxy compound having a specific structure and having a specific number and arrangement of hydroxyl groups in the molecule has been obtained. It was found that the above-mentioned problems can be solved by using the above ester as a photosensitive material, and the present invention has been completed based on this finding. That is, an object of the present invention is to contain an alkali-soluble resin and at least one kind of 1,2-naphthoquinonediazide sulfonic acid ester of a polyhydroxy compound represented by the following general formula (I) or (II). And a positive photoresist composition.

[0009]

Embedded image

In the formula, R _{1 to} R ₄ are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group, and R ₅ are the same or different, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, Acyl group, cycloalkyl group, aryl group R, R ': may be the same or different, hydrogen atom, alkyl group provided that when R and R'are hydrogen atoms at the same time, R ₁ , R ₄
Is not a hydrogen atom. m and n represent 0 to 3.

In the present invention, when a quinonediazide sulfonic acid ester of a polyhydroxy compound having the above-mentioned specific structure is used as a photosensitive material, it is excellent in film thickness dependency and development latitude, exhibits high resolution, and further balances other resist performances. Will be better. Although the details are not clear, it is considered that the above-mentioned specific effect is exhibited by appropriately selecting the number of benzene rings, the number of hydroxyl groups, and the position of hydroxyl groups in the molecule of the polyhydroxy compound. . This was unexpected from the conventional knowledge. Further, by setting the alkali-soluble resin and the phenolic low molecular weight compound to be specific ones, the above effect becomes more remarkable, and the developing latitude becomes particularly excellent.

The present invention will be described in detail below. The specific polyhydroxy compound used in the present invention is a compound represented by the above general formula (I) or (II). In the general formulas (I) and (II), the alkyl group represented by R _{1 to} R ₅ is a methyl group, an ethyl group, a propyl group, an isopropyl group,
n-butyl group, isobutyl group, sec-butyl group, te
An alkyl group having 1 to 4 carbon atoms such as an rt-butyl group is preferable, and a methyl group and an ethyl group are more preferable. As the halogen atom, chlorine atom, bromine atom and iodine atom are preferable, and chlorine atom is particularly preferable. The alkoxy group of R ₅ is a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and an acyl group is a formyl group or an acetyl group. A benzoyl group is preferred. A methoxy group is particularly preferred. As the cycloalkyl group, a cyclopentyl group and a cyclohexyl group are preferable, and a cyclohexyl group is particularly preferable. As the aryl group, a phenyl group, a toluyl group, a xylyl group, and a cumenyl group are preferable.

In the general formulas (I) and (II), R,
The alkyl group of R'is methyl group, ethyl group, propyl group
Group, isopropyl group, n-butyl group, isobutyl group,
Carbon number such as sec-butyl group, tert-butyl group
1-4 alkyl groups are preferred, more preferably methyl
Group. R₁As preferred, a methyl group and ethyl
Group, a tert-butyl group, R ₂, R₃As preferred
Specifically, a hydrogen atom and a methyl group are preferable, and a hydrogen atom is particularly preferable.
Good. R_FourIs preferably a hydrogen atom or a methyl group.
is there. R_FiveAs preferred, a hydrogen atom, a methyl group, and a salt
An elementary atom, a cyclohexyl group. Water as R and R '
Elemental atoms and methyl groups are preferred. General formula in the present invention
Specific examples of the compounds represented by (I) and (II) are shown below.
You. However, the contents of the present invention are not limited to these.
There is no.

[0014]

[Chemical 4]

[0015]

Embedded image

[0016]

[Chemical 6]

The photosensitive material used in the present invention is, for example, the above polyhydroxy compound and 1,2-naphthoquinonediazide-5.
It can be obtained by carrying out an esterification reaction with-(and / or -4-) sulfonyl chloride in the presence of a basic catalyst. That is, a predetermined amount of polyhydroxy compound and 1,2
-Naphthoquinonediazide-5- (and / or-4-) sulfonyl chloride, dioxane, acetone, tetrahydrofuran, methyl ethyl ketone, N-methylpyrrolidone, chloroform, trichloroethane, trichloroethylene, dichloroethane or γ-butyl lactone in a flask. Then, a basic catalyst such as sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethylamine, 4-dimethylaminopyridine, 4-methylmorpholine, N-methylpiperazine, N-methylpiperidine and the like is added dropwise for condensation. The product obtained is
After crystallization in water, it is washed with water and further purified and dried.

If necessary, 1,2-naphthoquinonediazide-5-sulfonic acid ester and 1,2-naphthoquinonediazide-4-sulfonic acid ester may be used in combination. The reaction temperature in the above method is usually -20.
-60 ° C, preferably 0-40 ° C.

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

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

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

In addition, JP-A-60-45238 and 60-
97347, 60-140235, 60-1897.
39, 64-14229, JP-A-1-276131,
2-60915, 2-275955, 2-282
745, 4-101147, 4-122938, etc., that is, it is preferable to use a technique in which low-molecular components of novolac resin are removed or reduced.

The novolak resin has a dispersity (ratio of weight average molecular weight Mw to number average molecular weight Mn, that is, Mw /
The Mn) is preferably 1.5 to 7.0, and more preferably 1.5 to 5.5. When the dispersity exceeds 7.0, the effect obtained by the present invention becomes small. If the dispersity is less than 1.5, a high degree of purification process is required,
Inappropriate due to lack of practicality. The weight average molecular weight of the thus obtained novolak resin is 1000 to 200.
It is preferably in the range of 00, more preferably 15
It is 00 to 15000. If it is less than 1,000, the film loss of the unexposed area after development is large, and if it exceeds 20,000, the developing speed becomes slow. 3000-1 is especially suitable.
It is in the range of 5000. Here, the weight average molecular weight is defined as a value in terms of polystyrene of gel permeation chromatography.

In the present invention, it is preferable to select various kinds of resins depending on the intended use of the composition. Specifically, the alkali-soluble resin is at least three or more of cresols other than m-cresol, that is, o-cresol, p-cresol, and 2,3-xylenol, 2,6-xylenol, and trimethylphenol. It is preferably a condensate of a mixture containing a phenolic monomer and an aldehyde compound. In addition, the alkali-soluble resin is a condensate of an aldehyde compound and a mixture containing at least one phenolic monomer selected from phenol, cresol other than m-cresol, xylenol, and trimethylphenol, in which m-cresol is essential. Preferably there is.

In the present invention, the above-mentioned photosensitive material should be used, but if necessary, 1,2-naphthoquinonediazide-5- (and / or-) of the polyhydroxy compound shown below is used.
4-) An esterified product with sulfonyl chloride can be used in combination. In this case, the ratio of the naphthoquinone diazide ester photosensitive material of these polyhydroxy compounds which can be used in combination and 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.

Examples of polyhydroxy compounds include 2,
3,4-trihydroxybenzophenone, 2,4,4 '
-Trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4 4'-
Tetrahydroxybenzophenone, 2,4,6,3 ',
4'-pentahydroxybenzophenone, 2,3,4
2 ', 4'-pentahydroxybenzophenone, 2,
3,4,2 ', 5'-pentahydroxybenzophenone, 2,4,6,3', 4 ', 5'-hexahydroxybenzophenone, 2,3,4,3', 4 ', 5'-hexahydroxy Polyhydroxybenzophenones such as benzophenone,

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

Bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) propane-1, bis (2,3,4-tri) Hydroxyphenyl) propane-1, nordihydroguaiaretic acid, 1,1-
Bis ((poly) hydroxyphenyl) alkanes such as 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-hydroxy-phenyl) 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, 2,3,3
4,2 ', 3', 4 ', 3 ", 4"-octahydroxy-5,5'-diacetyltriphenylmethane, 2,4
6,2 ', 4', 6'-Hexahydroxy-5,5'-
Polyhydroxytriphenylmethanes such as dipropionyltriphenylmethane, 4,4 '-(phenylmethylene) bisphenol, 4,4'-(1-phenyl-ethylidene) bis [2-methylphenol], 4,4 ',
Polyhydroxytriphenylethanes such as 4 ″ -ethylidene-trisphenol,

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
Polyhydroxyspirobiindanes such as 6,5 ′, 6 ′, 7′-hexool, 2,4,4-trimethyl-
Polyhydroxyflavans such as 2 ', 4', 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, 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, α , Α, α ', α',
α ″, α ″ -hexakis- (4-hydroxyphenyl)
Japanese Patent Application Laid-Open No. 5-22 such as -1,3,5-triethylbenzene
Polyhydroxy compounds described in No. 4410, 1, 2,
2,3-tetra (p-hydroxyphenyl) propane,
1,3,3,5-tetra (p-hydroxyphenyl) pentane and the like, JP-A-5-303200, EP-5301
48. Poly (hydroxyphenyl) alkane according to 48.

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-cresol, 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.

It is also possible to use a low molecular weight phenolic resin such as novolac resin.

The composition of the present invention preferably further contains a low molecular weight compound having a phenolic hydroxyl group (hereinafter, also referred to as a phenolic low molecular weight compound) in order to accelerate the dissolution in the developing solution. This can further improve the development latitude. The phenolic low molecular weight compound used in the present invention is at least one phenolic 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. is there. Among such compounds, compounds that increase the alkali dissolution rate of the alkali-soluble resin when added to the alkali-soluble resin are preferable. As a result, the development latitude is further improved. Also,
The ratio of the number of phenolic hydroxyl groups to the number of aromatic rings in one molecule is preferably 0.5 to 1.4.

If the total carbon number of the compound is more than 50, the effect of the present invention is reduced. On the other hand, if it is less than 12, a new defect such as a decrease in heat resistance occurs. In order to exert the effect of the present invention, it is necessary to have at least two phenolic hydroxyl groups in the molecule, but if it exceeds 8, the effect of improving the development latitude will be lost. Further, if the ratio of the number of phenolic hydroxyl groups to the number of aromatic rings in one molecule 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 dependency, which is not preferable.

Specific examples of the phenolic low molecular weight compound 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'-Bienyl 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 can be mentioned.

The amount of the low molecular weight compound added is preferably 1 to 80% by weight, more preferably 2 to 70% by weight, based on the alkali-soluble resin. If the amount added exceeds 80% by weight, the development residue deteriorates and a new defect that the pattern is deformed during development is not preferable.
The low molecular weight compound having a phenolic hydroxyl group used in the present invention is described in, for example, JP-A-4-122938 and JP-A-2.
-28531, US Pat. No. 4,916,210, European Patent No. 2
It can be easily synthesized by those skilled in the art by referring to the method described in 19294 and the like.

Solvents for dissolving the photosensitive material and the alkali-soluble novolak resin used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene. Glycol methyl ether acetate,
Propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 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,
A high-boiling solvent such as N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether can be mixed and used.

A surfactant may be added to the positive photoresist composition of the present invention in order to further improve the coating properties such as striation. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonyl Polyoxyethylene alkyl allyl ethers such as phenol ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristea Sorbitan fatty acid esters such as oleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sol Monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc., polyoxyethylene sorbitan fatty acid esters nonionic surface active agents such as, Efutotsupu EF
301, EF303, EF352 (Shin-Akita Kasei Co., Ltd.)
Manufactured by), Megafasc F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103,
SC104, SC105, SC106 (Made by Asahi Glass Co., Ltd.)
Fluorine-based surfactants such as organosiloxane polymer KP341 (produced by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymerization polyflow No. 7
5, No. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like. Among these surfactants, fluorine-based surfactants and silicon-based surfactants are particularly preferable. 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 of the present invention. These surfactants may be added alone,
It is also possible to add some combinations.

As the developer for the positive photoresist composition of the present invention, 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
Uses an aqueous solution of alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and cyclic amines such as pyrrole and piperidine, etc. 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. Of these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are more preferable.

The positive photoresist composition of the present invention may contain a light absorber, a cross-linking agent, an adhesion aid, etc., 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 described in "Technology and Markets of Industrial Dyes" (CMC Publishing) and the Handbook of Dyes (edited by the Society of Synthetic Organic Chemistry), such as CIDe
sperse Yellow 1,3,4,5,7,8,13,23,31,49,50,51,54,56,
60,64,66,68,79,82,88,90,93,102,114 and 124, CIDis
perse Orange 1,5,13,25,29,30,31,44,57,72 and 73, C.
I. Disperse Red 1,5,7,13,17,19,43,50,54,58,65,72,7
3,88,117,137,143,199 and 210, CIDisperse Violet 4
3, CIDisperse Blue 96, CI Fluorescent Brighteni
ng Agent112, 135 and 163, CI Solvent Yellow 14,16,
33 and 56, CISolvent Orange2 and 45, CISolvent R
ed 1,3,8,23,24,25,27 and 49, CI Pigment Green 10,
CI Pigment Brown 2 and the like can be preferably 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, 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. If the amount of the cross-linking agent is more than 10 parts by weight, the sensitivity is lowered and scum (resist 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.

A spinner or coater is provided on a substrate (eg, a silicon / silicon dioxide coating, a glass substrate, a transparent substrate such as an ITO substrate, etc.) on which the above positive photoresist composition is used for the production of precision integrated circuit devices. After applying a suitable coating method, such as pre-baking, exposing through a specified mask, and post-baking (PEB: Post Exposure Bak)
A good resist can be obtained by performing e), developing, rinsing and drying.

[0057]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. In addition,% indicates weight% unless otherwise specified. Synthesis Example (1) Synthesis of Compound [I-2] 4 equipped with stirrer, reflux condenser, thermometer, dropping device
A 4-necked flask was charged with 69.1 g of 4-ethylresorcinol, 1.2 kg of 4-hydroxybenzyl alcohol, and 1 liter of methanol, and the mixture was heated with stirring at 60 ° C. and homogenized, and then 5 g of sulfuric acid was slowly added, and the mixture was refluxed for 10 minutes. The mixture was heated and stirred for an hour. The reaction mixture was added to 10 liters of distilled water, and the obtained brown solid was purified by column chromatography to obtain 70 g of the target white solid [I-2].

Synthetic Example (2) Synthesis of Compound [I-3] In place of 4-ethylresorcinol in Synthetic Example (1), 4-
Compound [I-3] was synthesized by the same method as in Synthesis Example (1) except that tert-butylresorcinol was used. Synthetic Example (3) Synthesis of Compound [II-1] Instead of 4-ethylresorcinol of Synthetic Example (1), 2-
Compound [II-1] was synthesized by the same method as in Synthesis Example (1) except that methylresorcinol was used.

Synthesis Example (4) Synthesis of Photosensitive Material a A compound (I-2) (35.0 g), 1,2-naphthoquinonediazide-5-sulfonyl chloride (53.7 g), and acetone (800 ml) were charged into a three-necked flask and homogeneously charged. Dissolved in. Then, 20.8 g of N-methylpiperidine was gradually added dropwise, and the mixture was reacted at 25 ° C for 3 hours. The reaction mixture was concentrated and then redissolved in acetone to prepare a 1% aqueous hydrochloric acid solution 2.8.
Pour into a liter, filter the resulting precipitate, wash with water, and dry (4
0 ° C.) to give 1,2-naphthoquinonediazide-5-sulfonic acid ester of compound [I-2] (photosensitive material a) 7
3.3 g was obtained.

Synthesis Example (5) Synthesis of Photosensitive Material b Compound (I-2) 35.0 g, 1,2-naphthoquinonediazide-5-sulfonyl chloride 80.6 g, and acetone 1.0 liter were placed in a three-necked flask. Charged and dissolved uniformly. Then, 31.2 g of N-methylpiperidine
Was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was concentrated, then dissolved again in acetone, poured into 3.2 liters of a 1% hydrochloric acid aqueous solution, and the generated precipitate was filtered, washed with water and dried (40 ° C.) to give 1 of the compound [I-2]. , 2-naphthoquinonediazide-5-sulfonic acid ester (photosensitive material b) was obtained in an amount of 94.2 g.

Synthesis Example (6) Synthesis of Photosensitive Material c 37.8 g of compound [I-3], 53.7 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 800 ml of acetone were charged into a three-necked flask and homogeneously charged. Dissolved in. Then, 20.8 g of N-methylpiperidine was gradually added dropwise, and the mixture was reacted at 25 ° C for 3 hours. After concentrating the reaction mixture, it is dissolved again in acetone and a 1% aqueous hydrochloric acid solution of 3.0 is added.
Pour into a liter, filter the resulting precipitate, wash with water, and dry (4
0 ° C.) to give 1,2-naphthoquinonediazide-5-sulfonic acid ester of compound [I-3] (photosensitive material c) 7
5.9 g was obtained.

Synthesis Example (7) Synthesis of Photosensitive Material d 37.8 g of compound [I-3], 80.6 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1.0 liter of acetone were placed in a three-necked flask. Charged and dissolved uniformly. Then, 31.2 g of N-methylpiperidine
Was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was concentrated, then dissolved again in acetone, poured into 3.2 liters of a 1% aqueous hydrochloric acid solution, and the resulting precipitate was filtered off, washed with water and dried (40 ° C.) to give compound 1 of Compound [I-3]. , 2-naphthoquinonediazide-5-sulfonic acid ester (photosensitive material d) (96.8 g) was obtained.

Synthesis Example (8) Synthesis of Photosensitive Material e 33.6 g of the compound [II-1], 53.7 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 800 ml of acetone were charged into a three-necked flask and homogeneously charged. Dissolved in. Then, 20.8 g of N-methylpiperidine was gradually added dropwise, and the mixture was reacted at 25 ° C for 3 hours. After concentrating the reaction mixture, it is dissolved again in acetone and a 1% aqueous hydrochloric acid solution of 3.0 is added.
Pour into a liter, filter the resulting precipitate, wash with water, and dry (4
0 ° C.) to give 1,2-naphthoquinonediazide-5-sulfonic acid ester of compound [II-1] (photosensitive material e) 7
2.1 g was obtained.

Synthesis Example (9) Synthesis of Photosensitive Material f 33.6 g of compound [II-1], 80.6 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1.0 liter of acetone were placed in a three-necked flask. Charged and dissolved uniformly. Then, 31.2 g of N-methylpiperidine
Was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was concentrated, dissolved again in acetone, poured into 3.2 liters of a 1% aqueous hydrochloric acid solution, and the resulting precipitate was filtered off, washed with water and dried (40 ° C.) to give 1 of the compound [II-1]. , 2-naphthoquinonediazide-5-sulfonic acid ester (photosensitive material f) (93.0 g) was obtained.

Synthesis Example (10) Synthesis of Photosensitive Material g [Comparative Example] 32.1 g of the following polyhydroxy compound [XVI], 1,
2-naphthoquinonediazide-5-sulfonyl chloride 5
3.7 g and 800 ml of acetone were charged into a three-necked flask and uniformly dissolved. Then, 20.8 g of N-methylpiperidine was gradually added dropwise, and the mixture was reacted at 25 ° C for 3 hours. After concentrating the reaction mixture, dissolve it again in acetone and
% Hydrochloric acid aqueous solution, the resulting precipitate is filtered off, washed with water and dried (40 ° C.) to obtain 1,2-naphthoquinonediazide-5-sulfonic acid ester of compound [XVI] (photosensitive material g). 70.7 g was obtained.

[0066]

[Chemical 7]

Synthesis Example (11) Synthesis of Photosensitive Material h [Comparative Example] 33.6 g of the above compound [XVI], 80.6 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 1.0 liter of acetone Charge the mouth flask,
Dissolved uniformly. Then N-methylpiperidine 31.
2 g was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was concentrated, then dissolved again in acetone, poured into 3.2 liters of a 1% hydrochloric acid aqueous solution, and the generated precipitate was filtered off, washed with water,
Drying (40 ° C.) was performed to obtain 91.6 g of 1,2-naphthoquinonediazide-5-sulfonic acid ester of compound [XVI] (photosensitive material h).

The production examples of the novolac resin according to the present invention are shown below. Synthesis example (12) Synthesis of novolak resin (A) m-cresol 63.0 g, p-cresol 87.0
g, 71.4 g of 37% formalin aqueous solution and 0.084 g of oxalic acid dihydrate are charged into a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and stirred at 100 ° C.
The temperature was raised to 10, and the reaction was performed for 10 hours. After the reaction, the temperature was cooled to room temperature, the reflux condenser was removed, and the pressure was reduced to 25 mmHg. Then, the temperature was gradually raised to 188 ° C., water and unreacted monomers were removed, and 102 g of novolak resin (a) was obtained. When this is analyzed by GPC, Mw is 6830, Mw
/Mn=5.8.

Synthesis Example (13) Synthesis of novolac resin (B) m-cresol 299.2 g, p-cresol 189.
5 g and 257.2 g of a 37% aqueous formalin solution were charged into a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and stirred with heating in an oil bath at 110 ° C. When the internal temperature reached 92 ° C, 0.67 g of oxalic acid dihydrate was added. After that, the reaction was continued under reflux for 16 hours, the temperature of the oil bath was further raised to 210 ° C., and water and unreacted monomers were removed under reduced pressure except for the reflux condenser to obtain 363 g of novolak resin (B). When analyzed by GPC, Mw
Was 8550, and Mw / Mn = 6.2.

Synthesis Example (14) Synthesis of novolak resin (C) 55 g of novolak resin (B) was dissolved in 345 ml of acetone and 220 ml of toluene, and then 21
0 ml of hexane was added, and the mixture was heated to 40 ° C with stirring. This solution was allowed to stand at room temperature for 16 hours to obtain a precipitate. The precipitate was collected, filtered, and dried in a vacuum oven at 50 ° C. to give about 23 g of novolak resin (d).
I got When analyzed by GPC, Mw is 1020
0 and Mw / Mn = 3.3.

Synthesis Example (15) Synthesis of Novolac Resin (D) In a three-necked flask having an internal volume of 500 ml equipped with a stirrer and a reflux condenser, 56.4 g of m-cresol and 2,6-bis (hydroxymethyl) -4 were prepared. -Methylphenol 3.97
g, 2,5-xylenol 26.3 g and formalin (37% aqueous solution) 39.6 g were charged and well stirred while heating in an oil bath at 108 ° C., and oxalic acid 0.11 g was added to 1
The mixture was heated and stirred for 6 hours. Next, the temperature is raised to 205 ° C., the pressure is gradually reduced to 1-2 mmHg, and distillation is performed for 2 hours.
Unreacted monomers, water, formaldehyde, oxalic acid, etc. were removed. The temperature is lowered to room temperature and 61 g of novolac resin (D)
I got When this is analyzed by GPC, Mw is 4400,
It was Mw / Mn = 4.8.

Synthesis Example (16) Synthesis of novolak resin (E) 32 g of novolak resin (D) was dissolved in 96 g of methanol. 50 g of distilled water was gradually added to this while stirring to precipitate the resin component. The upper layer separated into two layers was removed by decanting. Next, 46 g of methanol was added to and dissolved in this, and 65 g of distilled water was gradually added again with stirring to precipitate the resin component. The separated upper layer was removed by decanting and the recovered resin component was heated to 40 ° C. in a vacuum dryer and
After drying for 4 hours, 15.2 g of novolak resin (E) was obtained. When analyzed by GPC, Mw was 8930, Mw /
It was Mn = 2.9.

Synthesis Example (17) Synthesis of novolac resin (F) 9 g of methylenebis-p-cresol, 2.2 g of o-cresol, 88.2 g of 2,3-dimethylphenol,
2,3,5-trimethylphenol 14.66 g, 2,
9.77 g of 6-dimethylphenol 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, 75.3 g of a 37% formalin aqueous solution was added, and the mixture was stirred while heating in an oil bath at 110 ° C. Inner temperature is 9
Upon reaching 0 ° C., 6.2 g of oxalic acid dihydrate was added. After that, the temperature of the oil bath was kept at 130 ° C. for 18 hours to continue the reaction, and then the reflux condenser was removed, followed by vacuum distillation at 200 ° C. to remove unreacted monomers. The obtained novolak resin had Mw of 3680 and Mw / Mn = 2.1.

Examples 1-18 and Comparative Examples 1-4 Novolak resins (A) obtained in the above Synthesis Examples 14-19.
~ (F) and the photosensitive materials (a) obtained in Synthesis Examples 1 to 9
(F), the comparative photosensitizers (g) and (h) obtained in Synthesis Examples 10 and 11, and optionally a low molecular weight compound and other photosensitizers S-1 to S-4 are shown in Table 1 below. Were mixed in the types and amounts described in 1), dissolved in 18 g of ethyl lactate and 4.5 g of ethoxyethyl propionate, and filtered using a 0.1 μm microfilter to prepare a photoresist composition. This photoresist composition was applied to a silicon wafer using a spinner, and a vacuum adsorption hot plate
It was dried at 0 ° C. for 90 seconds to obtain a resist film having a film thickness of 0.98 μm. A reduction projection exposure device (NS manufactured by Nikon Corp.)
R-200519C), and then exposed to a vacuum adsorption hot plate at 110 ° C. for 90 seconds, and then exposed to 2.38%.
Tetramethylammonium hydroxide aqueous solution of 1
It was developed for 1 minute, washed with water for 30 seconds and dried.

[0075]

[Table 1]

[0076]

[Table 2]

P-1: 1- [α-methyl-α- (4'-
Hydroxyphenyl) ethyl] -4- [α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene P-2: tris (4-hydroxyphenyl) methane P-3: 1,1-bis (4- Hydroxyphenyl) cyclohexane P-4: bis (2,5-dimethyl-4-hydroxyphenyl) -2'-hydroxyphenylmethane P-5: 2,6-bis (2'-hydroxy-5-methylbenzyl) -4 -Methylphenol S-1: 1,1-bis {3- (4'-hydroxybenzyl) -4-hydroxy-5-methylphenyl} cyclohexane 1,2-naphthoquinonediazide-5-sulfonic acid ester compound (2 etc.) Amount) S-2: 2,6-bis (4'-hydroxybenzyl)-
1,2-naphthoquinonediazide-5-sulfonic acid ester of 4-cyclohexyl-phenol (2 equivalents) S-3: 2,6-bis (4'-hydroxy-2 ', 5'
-Dimethyl-benzyl) -4-methylphenol 1,
2-naphthoquinonediazide-5-sulfonic acid ester compound (2 equivalents) S-4: methylenebis {2- (4'-hydroxy-3 '
-Cyclohexylbenzyl) -6-methylphenol}
1,2-naphthoquinonediazide-5-sulfonic acid ester compound (2 equivalents)

The resist pattern of the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the photoresist composition. The results are shown in Table 2 below. The sensitivity was defined as the exposure dose for reproducing a mask pattern of 0.4 μm. To evaluate the development latitude, the development time was changed to 40 seconds and 90 seconds, and the same evaluation was performed. The ratio of the sensitivities defined above in both cases was used as an index of the development latitude. The closer this value is to 1.0, the wider the development latitude and the more desirable the result. The resolving power represents a limiting resolving power at an exposure amount for reproducing a mask pattern of 0.4 μm. In order to evaluate the film thickness dependence, the film thickness of each sample is 1.00 μm
The silicon wafer applied according to the above was similarly exposed and developed. Film thickness of 0.98 μm and film thickness of 1.0
The ratio of the resolution of 0 μm was used as an index of the film thickness dependence.
The closer this ratio is to 1.0, the smaller the film thickness dependency, which is a desirable result. For heat resistance, use a hot plate on a silicone wafer with a resist pattern
It was heated for a minute, and the temperature was shown so that the pattern did not deform.

[0079]

[Table 3]

[0080]

[Table 4]

As shown in Table 2 above, the resist samples satisfying the requirements of the present invention were
It can be seen that the film thickness dependency, the development latitude are excellent, the high resolution is exhibited, and the other resist performance balance is excellent.

[0082]

The resist of the present invention is characterized in that it is excellent in film thickness dependence, has high resolution, has a wide development latitude, and is excellent in other resist performance balance. Therefore, it is most preferably used for mass production of semiconductor devices having an ultrafine circuit.

Front page continuation (72) Inventor Shinji Sakaguchi 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fuji Shashin Film Co., Ltd.

Claims (3)

[Claims] 1. A positive electrode containing an alkali-soluble resin and at least one 1,2-naphthoquinonediazide sulfonic acid ester of a polyhydroxy compound represented by the following general formula (I) or (II). -Type photoresist composition. Embedded image In the formula, R _{1 to} R ₄ : may be the same or different, hydrogen atom, halogen atom, alkyl group, R ₅ : may be the same or different, hydrogen atom, halogen atom, alkyl group, alkoxy group, acyl group, Cycloalkyl group, aryl group R, R ': may be the same or different, hydrogen atom, alkyl group, provided that when R and R'are hydrogen atoms at the same time, R ₁ and R ₄
Is not a hydrogen atom. m and n represent 0 to 3. 2. The positive type according to claim 1, wherein the alkali-soluble resin is an alkali-soluble phenol novolac resin having a weight average molecular weight to number average molecular weight ratio of 1.5 to 5.5. Photoresist composition. 3. The alkali-soluble resin is 2 to 7 relative to the alkali-soluble resin.
In an amount of 0% by weight, the total number of carbon atoms in one molecule is 12 to 50,
3. A low molecular compound having 2 to 8 phenolic hydroxyl groups in one molecule is contained.
The positive photoresist composition described in 1.