JPH08220749A - Positive type photoresist composition - Google Patents

Abstract

PURPOSE: To obtain a positive type photoresist having high resolving power, capable of accurately reproducing the dimensions of a mask and having a wide development latitude, superior heat resistance and low dependency on film thickness. CONSTITUTION: This photoresist compsn. contains an alkali-soluble resin (A), a 1,2-naphthoquinonediazide-5 (and/or -4)-sulfonic ester compd. (B), a low molecular compd. (C) having a specified acid-decomposable group and a mol.wt. of <=3,000 and an optical acid generating agent (D) so that the total amt. of the components B, C is regulated to 5-70wt.% of the total amt. of all the solid components and the relational formula 30<=100B/(B+C)<=95(wt.%) is satisfied.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art As a positive photoresist composition,
Generally, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. For example, "Novolak-type phenol resin / naphthoquinone diazide-substituted compound" is disclosed in US Pat. No. 3,666,47.
No. 3, No. 4,115,128 and No. 4,173,47
No. 0 and the like, and the most typical composition is "cresol-formaldehyde novolak resin /
An example of "trihydroxybenzophenone-1,2-naphthoquinone diazide sulfonate" is Thompson "Introduction toe microlithography".
(L.F. Thompson "Introducio
n to Microlithography ”) (A
CS Publishing, No. 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 in the photosensitive material itself acts as a dissolution inhibitor that reduces the alkali solubility of the novolak resin, but when decomposed by irradiation with light, generates an alkali-soluble substance and rather increases the alkali solubility of the novolak resin. It is unique in that it acts to enhance it, and is particularly useful as a photosensitive material for a positive photoresist because of its large property change to light. From this point of view, many positive photoresists containing novolac resin and naphthoquinonediazide-based photosensitive material have been developed and put into practical use from the viewpoint of 1.5 μm to 2 μm.
We have achieved sufficient results in line width processing up to about m.

However, the degree of integration of integrated circuits is increasing more and more, and in the manufacture of semiconductor substrates such as VLSIs,
It is becoming necessary to process an ultrafine pattern having a line width of μm or less. In such applications, particularly high resolution, a photoresist having high sensitivity from the viewpoint of high pattern shape reproducibility that accurately copies the shape of the exposure mask and high productivity is required, and a conventional naphthoquinonediazide-based photosensitive material, for example, US Pat. No. 3,046,1
No. 18, No. 3,106,465, No. 3,148,98
No. 3, each specification, Japanese Examined Patent Publication No. 37-18015, 56-2
In reality, it is not possible to deal with the positive type photoresists using 1,2-naphthoquinone diazide sulfonic acid esters of gallic acid esters and polyhydroxybenzophenones as described in JP-A No. 333, 62-28457 and the like. is there.

On the other hand, in place of 1,2-naphthoquinone diazide sulfonic acid ester of polyhydroxybenzophenones, 1,2-naphthoquinone diazide sulfonic acid ester of a specific polyhydroxy compound is used as a photosensitive component for ultrafine processing. A number of positive photoresist compositions having suitable properties have been proposed (for example, JP-A-60-163043 and 61-97278).
No. 62-10645, No. 62-10646, No. 62-198852, No. 63-220139, Japanese Patent Publication No. 62-3411, No. 1-38289, No. 1-
45901, JP-A-1-291240 and 1-29.
No. 1241, No. 1-291242, No. 1-28074
No. 8, JP-A-2-269351, and JP-A-2-296248.
No. 2-296249). However,
It cannot be said that the positive photoresist composition using these photosensitizers is practically sufficiently improved, and when it is stored in a solution, the photosensitive component is likely to be deposited, and the storage stability is improved. It often caused problems.

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 film thickness, it can be obtained by slightly changing the coating film thickness. Phenomenon that resolution deteriorates (hereinafter,
It is known that there is "film thickness dependency"). Surprisingly, the resolution changes greatly when the film thickness changes by only a few hundreds of μm, and more or less than any of the typical positive photoresists currently on the market. I also found that there was a tendency.

Specifically, if 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 resolving power obtained for this changes. The problem of this film thickness dependence is, for example, in the SPIE Process.
Its existence is pointed out in dings 1925, 626 (1993), and it is stated that this is caused by the multiple reflection effect of light in the resist film.

Here, 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 unevenness on the substrate surface or unevenness of the coating film thickness. Will be done. Therefore, this film thickness dependence has been one obstacle in performing fine processing close to the limit of its resolution using a positive photoresist.

To date, a large number of 1,2-naphthoquinonediazide compounds, which are polyhydroxy compounds having a specific structure, have been proposed in order to increase the resolution. For example,
JP-A-57-63526, JP-A-60-163043,
62-10645, 62-10646, 62
-150245, 63-220139, 64-64
76047, JP-A-1-189644 and 2-28.
No. 5351, No. 2-296248, No. 2-29624
No. 9, No. 3-48249, No. 3-48250, No. 3
-158856, 3-228057, and Tokuhyo Hira 4-
No. 502519, JP-A-4-365046, U.S. Pat. Nos. 4,957,846 and 4,992,356.
No. 5,151,340, No. 5,178,986
And European Patent No. 530,148. However, even if these photosensitive materials are used, they are insufficient from the viewpoint of reducing the film thickness dependency.

On the other hand, by using a photosensitive material having a hydroxyl group in the molecule, a resist having high contrast and high resolution can be obtained, for example, as described in JP-B-37-18.
015, JP-A-58-150948, JP-A 2-1
No. 9846, No. 2-103543, No. 3-22805
No. 7, 5-323597, European Patent No. 57
3,056, U.S. Pat. Nos. 3,184,310, 3,188,210, 3,130,047, 3,130,048, 3,130,049, 3,3. 102,809, 3,061,430, 3,180,733, West German Patent 938,233, SPIE Proceedings 631, 210, 1672, 231 (1992), 1167, 262 (1992) and 1925.
Volume 227 (1993) and the like. Although it is possible to increase the contrast by using the resist containing the photosensitive material described in these publications, it is not sufficient from the viewpoint of reducing the film thickness dependency. As described above, it has never been known how to design the resist material so as to reduce the film thickness dependency and obtain a high resolution regardless of the film thickness.

[0010]

Therefore, the object of the present invention is to (1) particularly in the manufacture of semiconductor devices.
A positive photoresist composition having high resolution,
(2) A positive photoresist composition that accurately reproduces mask dimensions over a wide range of photomask line width,
(3) A positive photoresist composition capable of producing a resist pattern having a cross-sectional shape having a high aspect ratio in a pattern having a line width of 1 μm or less, (4) producing a pattern having a sidewall whose cross-section is nearly vertical. The resulting positive photoresist composition, (5) a positive photoresist composition having a wide development latitude, (6) a positive photoresist composition in which the resulting resist image has excellent heat resistance, (7) excellent storage stability Positive photoresist composition, (8) Positive photoresist composition having high resolution and small thickness dependence of resolution [In the present invention, "thickness dependence" means the resist film thickness before exposure. λ / 4n
Is a variation in the resolving power of the resist obtained by exposure and (if necessary, baking) development when it changes in the range. ], To provide.

[0011]

Means for Solving the Problems The inventors of the present invention have made diligent studies by paying attention to the above various characteristics, and as a result, (A) an alkali-soluble resin, (B) 1,2-naphthoquinonediazide-5 (and / or
Or -4) -sulfonic acid ester compound, (C) acid-decomposable group-containing low molecular weight compound having a molecular weight of 3,000 or less, acid-decomposable group: tertiary alkyl ester group, tertiary alkyl carbonate group, cumyl ester The above object was achieved by a positive photoresist composition containing a group, a tetrahydropyranyl ether group, and (D) a photoacid generator. In the above positive photoresist composition, the blending ratio of the component (B) and the component (C) is 5 ≦ [B + C] ≦ 70 (wt%) ... wt% based on the total solid content, and 30 ≦ 100 B / (B + C) ) ≦ 95 (wt
%) Is preferably satisfied. Hereinafter, the present invention will be described in detail. It has been proposed so far to use a naphthoquinonediazide sulfonic acid ester compound in a chemically amplified resist that utilizes an acid-decomposable compound. For example, in Japanese Patent Laid-Open No. 3-276157, a naphthoquinone diazide is used for a two-component chemically amplified resist consisting of a binder resin in which a part of hydroxyl groups of poly (p-hydroxystyrene) is protected with an acid-decomposable group and a photo-acid generator. A technique of utilizing an ester as a dye for photobleaching is disclosed. In addition, JP-A-5-127386 and JP-A-5-18127
No. 9, each publication discloses a technique of using naphthoquinonediazide ester as a photoacid generator of a two-component chemically amplified resist.

The present invention uses a naphthoquinonediazide type dissolution inhibiting compound in a three-component chemical amplification type resist consisting of an alkali-soluble resin, an acid decomposable dissolution inhibiting compound and a photoacid generator. different. Surprisingly, the combined use of the acid-decomposable dissolution-inhibiting compound and the naphthoquinonediazide-type dissolution-inhibiting compound shows that the performance (high γ value, high resolution) that cannot be obtained by using a single dissolution-inhibiting compound is obtained. The present invention has been completed and the present invention has been completed.

In the present invention, the blending ratio of the component (B) and the component (C) is 5 ≦ [B + C] ≦ 70 (wt%) 30 ≦ 100B / (B + C) ≦ 95 (wt%). More preferably, 10 ≦ [B + C] ≦ 65 (wt%) 40 ≦ 100B / (B + C) ≦ 90 (wt%), and particularly preferably 20 ≦ [B + C] ≦ 60 (wt%) 50 ≦ 100B / (B + C) ≦ 90 (wt%). If the proportion of [B + C] is less than 5% by weight, the residual film rate is remarkably lowered, and if it exceeds 70% by weight, the sensitivity and the solubility in a solvent are lowered. As the 1,2-naphthoquinonediazide-5 (and / or -4) -sulfonic acid ester compound used in the present invention, 1,2-naphthoquinonediazide-5 (and / or-) of the polyhydroxy compound shown below is used.
4) Esters with sulfonyl chloride can be mentioned, but not limited thereto. 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,
Polyhydroxybenzophenones such as 3,4,3 ′, 4 ′, 5′-hexahydroxybenzophenone,

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

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 Polyhydroxybiphenyls such as'-biphenylhexol, 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'-tetrahydroxydiphenyl sulfoxide,

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

Tris (4-hydroxyphenyl) methane, 4,4 ', 4 "-trihydroxy-3,5,3',
5'-tetramethyltriphenylmethane, 4,4 ',
3 ", 4" -tetrahydroxy-3,5,3 ', 5'-
Tetramethyltriphenylmethane, 4,4 ', 2 ",
3 ", 4" -pentahydroxy-3,5,3 ', 5'-
Tetramethyltriphenylmethane, 2,3,4,2 ',
3 ', 4'-hexahydroxy-5,5'-diacetyltriphenylmethane, 2,3,4,2', 3 ', 4',
3 ", 4"-octahydroxy-5,5'-diacetyltriphenylmethane, 2,4,6,2 ', 4', 6'-
Hexahydroxy-5,5'-dipropionyltriphenylmethane and other polyhydroxytriphenylmethanes,

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,

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

Flavono pigments such as morin, quercetin 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 the like are described in JP-A-4-253058. A polyhydroxy compound of

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 (2,3,5-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'-hydroxy-
3 ', 5'-di-t-butyl-benzyl) -p-cresol, 2,6-bis (2'-hydroxy-5'-ethyl-benzyl) -p-cresol, 2,6-bis (2' ，
4'-dihydroxy-benzyl) -p-cresol,
2,6-bis (2'-hydroxy-3'-t-butyl-
5'-methyl-benzyl) -p-cresol, 2,6-
Bis (2 ', 3', 4'-trihydroxy-5'-acetyl-benzyl) -p-cresol, 2,6-bis (2 ', 4', 6'-trihydroxy-benzyl) -p
-Cresol, 2,6-bis (2 ', 3', 4'-trihydroxy-benzyl) -p-cresol, 2,6-bis (2 ', 3', 4'-trihydroxy-benzyl)-
3,5-dimethyl-phenol, 4,6-bis (4'-
Hydroxy-3 ', 5'-dimethyl-benzyl) -pyrogallol, 4,6-bis (4'-hydroxy-3',
5'-dimethoxy-benzyl) -pyrogallol, 2,6
-Bis (4'-hydroxy-3 ', 5'-dimethyl-benzyl) -1,3,4-trihydroxy-phenol,
4,6-bis (2 ', 4', 6'-trihydroxy-benzyl) -2,4-dimethyl-phenol, 4,6-bis (2 ', 3', 4'-trihydroxy-benzyl)-
2,5-Dimethyl-phenol, a low molecular weight phenol resin such as novolac resin and the following general formulas (I) to (VII)
The polyhydroxy compound represented by These naphthoquinone diazide ester photosensitive materials of polyhydroxy compounds are used alone or in combination of two or more kinds.

General formula (I)

Embedded image

R _{1 to} R ₄ ; single bond, C _{1 to} C ₆ linear or branched alkylene group, R _{5 to} R ₈ ; C _{1 to} C ₄ alkyl, alkoxy, acyl group, halogen, cyano group, nitro group , 1 to Q; an integer of 0 to 3.

General formula (II)

Embedded image

Here, R _{9 to} R ₁₂ ; which may be the same or different, each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, A: --S-- or --SO _2- .

General formula (III)

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R _{13 to} R _22, which may be the same or different, are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an acyl group, an alkenyl group, an aralkyl group, an alkoxycarbonyl group or an arylcarbonyl group. , An acyloxy group, a nitro group or a cyano group (provided that at least one of R ₁₅ and R ₁₆ is not a hydrogen atom when either one of R ₁₃ and R ₁₄ is a group other than a hydrogen atom). And when either one or both of R ₁₇ and R ₁₈ is a group other than a hydrogen atom, at least one of R ₁₉ and R ₂₀ is not a hydrogen atom) a, b: 1 or 2 Represent.

General formula (IV)

[Chemical 4]

Here, R _{23 to} R _26, which may be the same or different, are a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group,
Aryl group, alkoxy group, acyl group, alkenyl group,
Aralkyl group, alkoxycarbonyl group, arylcarbonyl group, acyloxy group, nitro group, cyano group, or

[0039]

Embedded image

R _{31 to} R ₃₄ : same or different, hydrogen atom, alkyl group or alkoxy group, R _{27 to} R ₃₀ ; same or different, hydrogen atom, hydroxyl group, halogen atom, alkyl group, aryl Group, alkoxy group, acyl group, alkenyl group, aralkyl group.

General formula (V)

[Chemical 6]

Here, R _{35 to} R _37, which may be the same or different, each represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group or an alkoxy group, and m, n, o: an integer of 1 to 3.

General formula (VI)

[Chemical 7]

General formula (VII)

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R _{38 to} R _48, which may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group. However, at least one is a cycloalkyl group, R _{49 to} R _59, which may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a cycloalkyl group. However, at least one represents a cycloalkyl group.

Specific examples of the compounds represented by formulas (I) to (VII) include the following.

[0047]

[Chemical 9]

[0048]

[Chemical 10]

[0049]

[Chemical 11]

[0050]

[Chemical 12]

[0051]

[Chemical 13]

[0052]

Embedded image

[0053]

[Chemical 15]

[0054]

Embedded image

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

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

When the photosensitive compound of the present invention synthesized by the above-mentioned method is used as a resin composition, it may be used alone or as a mixture of two or more kinds thereof by blending it with an alkali-soluble resin. Examples of the low molecular weight compound having an acid-decomposable group and having a molecular weight of 3,000 or less used in the present invention include, but are not limited to, the compounds shown below.

[0058]

[Chemical 17]

[0059]

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[0060]

[Chemical 19]

[0061]

Embedded image

[0062]

[Chemical 21]

[0063]

[Chemical formula 22]

[0064]

[Chemical formula 23]

[0065]

[Chemical formula 24]

[0066]

[Chemical 25]

[0067]

[Chemical formula 26]

[0068]

[Chemical 27]

[0069]

[Chemical 28]

[0070]

[Chemical 29]

[0071]

Embedded image

[0072]

[Chemical 31]

[0073]

Embedded image

[0074]

[Chemical 33]

[0075]

Embedded image

[0076]

Embedded image In the compounds (1) to (63), R is a hydrogen atom,

[0077]

Embedded image

Represents However, at least two, or three depending on the structure, are groups other than hydrogen atoms, and the respective substituents R may not be the same group.

Examples of the alkali-soluble resin used in the present invention include novolac resin, hydrogenated novolac resin, acetone-pyrogallol resin, polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, and hydroxystyrene-N-substituted maleimide copolymer. Examples thereof include, but are not limited to, partially O-alkylated or O-acylated polyhydroxystyrene, styrene-maleic anhydride copolymer, carboxyl group-containing methacrylic resin and derivatives thereof. . Particularly preferred alkali-soluble resins are novolac resins and polyhydroxystyrenes. The novolak resin is 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-cresol, o-cresol and other cresols, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3-xylenol and other xylenols, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, p-t-butylphenol, p-octylphenol, 2,3,5-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. -Isopropylpheno Bis alkylphenols such like, m
-Hydroxy aromatic compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or in combination of two or more. It is not limited.

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 or the like can be used. The weight average molecular weight of the novolak resin thus obtained is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed area after development is large, and if it exceeds 30,000, the developing speed becomes small. 2,000 is particularly suitable
It is in the range of 0 to 20,000.

Here, the weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography. Two or more of these alkali-soluble resins in the present invention may be mixed and used. The amount of the alkali-soluble resin used is 30 to 95% by weight, preferably 35, based on the total weight of the photosensitive composition (excluding the solvent).
~ 90% by weight. Examples of the compound used in the present invention that decomposes upon irradiation with actinic rays or radiation to generate an acid include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photobleaching agents for dyes, and photochromic A known compound used for an agent or a micro resist, which generates an acid by light, and a mixture thereof can be appropriately selected and used.

For example, S. I. Schlesinge
r, Photogr. Sci. Eng. , 18,387
(1974), T.S. S. Bal etal, Polym
er, 21, 423 (1980) and the like, diazonium salts, US Pat. Nos. 4,069,055 and 4,06.
9,056, Re27,992 each specification, Japanese Patent Application No. 3-140140, etc. ammonium group,
D. C. Necker et al, Macromole
cules, 17, 2468 (1984), C.I. S. W
en et al, Teh, Proc. Conf. Ra
d. Curing ASIA, p478 Tokyo,
Oct (1988), U.S. Pat. No. 4,069,055.
No. 4,069,056, the phosphonium group described in each specification, etc .; V. Crivello et al, Ma
chromorecules, 10 (6), 1307 (1
977), Chem, & Eng, News, Nov.
28, p31 (1988), European Patent No. 104,143.
U.S. Pat. Nos. 339,049 and 410,201.
Each specification, JP-A-2-150,848, JP-A-2-
Iodonium salts described in JP 296,514, etc .;
V. Crivello et al, Polymer
J. 17, 73 (1985), J. V. Crivell
o et al. Org. Chem. , 43, 305
5 (1978), W.A. R. Watt et al. P
polymer Sci. , Polymer Chem.
Ed. , 22, 1789 (1984), J. V. Cri
vello et al, Polymer Bull. ，
14, 279 (1985), J. V. Crivello
et al, Macromorecules, 14
(5), 1141 (1981), J. V. Crivel
lo et al. PolymerSci. , Pol
ymer Chem. Ed. , 17, 2877 (197)
9), European Patent Nos. 370,693 and 3,902,1
14, 233,567, 297,443, 297,442, U.S. Pat. No. 4,933,377,
161, 811, 410, 201, 339,
049, 4,760,013, 4,734,4
44, 2,833,827, German Patent 2,90
4,626, 3,604,580, 3,60
No. 4,581, sulfonium groups described in each specification, J.
V. Crivello et al, Macromore
cules, 10 (6), 1307 (1977), J.
V. Crivello et al. Polymer
Sci. , Polymer Chem. Ed. , 1
7, 1047 (1979) and the like, selenonium salts,
C. S. Wen et al, Teh, Proc. Con
f. Rad. Curing ASIA, p478 To
Kyo, Oct (1988) and other onium salts such as aluminum salts, U.S. Pat. No. 3,905,815, JP-B-46-4605, and JP-A-48-36281.
No. 5, JP-A-55-32070, JP-A-Sho 60-2397.
36, JP-A-61-169835, JP-A-61-1
69837, JP-A-62-58241, JP-A-62.
-212401, JP-A-63-70243, JP-A-63-298339, and the like. Meier et al. Rad. Cur
ing, 13 (4), 26 (1986), T.W. P. Gi
ll, et al, Inorg. Chem. , 19, 30
07 (1980), D.I. Astruc, Acc. Che
m. Res. , 19 (12), 377 (1896), Japanese Patent Application Laid-Open No. 2-161445, etc., S. Hayase et al. Po
lymer Sci. , 25, 753 (1987),
E. FIG. Reichmanis et al. Polym
er Sci. , Polymer Chem. E
d. 23, 1 (1985), Q.I. Q. Zhu eta
l, J. Photochem. , 36, 85, 39, 3
17 (1987), B.I. Amit et al, Tetr
ahedron Lett. , (24) 2205 (197)
3), D.I. H. R. Barton et al. Ch
em Soc. 3571 (1965), p. M. Co
llins et al. Chem. Soc. , Pe
rkin I, 1695 (1975), M.R. Rudin
Stein et al, Tetrahedron Le
tt. , (17), 1445 (1975), J. W. W
alker et al. Am. Chem. So
c. , 110, 7170 (1988), S.I. C. Bus
man et al. Imaging Techno
l. 11 (4), 191 (1985), H .; M. Ho
ulihan et al, Macromolecule
s, 21, 2001 (1988), p. M. Colli
ns et al. Chem. Soc. Chem.
Commun. , 532 (1972), S.M. Hayas
e et al, Macromolecules
s, 18, 1799 (1985), E.I. Reichma
nis et al. Electrochem. So
c. , Solid State Sci. Techno
l. 130 (6), F.I. M. Houlihan et
al, Macromolecules, 21, 2001
(1988), European Patent Nos. 0290,750 and 04.
No. 6,083, No. 156,535, No. 271,851
No. 0,388,343, US Pat. No. 3,901,
No. 710, No. 4,181, 531, each specification, JP-A-6
No. 0-198538, JP-A No. 53-133022, and other photo-acid generators having an o-nitrobenzyl type protecting group, M.K. TUNOOKA et al, Polymer
r Preprints Japan, 35 (8),
G. Berner et al. Red. Curin
g, 13 (4), W. J. Mijsetal, Coat
ing Technol. , 55 (697), 45 (1
983), Akzo, H .; Adachi et al, P
polymer Preprints Japan, 37
(3), European Patent Nos. 0199,672 and 84,51
No. 5, No. 199,672, No. 044,115, No. 0
101,122, U.S. Pat. No. 4,618,564,
Nos. 4,371,605, 4,431,774, JP-A-64-18143 and JP-A-2-2457.
No. 56, Japanese Patent Application No. 3-140109, etc., and compounds that generate sulfonic acid by photolysis, represented by iminosulfonates, and the like, JP-A-61-166544.
Examples thereof include disulfone compounds described in JP-A No.

Further, a group generating an acid by these light,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, M.I. E. FIG. Woodhouse eta
l, J. Am. Chem. Soc. , 104, 5586
(1982), S.H. P. Pappas et al.
Imaging Sci. , 30 (5), 218 (19
86), S. Kondo et al, Makrom
l. Chem. , Rapid Commun. , 9, 6
25 (1988), Y. Yamada et al, Ma
kromol, Chem. , 152, 153, 163
(1972), J. V. Crivello et al,
J. Polymer Sci. , Polymer Ch
em. Ed. , 17,3845 (1979), U.S. Pat. No. 3,849,137, German Patent No. 3,914,40.
No. 7, each specification, JP-A-63-26653, JP-A-55
-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452,
JP-A-62-153853, JP-A-63-14602
The compounds described in Japanese Patent No. 9 and the like can be used.

Furthermore, V. N. R. Pillai, Sy
nthesis, (1), 1 (1980), A.S. Aba
d et al, Tetrahedron Lett. ，
(47) 4555 (1971), D.I. H. R. Bart
on et al. Chem. Soc. , (C), 3
29 (1970), U.S. Pat. No. 3,779,778,
The compounds capable of generating an acid by light described in European Patent Nos. 126,712 and the like can also be used.

Among the compounds which decompose to generate an acid upon irradiation with actinic rays or radiation, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
1) or an oxazole derivative represented by the general formula (PA
An S-triazine derivative represented by G2).

Embedded image In the formula, R ¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group or —CY ₃ . Y represents a chlorine atom or a bromine atom. The following compounds can be specifically mentioned, but the compounds are not limited to these.

[0087]

[Chemical 38]

[0088]

[Chemical Formula 39]

[0089]

[Chemical 40]

(2) An iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the following general formula (PAG4).

[0091]

Embedded image

Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group and a halogen atom.

R ³ , R ⁴ and R ⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferred are an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and a substituted derivative thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom for the aryl group, and an alkyl group for the alkyl group. An alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

Z^-Represents a counter anion, for example, B
F_Four ^-, AsF₆ ^-, PF₆ ^-, SbF₆ ^-, SiF₆
^2-, ClO_Four ^-, CF₃SO₃ ^-Perfluoroal
Cansulfonate anion, pentafluorobenzenesulfate
Fonate anion, naphthalene-1-sulfonate anion
Polynuclear aromatic sulfonate anions such as anthraquino
Sulfonic acid anions, sulfonic acid group-containing dyes, etc.
However, the present invention is not limited to these.

Two of R ³ , R ⁴ and R ⁵ and Ar ¹ and Ar ² may be bonded to each other via a single bond or a substituent. Specific examples include the following compounds, but are not limited thereto.

[0096]

Embedded image

[0097]

[Chemical 43]

[0098]

[Chemical 44]

[0099]

Embedded image

[0100]

Embedded image

[0101]

[Chemical 47]

[0102]

Embedded image

[0103]

[Chemical 49]

[0104]

Embedded image

[0105]

[Chemical 51]

[0106]

Embedded image

[0107]

Embedded image

The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and are described, for example, in J. W.
Knapczyk et al. Am. Chem. S
oc. , 91, 145 (1969), A.S. L. Mayc
ok et al. Org. Chem. , 35, 25
32 (1970), E.I. Goethas et al, B
all. Soc. Chem. Belg. , 73,546
(1964), H .; M. Leicester, J .; Am
e. Chem. Soc. 51, 3587 (1929),
J. V. Crivello et al. Poly
m. Chem. Ed. , 18, 2677 (1980),
U.S. Pat. Nos. 2,807,648 and 4,247,
It can be synthesized by the method described in each specification of Japanese Patent No. 473, JP-A-53-101331, or the like.

(3) A disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (6AG5).

[0110]

[Chemical 54]

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

[0112]

[Chemical 55]

[0113]

[Chemical 56]

[0114]

[Chemical 57]

[0115]

Embedded image

[0116]

Embedded image

The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.0 based on the total weight of the photosensitive composition (excluding the coating solvent).
It is used in the range of 01 to 40% by weight, preferably 0.0
It is used in the range of 1 to 20% by weight, more preferably 0.1 to 5% by weight.

In the photosensitive composition of the present invention, if necessary,
Further, a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, and a compound having two or more phenolic OH groups for promoting solubility in a developer can be contained.
Suitable dyes include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 1
03, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-5.
05 (all manufactured by Orient Chemical Industries, Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170)
B), malachite green (CI42000), methylene blue (CI52015) and the like.

Further, the following spectral sensitizers are added to the photosensitive composition of the present invention by sensitizing it to a longer wavelength region than the far ultraviolet rays which the photo-acid generator used has no absorption. Sensitivity can be imparted to the i or g line. Examples of suitable spectral sensitizers include benzophenone,
p, p'-tetramethyldiaminobenzophenone, p,
p'-tetraethylethylaminobenzophenone, 2-
Chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline,
N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine,
Picramid, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-
1,9-benzanthrone, dibenzalacetone, 1,
2-naphthoquinone, 3,3'-carbonyl-bis (5,5
7-dimethoxycarbonylcoumarin), coronene, and the like, but are not limited thereto.

The composition of the present invention may further contain a polyhydroxy compound in order to accelerate the dissolution in the developing solution. Preferred polyhydroxy compounds include phenols, resorcin, phloroglucin, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, phlorogluside, 2,4
2 ', 4'-biphenyl tetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2', 4
4'-tetrahydroxydiphenyl ether, 2,
2 ', 4,4'-tetrahydroxydiphenyl 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-hydroxydiphenyl) -1,3,5-triisopropylbenzene, α, α ', α"- Examples include tris (4-hydroxydiphenyl) -1-ethyl-4-isopropylbenzene and the like. These polyhydroxy compounds are usually used in an amount of 100 parts by weight based on 100 parts by weight of the quinonediazide compound.
It may be added in an amount of not more than 5 parts by weight, preferably 5 to 50 parts by weight.

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

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

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 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, 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, FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC10.
3, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymerization polyflow No. 75, No. 95 (Kyoeisha Yushi Kagaku Kogyo Co., Ltd.)
Manufactured). 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 or in 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
Use an aqueous solution of alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, cyclic amines such as pyrrole and piperidine, and alkalis such as You can Further, an appropriate amount of alcohols and surfactants may be added to the above aqueous solution of alkalis for use.

The positive photoresist composition of the present invention may contain a dye, a plasticizer and an adhesion aid, if necessary. Specific examples thereof include dyes such as methyl violet, crystal violet and malachite green, plasticizers such as stearic acid, acetal resin, phenoxy resin and alkyd resin, and adhesion aids such as hexamethyldisilazane and chloromethylsilane.

The positive photoresist composition is applied onto a substrate (eg, silicon / silicon dioxide coating) used in the production of precision integrated circuit devices by a suitable coating method such as a spinner or coater, and then prebaked. Exposure through a predetermined mask, and if necessary post-heating (PEB:
A good resist can be obtained by performing Post Exposure Bake), developing, rinsing and drying.

[0127]

[Examples] The positive photoresist compositions according to the present invention will be more clearly described below with reference to Examples.

Synthesis Example (1) Synthesis of Novolac Resin A1 m-cresol 45 g, p-cresol 55 g, 37%
Formalin aqueous solution (49 g) and oxalic acid (0.18 g) were charged into a three-necked flask, heated to 100 ° C. with stirring, and reacted for 15 hours. Then raise the temperature to 200 ° C,
The pressure was gradually reduced to 5 mmHg, and water, unreacted monomer,
Formaldehyde, oxalic acid, etc. were removed. Then, the molten alkali-soluble novolac resin was returned to room temperature and recovered. The obtained novolak resin A has a weight average molecular weight of 75.
It was 00 (polystyrene conversion).

Synthesis Example (2) Synthesis of Novolac Resin A2 60 g of m-cresol, 20 g of p-cresol, 2,5
-Xylenol 22 g, 37% formalin aqueous solution 53 g
Then, 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 performed for 12 hours. After that, the temperature was raised to 200 ° C. and the pressure was gradually reduced to 1 mmHg to remove 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 had a weight average molecular weight of 4,500 (in terms of polystyrene). Next, 20 g of this novolak resin was completely melted 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 novolak resin B. The obtained novolak resin had a weight average molecular weight of 9,800 (in terms of polystyrene).

Synthesis Example (3) Synthesis of Novolac Resin A3 2,3-Dimethylphenol 175.62 g, 2,3
68.10 g of 5-trimethylphenol, 35.67 g of methylenebis-p-cresol, 24.43 g of 2,6-dimethylphenol and 5.41 g of o-cresol.
And formalin aqueous solution (37.10%) 165.07g
And 50.0 g of ethyl 3-ethoxypropionate were charged into a 1-liter three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, and oxalic acid 2 dissolved in 24.00 g of deionized water was stirred at 60 ° C. Hydrate 9.46
g was added. After stirring at 60 ° C for 1 hour, the temperature of the oil bath was raised to 130 ° C over 1 hour to reflux the contents. When stirring was continued for 10 hours after the bath temperature reached 130 ° C, ethyl 2-ethoxypropionate 2
5.00 g was added. After continuing heating at 130 ° C. for a further 6 hours, ethyl 3-ethoxypropionate 25.
After adding 00 g, the reflux condenser was replaced with a Liebig condenser, and the bath temperature was raised to 200 ° C. over 2 hours and 30 minutes to remove unreacted formalin, water and the like. After the bath temperature reached 200 ° C, distillation was continued for another 2 hours and 30 minutes, and then the bath temperature was cooled to 180 ° C. Internal temperature is 180
When the temperature fell below the temperature, 580.00 g of ethyl 2-hydroxypropionate was slowly added to obtain a novolac resin solution. The weight average molecular weight (GPC polystyrene conversion) of the obtained novolak resin was 2010.

Synthesis Example (4) Synthesis of Photosensitive Material (B1) 10 g of the following compound (B1 ′), 18.5 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 220 ml of acetone were charged in a three-necked flask and uniformly mixed. Dissolved. Then triethylamine / acetone = 7.2 g / 3
0 ml of the mixed solution was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was poured into 1000 ml of a 1% aqueous hydrochloric acid solution, the precipitate formed was filtered off, washed with water and dried (40 ° C.) to obtain a photosensitive material (B1).

[0132]

Embedded image

Synthesis Example (5) Synthesis of Photosensitive Material (B2) 10 g of the following compound (B2 ′), 16.5 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 200 ml of acetone were charged into a three-necked flask and uniformly mixed. Dissolved. Then triethylamine / acetone = 6.3 g / 2
7 ml of the mixed solution was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was poured into 900 ml of a 1% hydrochloric acid aqueous solution, the precipitate formed was filtered off, washed with water and dried (40 ° C.) to obtain a photosensitive material (B2).

[0134]

[Chemical formula 61]

Synthesis Example (6) Synthesis of Photosensitive Material (B3) 10 g of the following compound (B3 ′), 13.1 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 160 ml of acetone were charged into a three-necked flask and uniformly mixed. Dissolved. Then triethylamine / acetone = 5.2 g / 2
2 ml of the mixed solution was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was poured into 700 ml of a 1% aqueous hydrochloric acid solution, the precipitate formed was filtered off, washed with water and dried (40 ° C.) to obtain a photosensitive material (B3).

[0136]

Embedded image

Synthesis Example (7) Synthesis of Photosensitive Material (B4) 10 g of the following compound (B4 ′), 6.5 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 80 ml of acetone were charged into a three-necked flask and uniformly mixed. Dissolved.
Then triethylamine / acetone = 2.6 g / 15 m
The mixed liquid of 1 was gradually added dropwise and reacted at 25 ° C. for 3 hours. Pour the reaction mixture into 400 ml of 1% aqueous hydrochloric acid,
The resulting precipitate was filtered off, washed with water and dried (40 ° C) to obtain a photosensitive material (B4).

[0138]

[Chemical formula 63]

Synthesis Example (8) Synthesis of Photosensitive Material (B5) 10 g of the following compound (B5 ′), 10.4 g of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 130 ml of acetone were charged into a three-necked flask and uniformly charged. Dissolved. Then triethylamine / acetone = 4.1 g / 2
5 ml of the mixed solution was gradually added dropwise and reacted at 25 ° C. for 3 hours. The reaction mixture was poured into 650 ml of a 1% aqueous hydrochloric acid solution, the precipitate formed was filtered off, washed with water and dried (40 ° C.) to obtain a photosensitive material (B5).

[0140]

[Chemical 64]

Synthesis Example (9) Synthesis of Compound (C1) 20 g of the following compound (C1 ′) was added to tetrahydrofuran 40
It was dissolved in 0 ml. This solution is tert.
14 g of potassium butoxide was added, and after stirring at room temperature for 10 minutes, 29.2 g of di-tert-butyl dicarbonate
Was added. The reaction was carried out at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate layer was further washed with water, dried and the solvent was distilled off. The obtained crystalline solid was recrystallized (diethyl ether) and dried to give a compound example (31: R is all t-BOC group) 25.6.
g was obtained.

[0142]

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Synthesis Example (10) Synthesis of Compound (C2) 20 g of the above compound (C1 ′) was added to diethyl ether 400
Dissolved in ml. To this solution was added 3,4-dihydro-2H-pyran (31.6 g) and a catalytic amount of hydrochloric acid under a nitrogen atmosphere, and the mixture was reacted under reflux for 24 hours. After the reaction,
A small amount of sodium hydroxide was added and filtered. The solvent of the filtrate was distilled off, and the obtained product was purified by column chromatography and dried to obtain a compound example (31: R is all THP
Group) was obtained.

Synthesis Example (11) Synthesis of Compound (C3) 11.2 g (0.040 mol) of the above compound (C1 ′) in 120 ml of N, N-dimethylacetamide solvent, 21.2 g (0.15 mol) of potassium carbonate. ), And 27.1 g (0.14 mol) of t-butyl bromoacetate was added, and 12
The mixture was stirred at 0 ° C for 7 hours. Then the reaction mixture is treated with water 1.5.
The mixture was added to liter and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 3/7 (volume ratio)), which was a pale yellow viscous solid. 30 g was obtained. According to NMR, this is a compound example (31: R are all -CH ₂ COOC ₄ H ₉ ^t groups).
Was confirmed.

Synthesis Example (12) Synthesis of Compound (C4) The following compound (C4 ′)

[0146]

[Chemical formula 66]

42.4 g (0.10 mol) was dissolved in 300 ml of N, N-dimethylacetamide, and 49.5 g (0.35 mol) of potassium carbonate and 84.8 g (0.33) of cumyl bromoacetate were added thereto. Mol) was added.
Thereafter, the mixture was stirred at 120 ° C. for 7 hours. The reaction mixture was added to 2 liters of ion-exchanged water and extracted with ethyl acetate. Concentration of the ethyl acetate extracts were purified in the same manner as in Synthesis Example (11), compound example (18: R are all -CH ₂ COOC
70 g of (CH ₃ ) ₂ C ₆ H ₅ group) was obtained.

Synthesis Example (13) Synthesis of Compound (C5) The following compound (C5 ′)

[0149]

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14.3 g (0.20 mol) was added to a solution of N, N-dimethylacetamide (120 ml) and potassium carbonate (2).
1.2 g (0.15 mol) and t-butyl bromoacetate (27.1 g, 0.14 mol) were added, and the mixture was added at 120 ° C. to 7
Stir for hours. Then, the reaction mixture was poured into 1.5 liters of water and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 2/8 (volume ratio)), resulting in a pale yellow powder. 24 g was obtained. According to NMR, this is an example compound (6
2: It was confirmed that all R were —CH ₂ COO—C ₄ H ₉ ^t groups).

Synthesis Example (14) Synthesis of Compound (C6) 20 g (0.0042 mol) of the above compound (C1 ′) was dissolved in 400 ml of tetrahydrofuran (THF). 9.3 g of potassium t-butoxide was added to this solution under a nitrogen atmosphere.
(0.083 mol) and after stirring at room temperature for 10 minutes,
19.5 g of di-t-butyl dicarbonate (0.087
Mol) was added. The reaction was carried out at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate extract was concentrated and subjected to column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 1 /
5 (volume ratio)), as a result of the fractional purification, the compound example (3
1: 2 R is a t-BOC group, 1 R is a hydrogen atom) 7
g was obtained.

Synthesis Example (15) Synthesis of Compound (C7) 48.1 g (0.10 mol) of the above compound (C1 ′) was dissolved in 300 ml of dimethylacetamide, and 22.1 g (0.16 mol) of potassium carbonate was added thereto. , And bromoacetic acid t
-Butyl 42.9 g (0.22 mol) was added. Then, it stirred at 120 degreeC for 5 hours. The reaction mixture was poured into 2 liters of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate. The ethyl acetate extract was concentrated and fractionated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 1/5 (volume ratio)). As a result, a compound example (31: 2 R is -CH ₂ CO
10 g of an O—C ₄ H ₉ ^t group and one R is a hydrogen atom was obtained.

Synthesis Example (16) Synthesis of Compound (C8) The following compound (C8 ′)

[0154]

[Chemical 68]

44 g (0.10 mol) was dissolved in 300 ml of N, N-dimethylacetamide, and 70.2 g (0.497 mol) of potassium carbonate and t-bromoacetate were dissolved therein.
89.8 g (0.464 mol) of butyl were added. Thereafter, the mixture was stirred at 120 ° C. for 7 hours. Then, the reaction mixture was poured into 1.5 liters of water and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 2/8 (volume ratio)), resulting in a pale yellow powder. 135 g are obtained. According to NMR, this is an example of a compound (60: R are all —CH ₂ COO).
-C ₄ H ₉ ^t group) was confirmed.

Examples 1 to 13 Resists were prepared using the compounds shown in the above synthesis examples. The prescription at that time is shown in Table-1.
It was shown to.

[0157]

[Table 1]

[Comparative Examples 1 and 2] Table-1 shows the formulations. E1 and E2 in Table 1 represent the following compounds.

[0159]

[Chemical 69]

[Preparation and Evaluation of Photosensitive Composition] Each material shown in Table 1 was prepared by using diethylene glycol dimethyl ether 3
It was dissolved in 0 g and filtered through a 0.2 μm filter to prepare a resist solution. This resist composition was applied to a silicon wafer using a spinner and dried on a vacuum adsorption hot plate at 120 ° C. for 60 seconds to obtain resist films having film thicknesses of 0.97 μm and 1.02 μm, respectively. This film was exposed using a reduction projection exposure apparatus (reduction projection exposure apparatus NSR-2005i9C manufactured by Nikon Corporation) and then exposed at 110 ° C.
PEB for 60 seconds, developed with a 3.0% aqueous solution of tetramethylammonium hydroxide for 1 minute, washed with water for 30 seconds and dried. 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 Table-2 and Table-3.

[0161]

[Table 2]

[0162]

[Table 3]

The sensitivity was defined as the reciprocal of the exposure dose for reproducing a mask pattern of 0.60 μm, and shown as a relative value to the sensitivity of the resist film of Comparative Example 1 of 1.02 μm. The resolving power represents a limiting resolving power at an exposure amount for reproducing a mask pattern of 0.60 μm. The heat resistance was the temperature at which a resist-patterned silicon wafer was baked on a hot plate for 4 minutes and no deformation of the pattern occurred. The shape of the resist is represented by the angle (θ) formed by the resist wall surface and the plane of the silicon wafer in the resist pattern cross section of 0.50 μm. Regarding the storage stability, the solution of the positive photoresist composition was allowed to stand at room temperature and the presence or absence of precipitates in the solution was examined after 3 months. The thing which precipitation was not observed was represented by (circle), and the thing observed was represented by x.

[0164]

As described above, the positive type photoresist according to the present invention has high resolution, accurately reproduces the mask dimension over a wide range of the photomask line width, and has a thickness of 1 μm.
A cross-sectional shape with a high aspect ratio can be generated in patterns with the following line widths, the side walls of the pattern cross section are nearly vertical, have a wide latitude, have heat resistance, are excellent in storage stability, and have a film thickness with a high resolution. It has excellent characteristics such as low dependence.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadayoshi Kokubo 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fuji Shashin Film Co., Ltd.

Claims (2)

[Claims] 1. An (A) alkali-soluble resin, (B) 1,
2-naphthoquinonediazide-5 (and / or -4) -sulfonic acid ester compound, (C) low molecular weight compound having an acid-decomposable group and having a molecular weight of 3,000 or less, acid-decomposable group: tertiary alkyl ester group, A positive photoresist composition comprising a tertiary alkyl carbonate group, a cumyl ester group, a tetrahydropyranyl ether group, and (D) a photoacid generator. 2. The blending ratio of the component (B) and the component (C) is 5 ≦ [B + C] ≦ 70 (wt%) ... wt% based on the total solid content, and 30 ≦ 100B / (B + C) ≦ 95. (Wt
%) The positive photoresist composition according to claim 1, which satisfies the following relational expression.