JP2001249460A - Positive type radiation sensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type radiation sensitive composition excellent in density dependency and margin for exposure. SOLUTION: The positive type radiation sensitive composition contains a resin having an acid decomposable group with a specified acetal structure and having solubility in an alkali developing solution increased by decomposition by the function of the acid, at least one compound which generates the acid when irradiated with active light or radiation and contributes to the decomposition reaction of the acid decomposable group, at least one compound which generates an acid when irradiated with active light or radiation and does not contribute to the decomposition reaction of the acid decomposable group, a surfactant and a solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lithographic printing plate or an IC.
The present invention relates to a positive-type radiation-sensitive composition used in a semiconductor manufacturing process such as the above, a circuit substrate such as a liquid crystal and a thermal head, and other photofabrication processes.

[0002]

2. Description of the Related Art As a resist used for lithography pattern formation using deep ultraviolet light or excimer laser light, there is a chemically amplified resist composition described in U.S. Pat. No. 4,491,628, European Patent No. 29,139 and the like. The chemically amplified positive resist composition generates an acid in the exposed area by irradiation with radiation such as far ultraviolet light, and the acid-catalyzed reaction causes the active and non-irradiated parts of the active radiation to dissolve in the developing solution. Is a pattern forming material for forming a pattern on a substrate by changing the pattern.

The above chemically amplified positive resist composition comprises an alkali-soluble resin, a compound that generates an acid upon exposure to radiation (photoacid generator), and a compound that inhibits dissolution of the alkali-soluble resin having an acid-decomposable group. A three-component system, a two-component system composed of a resin having a group which becomes alkali-soluble by being decomposed by reaction with an acid, and a resin having a group which becomes alkali-soluble by being decomposed by a reaction with an acid; It can be broadly classified into a hybrid system comprising a low molecular weight dissolution inhibiting compound having an acid-decomposable group and a photoacid generator.

JP-A-2-19847 discloses a resist composition containing a resin in which the phenolic hydroxyl group of poly (p-hydroxystyrene) is wholly or partially protected by a tetrahydropyranyl group. Have been. Japanese Patent Application Laid-Open No. 219957/1992 discloses a resist composition comprising a resin in which 20 to 70% of phenolic hydroxyl groups of poly (p-hydroxystyrene) are substituted with acetal groups. I have. Further, JP-A-5-249682 discloses a photoresist composition using a similar acetal-protected resin. JP-A-8-123032 discloses a photoresist composition using a terpolymer containing a group substituted with an acetal group. Further, Japanese Unexamined Patent Application Publication No.
No. 53534 includes a group substituted with an acetal group,
A photoresist composition using a partially crosslinked polymer is shown.

JP-A-5-323590 discloses that two types of photoacid generators are used.
No. 1279 describes the use of a photoacid generator that generates a strong acid and a photoacid generator that generates a weak acid.
1-1125907 describes the use of a compound that generates a carboxylic acid having a boiling point of 150 ° C. or higher and a compound that generates an acid other than the carboxylic acid.

However, there is still room for improvement in the density dependency even in the above technique. Since various patterns are included as a tendency of recent devices, various performances are required for resists. One of them is sparse / dense dependency. The device has a pattern in which the space is wider than the line, and an isolated line, as opposed to a portion where the line is dense.
Therefore, it is important to resolve various lines with high reproducibility. However, it is not always easy to reproduce various lines due to optical factors, and the solution at present is not clear. Further, there has been a strong demand for further improving the exposure margin. Here, the exposure margin refers to a phenomenon in which when the exposure amount changes, the line width of the obtained pattern changes.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive-type radiation-sensitive composition having excellent dependency on density. A further object of the present invention is to provide a positive radiation-sensitive composition having an excellent exposure margin.

[0008]

The above object of the present invention has been attained by the following constitutions. (1) (a) a resin having an acid-decomposable group represented by the following general formula (I), decomposed by the action of an acid, and having increased solubility in an alkali developer; (b-1) an actinic ray or (B-2) an acid is generated by irradiation of an actinic ray or radiation, and at least one of compounds that generate an acid upon irradiation with radiation and contribute to the decomposition reaction of the acid-decomposable group; At least one of the compounds that do not contribute to the decomposition reaction
A body-type radiation-sensitive composition comprising: a seed; (c) a surfactant; and (d) a solvent.

[0009]

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In the general formula (I), R ₁ represents an alkyl group having 1 to 4 carbon atoms. W is an organic group containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom and at least one carbon atom, an amino group, an ammonium group, a mercapto group, Represents a substituted or unsubstituted aryl group or a substituted or unsubstituted cyclic alkyl group. n represents an integer of 1 to 4.

(2) In the resin (a), at least a part of the phenolic hydroxyl group in the alkali-soluble resin containing a phenolic hydroxyl group is protected by the acid-decomposable group represented by the general formula (I). The radiation-sensitive composition according to the above (1), which is a resin. (3) W in the general formula (I) is at least one kind of substituent selected from the group of substituents shown below, wherein the body-type radiation-sensitive material according to the above (1), Composition.

[0012]

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In the above formula: R ₂ is a hydrogen atom, having 1 to 1 carbon atoms.
6 linear, branched or cyclic alkyl groups, 2 to 6 carbon atoms, linear, branched or cyclic alkenyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted aralkyl groups Represents R ₃ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group. , An amino group, a hydroxyl group, or a cyano group. X represents a halogen atom.
R ₄ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted cyclic alkyl group having 3 to 15 carbon atoms. m is a natural number of 1 to 4. (4) The compound (b-1) is a compound that generates a sulfonic acid upon irradiation with actinic rays or radiation, and (b-
The bodi-type radiation-sensitive composition according to the above (1), wherein the compound (2) is a compound that generates a carboxylic acid upon irradiation with actinic rays or radiation. (5) The body-type radiation-sensitive composition according to any one of the above (1) to (4), which contains an organic basic compound.

The positive-working radiation-sensitive composition of the present invention generates an acid by irradiation with actinic rays or radiation together with an acid-decomposable resin having an acetal group having a substituent having a specific structure at the terminal as an acid-decomposable group. As a compound, a compound that contributes to the decomposition of the specific acid-decomposable group and a compound that does not contribute to the decomposition are used in combination, whereby the density dependence is improved brilliantly, and the exposure margin (exposure latitude) is improved. .

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, components such as a compound and a resin contained in the positive radiation-sensitive composition of the present invention will be described in detail. [I] Acid-decomposable resin of component (a) In the present invention, the acid-decomposable resin has an alkali-soluble group having an acid-decomposable group represented by the general formula (I) (protecting group)
Is a resin having a structure protected by Here, examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, and a sulfonic acid group. Of these, phenolic hydroxyl groups are preferred. The acid-decomposable resin in the present invention is preferably an alkali-soluble resin having a phenolic hydroxyl group in which the phenolic hydroxyl group is protected by the group represented by the above general formula (I).

The alkali-soluble resin having a phenolic hydroxyl group used in the present invention comprises at least 30 mol% of o-, m- or p-hydroxystyrene, or o-, m- or p-hydroxy-α-methylstyrene. Preferably, it is a copolymer containing 50 mol% or more or a homopolymer thereof, or a partially hydrogenated resin, and more preferably a p-hydroxystyrene homopolymer. As the above copolymerized monomers, acrylic esters, methacrylic esters, acrylamides, methacrylamides, acrylonitrile, methacrylonitrile, maleic anhydride, styrene, α-methylstyrene, acetoxystyrene, alkoxystyrenes are preferred, Styrene, acetoxystyrene and t-butoxystyrene are more preferred. The range of the weight-average molecular weight of the alkali-soluble resin is preferably from 3,000 to 8,000 as a value in terms of polystyrene measured by a GPC method.
0, more preferably 7000 to 50,000. The range of the molecular weight distribution (Mw / Mn) is 1.01-4.
0, preferably 1.05 to 1.20. In order to obtain a polymer having this molecular weight distribution, it is preferable to use a technique such as anionic polymerization.

In the general formula (I), n is a natural number of 1 to 4, preferably 2 or 3. R ₁ is methyl,
Preferred examples include ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and t-butyl, and among them, methyl is more preferred. The organic group of W is composed of at least one kind of oxygen atom, nitrogen atom, sulfur atom, phosphorus atom and silicon atom and at least one carbon atom. More specifically, W is preferably a group shown below.

[0018]

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In the formula, R ₂ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, Alternatively, it represents a group selected from the group consisting of an unsubstituted aryl group and a substituted or unsubstituted aralkyl group. R ₃ is
A hydrogen atom, a C1-C6 linear, branched and cyclic alkyl group, a C1-C6 linear, branched and cyclic alkoxy group, a halogen atom, a nitro group, an amino group, a hydroxyl group, And a group selected from the group consisting of a cyano group. X represents a halogen atom. R ₄ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted cyclic alkyl group having 3 to 15 carbon atoms. m is a natural number of 1 to 4, preferably 1 or 2.

In the above R ₂ and R ₃ , the linear, branched and cyclic alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, t-
Butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl and the like are preferred,
Methyl and ethyl are more preferred. Carbon atoms in R ₂ 2
And linear, branched, and cyclic alkenyl groups such as vinyl, 1-propenyl, allyl, isopropenyl,
-Butenyl, 2-butenyl, 2-pentenyl, cyclohexenyl and the like are preferred, and vinyl and isopropenyl are more preferred.

As the aryl group for R ₂ and R ₄ , phenyl, tolyl, xylyl, mesityl, cumenyl and the like are preferable, and phenyl is more preferable. As the aralkyl group for R ₂ , benzyl, phenethyl, α-methylbenzyl, benzhydryl and the like are preferable, and benzyl is more preferable.
As the cyclic alkyl group having 3 to 15 carbon atoms for R ₄ , a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like are preferable. These, aryl, aralkyl,
The cyclic alkyl group may be substituted with a halogen atom, a nitro group, an alkoxy group, an acetyl group, an amino group, an ester group, an amide group and the like. 1 to 6 carbon atoms in R ₃
As the linear, branched and cyclic alkoxy groups, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy and the like are preferable,
Methoxy and ethoxy groups are more preferred.

The halogen atom is preferably fluorine, chlorine, bromine or iodine, more preferably chlorine or bromine. Also, W
May be a cyano group or a formyl group as described above.

Specific examples of the protecting group represented by the general formula (I) are shown below, but it should not be construed that the invention is limited thereto. Here, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.

[0024]

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[0025]

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[0026]

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The resin (a) in which the phenolic hydroxyl group is protected by the above protective group is synthesized from the corresponding vinyl ether, and is known as a phenolic hydroxyl group-containing alkali-soluble resin dissolved in an appropriate solvent such as tetrahydrofuran. It can be obtained by reacting according to the method. The reaction is usually an acidic catalyst, preferably an acidic ion exchange resin, hydrochloric acid, p-toluenesulfonic acid or
It is carried out in the presence of a salt such as pyridinium tosylate. The corresponding vinyl ether can be synthesized from an active substance such as chloroethyl vinyl ether by a method such as a nucleophilic substitution reaction.

The structure of the resin constituting the resin (a) will be exemplified below, but the present invention is not limited thereto. Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, tBu represents a t-butyl group, and Ac represents an acetyl group.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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The composition of the present invention contains the above resin in which a phenolic hydroxyl group is protected by a protecting group represented by the general formula (I). The protection ratio by the protecting group represented by the general formula (I) is preferably from 5 to 45 mol%, more preferably from 10 to 30 mol%, based on all phenolic hydroxyl groups in the resin. In the composition of the present invention, the total amount of the acid-decomposable resin (a) used is preferably from 10 to 99.9% by weight, more preferably from 50 to 99.9% by weight, based on the total weight of the composition (excluding the solvent). 5% by weight, more preferably 70 to
99.0% by weight.

The composition of the present invention can contain, for example, an alkali-soluble resin not containing an acid-decomposable group exemplified by the protecting group represented by the general formula (I), whereby the sensitivity is improved. I do. Examples of the alkali-soluble resin containing no acid-decomposable group (hereinafter, simply referred to as “alkali-soluble resin”) include novolak resins, derivatives of novolak resins; poly (p-hydroxystyrene), p / m-hydroxystyrene copolymer , P / o-hydroxystyrene copolymers, copolymers containing p-hydroxystyrene units such as p-hydroxystyrene-styrene copolymer; 4-hydroxy-3-methylstyrene resin, 4-hydroxy-3, Alkyl-substituted hydroxystyrene resins such as 5-dimethylstyrene resin; and alkylated or acetylated OH moieties of these resins are preferred.

Further, a resin in which a part of the phenol nucleus (30 mol% or less of all phenol nuclei) of the above resin is hydrogenated is preferable in terms of improving the transparency of the resin, sensitivity, resolution, and forming a good profile. . Such resins include partially hydrogenated novolak resins, partially hydrogenated polyhydroxystyrene, and the like.

Other alkali-soluble resins which can be contained in the composition of the present invention include acetone-pyrogallol resin, hydroxystyrene-N-substituted maleimide copolymer, partially O-alkylated polyoxystyrene or O-alkylstyrene. Examples include acylated products, styrene-maleic anhydride copolymers, carboxyl group-containing methacrylic resins and derivatives thereof, and styrene-polyhydroxystyrene copolymers, but are not limited thereto.

Particularly preferred alkali-soluble resins for use in the present invention are novolak resins, alkali-soluble resins containing p-hydroxystyrene units (preferably poly (p-hydroxystyrene), p / m-hydroxystyrene copolymer, p / o-hydroxystyrene copolymer, p-hydroxystyrene-styrene copolymer), 4
-Hydroxy-3-methylstyrene resin, alkyl-substituted hydroxystyrene resin such as 4-hydroxy-3,5-dimethylstyrene resin, alkylated or acetylated OH moiety of the above resin, polyhydroxystyrene resin, partially hydrogenated novolak Resin, partially hydrogenated polyhydroxystyrene resin.

In the present invention, the term "polyhydroxystyrene" refers to a p-hydroxystyrene monomer, an m-hydroxystyrene monomer, an o-hydroxystyrene monomer or a hydroxystyrene monomer having an ortho-substituted alkyl group having 1 to 4 carbon atoms. It shows a polymer obtained by polymerizing at least one kind of monomer selected from the above.

The novolak resin is obtained by subjecting a predetermined monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
Cresols such as -cresol, p-cresol and o-cresol, xylenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and 2,3-xylenol, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, Alkoxyphenols such as -methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol, 2-methyl-4-isopropyl Fenault Bis alkylphenols etc., dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and the hydroxyaromatic compounds of naphthol or the like can be used alone or two or more kinds, but the invention is not limited thereto.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde , O-nitrobenzaldehyde,
m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde,
Furfural and acetal forms thereof can be used, but among these, formaldehyde is preferably used.

These aldehydes are used alone or in combination of two or more. As the acidic catalyst, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used. The content of the alkali-soluble resin not containing an acid-decomposable group is 50% by weight or less, preferably 30% by weight or less, more preferably 20% by weight, based on the total of the resin and the acid-decomposable group-containing resin. % By weight or less.

(B) Photoacid Generator In the present invention, as the photoacid generator, (b-1) a compound that generates an acid upon irradiation with actinic rays or radiation and contributes to the decomposition reaction of the acid-decomposable group (B-1) a compound that generates an acid upon irradiation with actinic rays or radiation and does not contribute to the decomposition reaction of the acid-decomposable group; (B-2) Photoacid generator].

In the present invention, “contributes to the decomposition reaction”
Is a protective group in which, when a composition film containing each component is formed and an actinic ray or radiation is irradiated thereon, the acid generated from the photoacid generator protects the alkali-soluble group of the alkali-soluble resin ( Decomposes the above-mentioned acetal structure) and remarkably increases the dissolution rate of the composition film in a developer. In the present invention, "does not contribute to the decomposition reaction" means that a composition film containing each component is formed, and when an actinic ray or radiation is applied thereto, the acid generated from the photoacid generator is an alkali-soluble resin. Without decomposing the protecting group (acetal structure) protecting the alkali-soluble group,
It means an action that does not change the dissolution rate of the composition film in a developer.

(B-1) The photoacid generator is a compound which generates an acid capable of decomposing the above-mentioned specific acetal structure, and specific examples thereof include compounds described in detail below. . (B-1) Compounds that generate an acid upon irradiation with actinic rays or radiation include, for example, SI Schlesinger, Phot
ogr. Sci. Eng., 18, 387 (1974), TS Bal et al, Po
lymer, 21, 423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055, 4,069,056, Re 27,992,
Ammonium salts described in JP-A-3-140140, DC Ne
cker et al, Macromolecules, 17, 2468 (1984), CS
Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478
Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055 and 4,069,
No. 056, etc., JV Crivello et a
l, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng.
News, Nov. 28, p31 (1988), EP 104,143, 3
39,049, 410,201, JP-A-2-150848, JP-A-2
-296514 and other iodonium salts, JV Crivello
et al, Polymer J. 17, 73 (1985), JV Crivello et
al., J. Org.Chem., 43, 3055 (1978), WR Watt et.
al, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1
984), JV Crivello et al, Polymer Bull., 14, 279
(1985), JV Crivello et al, Macromorecules, 14
(5), 1141 (1981), JV Crivello et al, J. Polymer
Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patent No.
370,693, 161,811, 410,201, 339,049,
No. 233,567, No. 297,443, No. 297,442, U.S. Pat.
4,933,377, 3,902,114, 4,760,013, 4,73
No. 4,444, No. 2,833,827, Dokoku Patent No. 2,904,626, No.
Nos. 3,604,580 and 3,604,581, sulfonium salts described in JV Crivello et al, Macromorecules, 10 (6), 1
307 (1977), JV Crivello et al, J. Polymer Sci.,
Selenonium salts described in Polymer Chem. Ed., 17, 1047 (1979), etc., CS Wen et al, Teh, Proc. Conf. Rad. C
Onium salts such as arsonium salts described in uring ASIA, p478 Tokyo, Oct (1988) and the like, U.S. Pat.
JP-A-60-239736, JP-A-61-169835, JP-A-61-169
No. 837, JP-A-62-58241, JP-A-62-212401, JP-A-62-212401
63-70243, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al, J. Rad. Curing, 13 (4), 2
6 (1986), TP Gill et al, Inorg. Chem., 19, 3007
(1980), D. Astruc, Acc. Chem. Res., 19 (12), 377 (18
96), and organometallic / organic halides described in JP-A-2-14145, etc., S. Hayase et al, J. Polymer Sci., 25, 753
(1987), E. Reichmanis et al, J. PholymerSci., Poly
mer Chem. Ed., 23, 1 (1985), QQ Zhuetal, J. Phot
ochem., 36, 85, 39, 317 (1987), B. Amit et al, Tetra
hedron Lett., (24) 2205 (1973), DHR Barton et a
l, J. Chem Soc., 3571 (1965), PM Collins et al,
J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinstein
et al, Tetrahedron Lett., (17), 1445 (1975), JW
Walker et al, J. Am. Chem. Soc., 110, 7170 (198
8), SC Busman et al, J. Imaging Technol., 11
(4), 191 (1985), HM Houlihan et al, Macormolecul
es, 21, 2001 (1988), PM Collins et al, J. Chem.
Soc., Chem. Commun., 532 (1972), S. Hayase et al,
Macromolecules, 18, 1799 (1985), E. Reichmanis et a
l, J. Electrochem. Soc., Solid State Sci. Techno
l., 130 (6), FM Houlihan et al, Macromolcules, 2
1, 2001 (1988), European Patent Nos. 0290,750 and 046,083,
No. 156,535, No. 271,851, No. 0,388,343, U.S. Pat.No. 3,901,710, No. 4,181,531, JP-A-60-198538,
Photo-acid generators having a 0-nitrobenzyl-type protecting group described in JP-A-53-133022 and the like, M. TUNOOKA et al., Polymer Pr.
eprints Japan, 35 (8), G. Berner et al, J. Rad. Cur
ing, 13 (4), WJ Mijs et al, Coating Technol., 5
5 (697), 45 (1983), Akzo, H. Adachi et al, Polymer P
reprints, Japan, 37 (3), European Patent Nos. 0199,672, 84
No. 515, No. 044,115, No. 618,564, No. 0101,122, U.S. Pat.Nos. 4,371,605, 4,431,774, JP-A-64-1814
No. 3, JP-A-2-245756, compounds that generate sulfonic acid upon photodecomposition represented by iminosulfonate and the like described in JP-A-3-140109 and the like, described in JP-A-61-166544 and the like Disulfone compounds can be mentioned.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into a main chain or a side chain of a polymer, for example, ME Woodhouse et al, J. Am. Che.
m. Soc., 104, 5586 (1982), SP Pappas et al, J. I.
maging Sci., 30 (5), 218 (1986), S. Kondo et al, Mak
romol. Chem., Rapid Commun., 9, 625 (1988), Y. Yama
da et al, Makromol.Chem., 152, 153, 163 (1972);
V. Crivello et al, J. Polymer Sci., Polymer Chem.
Ed., 17, 3845 (1979), U.S. Patent No. 3,849,137, Dokoku Patent No. 3,914,407, JP-A-63-26653, JP-A-55-164824.
No., JP-A-62-69263, JP-A-63-146038, JP-A-63-69263
Compounds described in JP-A-163452, JP-A-62-153853, JP-A-63-146029 and the like can be used.

Further, VNR Pillai, Synthesis, (1),
1 (1980), A. Abad et al, Tetrahedron Lett., (47) 45
55 (1971), DHR Barton et al, J. Chem. Soc.,
(C), 329 (1970), U.S. Patent 3,779,778, European Patent 1
Compounds that generate an acid by light described in No. 26,712 and the like can also be used.

Among the compounds (b-1) which decompose upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PAG)
An S-triazine derivative represented by 2).

[0061]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Is shown. Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0063]

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[0064]

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[0065]

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

[0067]

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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 ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents for the aryl group include an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, a nitro group, a carboxyl group, a mercapto group, a hydroxy group and a halogen atom. And an alkyl group includes an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

[0070] Z chromatography represents a counter anion, for example BF ₄ over,
AsF ₆ over, PF ₆ over, SbF ₆ over, SiF ₆ ² over, ClO ₄ over,
Optionally substituted alkanesulfonic acid anion, optionally substituted benzenesulfonic acid anion, optionally substituted naphthalenesulfonic acid anion, optionally substituted anthracenesulfonic acid anion, optionally substituted Examples thereof include camphorsulfonic acid anions and sulfonic acid group-containing dyes, but are not limited thereto.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

Further, the performance over time from the exposure to the heat treatment
Light with little change (T-Top formation, line width change, etc.)
Acid generators are preferred. Examples of such photoacid generators
For example, in the general formulas (PAG3) and (PAG4)
And Ar¹, Ar^Two, R²⁰³~ R^{Two 05}Is replaced or unsubstituted
Wherein Z- is an acid
When it occurs, the diffusivity is relatively small in the resist film.
It is. Specifically, Z- is a branched or cyclic carbon.
From the group of several or more alkyl or alkoxy groups
It has at least one selected group, or is linear or branched
Or a cyclic alkyl group having 4 to 7 carbon atoms or alkoxy
Having at least two groups selected from the group of groups,
Or a linear or branched alkyl having 1 to 3 carbon atoms
At least a group selected from the group consisting of
Benzenesulfonic acid, naphthalenesulfonic acid having three
Or an anthracenesulfonic acid anion.

Specific examples include the following compounds, but are not limited thereto.

[0074]

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[0075]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JW Knapcz
yk et al, J. Am. Chem. Soc., 91, 145 (1969), AL
Maycok et al, J. Org.Chem., 35, 2532, (1970), E.
Goethas et al, Bull.Soc.Chem.Belg., 73, 546, (196
4), HM Leicester, J. Ame. Chem. Soc., 51, 3587.
(1929), JV Crivello et al, J. Polym. Chem. Ed.,
18, 2677 (1980), U.S. Pat.Nos. 2,807,648 and 4,247,
No. 473, JP-A-53-101331, and the like.

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0086]

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In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
It represents an unsubstituted alkyl group or aryl group. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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(4) A diazodisulfone derivative represented by the following general formula (PAG7).

[0095]

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Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0097]

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In the present invention, (b-1) a compound capable of generating an acid upon irradiation with actinic rays or radiation is preferably an onium salt or diazodisulfone, and among these, a compound capable of generating a sulfonic acid is particularly preferred. . Two or more kinds may be mixed. In this case, similar structures such as onium salts may be mixed, or an onium salt and a compound having a different skeleton such as diazodisulfone may be mixed.

The amount of the compound (b-1) which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.1% based on the total weight of the composition of the present invention (excluding the coating solvent). It is used in the range of 001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 5% by weight.
Used in the range of weight percent.

The photoacid generator (b-2) used in the present invention generates an acid upon irradiation with actinic rays or radiation, but does not contribute to the decomposition of the acid-decomposable resin.
As such a photoacid generator, a compound that generates a carboxylic acid is preferable. Examples of such a photoacid generator include an iodonium salt or a sulfonium salt having an anion of a carboxylic acid as a counter anion, an imide carboxylate compound having a carboxylic acid ester group, or a nitrobenzyl ester compound. Examples of the photoacid generator (b-2) that can be used in the present invention include compounds represented by the following general formulas (AI) to (AV).

[0101]

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In the above formula, R _{301 to} R ₃₃₇ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group;
Linear, branched or cyclic alkoxy groups, hydroxy groups,
Represents a halogen atom or a —S—R ₀ group. R ₀ is a straight chain,
Represents a branched, cyclic alkyl or aryl group. Ra,
Rb independently represents a hydrogen atom, a nitro group, a halogen atom, an alkyl group or an alkoxy group which may have a substituent. Rc and Rd each independently represent a halogen atom,
Represents an alkyl group or an aryl group which may have a substituent. Rc and Rd may combine to form an aromatic ring, a monocyclic or polycyclic hydrocarbon (these rings may contain an oxygen atom or a nitrogen atom). Y ₁ , Y ₂
Represents a carbon atom, and the Y ₁ -Y ₂ bond may be a single bond or a double bond. X ^- represents a carboxylic acid compound represented by the following formula converted to an anion. X ₁ and X ₂ are
Each independently represents a carboxylic acid compound represented by the following formula converted to an ester group at the carboxyl group portion.

[0103]

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[0104]

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In the above formula, R ₃₃₈ represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms (here, the alkyl group may contain an oxygen atom or a nitrogen atom in the chain). A C 1-20 linear, branched or cyclic alkenyl group, a C 1-20 linear, branched or cyclic alkynyl group, a C 1-20 linear, branched or A cyclic alkoxyl group, a group in which at least a part of the hydrogen atom of the alkyl group is substituted with a halogen atom and / or a hydroxyl group, and a group in which at least a part of the hydrogen atom of the alkenyl group is substituted with a halogen atom and / or a hydroxyl group Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Here, examples of the substituent of the aryl group include an alkyl group, a nitro group, a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, and a halogen atom.

R ₃₃₉ is a single bond or a group having 1 to 2 carbon atoms.
0 linear, branched or cyclic alkylene group (here, the chain of the alkylene group may contain an oxygen atom or a nitrogen atom); a linear, branched or cyclic C 1-20 alkyl group; An alkenylene group, a group in which at least a part of the hydrogen atoms of the alkylene group is substituted with a halogen atom and / or a hydroxyl group, a group in which at least a part of the hydrogen atoms of the alkenylene group is substituted with a halogen atom, or C 2 And represents an alkoxyalkylene group of -20, and a plurality of R ₃₃₈ and R ₃₃₉ may be the same or different from each other.

R ₃₄₀ represents a hydroxyl group or a halogen atom, and a plurality of R _340s may be the same or different. m, n, p and q are each independently an integer of 0 to 3, and m + n ≦ 5 and p + q ≦ 5. z is 0 or 1.

In the general formulas (AI) to (AV),
As the linear or branched alkyl group for R _{301 to} R337, Ra, Rb, Rc, Rd and R ₀ , a methyl group, an ethyl group, a propyl group, an n-butyl group, which may have a substituent,
1-4 carbon atoms such as a sec-butyl group and a t-butyl group
Individual ones. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms which may have a substituent, such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. The alkoxy group of R _{301 to} R337, Ra and Rb includes a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group. To four. R _{301 to} R337,
Examples of the halogen atom of Ra, Rb, Rc, and Rd include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the aryl group of R ₀ , Rc, and Rd include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group. As these substituents, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom,
A chlorine atom, an iodine atom), an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, and a nitro group.

Examples of the aromatic ring, monocyclic or polycyclic hydrocarbon (which may contain an oxygen atom or a nitrogen atom in these rings) formed by combining Rc and Rd include:
Benzene structure, naphthalene structure, cyclohexane structure,
Examples include a norbornene structure and an oxabicyclo structure.

The general formulas (AI) to (A) used in the present invention
Sulfonium represented III), or an iodonium compound, its counter anion X ^- is the above formula (C1) ~ (C
At least one of the carboxylic acid compounds represented by 10)
Including those became ^- carboxyl group of species of the compound (-COOH) is an anion (-COO). The compounds represented by the general formulas (AIV) to (AV) used in the present invention have, as the substituents X ₁ and X ₂ , at least one of the carboxylic acid compounds represented by the above formulas (C1) to (C10). The carboxyl group (-COOH) of some compounds is converted to an ester group (-COOH)
O-).

A linear, branched or cyclic alkyl group having 1 to 30 carbon atoms for R ₃₃₈ (here, the chain of the alkyl group may contain an oxygen atom or a nitrogen atom)
Examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, dodecyl, 1-ethoxyethyl, adamantyl and the like. Carbon number 1-2
Examples of the 0 linear, branched or cyclic alkenyl group include ethenyl, propenyl, isopropenyl, cyclohexene and the like. As a linear, branched or cyclic alkynyl group having 1 to 20 carbon atoms, acetylene,
And propenylene. Examples of the linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, propyloxy, butoxy, cyclohexyloxy, isobutoxy, dodecyloxy and the like. Examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms include phenyl, naphthyl, and anthranyl. As a substituent of the aryl group, an alkyl group,
Examples include a nitro group, a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, and a halogen atom.

Examples of the linear, branched or cyclic alkylene group having 1 to 20 carbon atoms for R ₃₃₉ (here, the chain of the alkylene group may contain an oxygen atom or a nitrogen atom) include: Examples include methylene, ethylene, propylene, butylene, isobutylene, ethoxyethylene, cyclohexylene and the like. As a linear, branched or cyclic alkenylene group having 1 to 20 carbon atoms, vinylene,
Arylene and the like.

In the present invention, the photoacid generator (b-2) is preferably an iodonium salt or a sulfonium salt.
Hereinafter, specific examples of these (b-2) photoacid generators are shown, but the present invention is not limited thereto.

[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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The compounds represented by the general formulas (AI) to (AV) can be used alone or in combination of two or more. (B-2) The photoacid generator, that is, the general formula (AI), the general formula (AII), and the general formula (AIII)
Can be prepared by the method described in U.S. Pat. No. 3,734,928, Macromolecules, vol. 10, 1307.
(1977), Journal of Organic Chemistry, vol. 55, 422
2 (1990), J. Radiat. Curing, vol. 5 (1), 2 (1978), etc., and further by exchanging the counter anion. The compounds represented by the general formulas (AIV) and (AV) are obtained by reacting an N-hydroxyimide compound with a carboxylic acid chloride under basic conditions.
Alternatively, it can be obtained by reacting nitrobenzyl alcohol and carboxylic acid chloride under basic conditions. (B
-2) The content of the photoacid generator in the composition is suitably from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, more preferably from 1 to 20% by weight, based on the total solid content of the composition. ~ 7% by weight. The weight ratio of the photoacid generators (b-1) and (b-2) used in the composition is (b-2) / (b-1), and is usually in the range of 0.01 to 5. , Preferably 0.05 to 3
And more preferably in the range of 0.1 to 2.

It is preferable to use an organic basic compound in the composition of the present invention. Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound having a structure represented by the following (A) to (E) is preferable. By using the nitrogen-containing basic compound, the performance change is small even with the lapse of time from exposure to post-heating.

[0121]

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Here, R²⁵⁰, R²⁵¹And R²⁵²Are each
Independently, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
1-6 aminoalkyl groups, hydroxy having 1-6 carbon atoms
Alkyl group or substituted or unsubstituted 6 to 20 carbon atoms
An aryl group, where R ²⁵¹And R²⁵²Are connected to each other
To form a ring.

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Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Is the same or different and represents an alkyl group having 1 to 6 carbon atoms). Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted amino Examples include morpholine, substituted or unsubstituted aminoalkyl morpholine, and the like, and include mono, di, trialkylamine, substituted or unsubstituted aniline, substituted or unsubstituted piperidine, mono and diethanolamine, and the like. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

Preferred compounds include guanidine, 1,
1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6
-Methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-
Aminoethyl) piperidine, 4-amino-2,2,6,
6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl)
Pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine ,
4,6-dihydroxypyrimidine, 2-pyrazoline, 3
-Pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0] Undec-7-ene, 2,4,5-triphenylimidazole, tri (n-butyl) amine,
Tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine, 2,6-
Diisopropylaniline, N-cyclohexyl-N'-
Examples include, but are not limited to, morpholinoethylthiourea, N-hydroxyethylmorpholine, and the like.

Of these, particularly preferred compounds include 1,5-diazabicyclo [4,3,0] non-5-
Ene, 1,8-diazabicyclo [5,4,0] undec-7-ene, 2,4,5-triphenylimidazole,
Tri (n-butyl) amine, tri (n-octyl) amine, N-phenyldiethanolamine, N-hydroxyethylpiperidine, 2,6-diisopropylaniline,
N-cyclohexyl-N'-morpholinoethylthiourea and N-hydroxyethylmorpholine. These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound used is usually 0.001 to 10% by weight, based on the solid content of the composition,
Preferably it is 0.01 to 5% by weight. If the amount is less than 0.001% by weight, the effect of the addition of the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

[VII] Other components used in the present invention The positive-working radiation-sensitive composition of the present invention may further contain a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, A compound having two or more phenolic OH groups that promote solubility in a developer and a molecule dissolution inhibiting compound can be contained.

The compound having two or more phenolic OH groups that can be used in the present invention is preferably a phenol compound having a molecular weight of 1,000 or less. Further, it is necessary to have at least two phenolic hydroxyl groups in the molecule. If the number exceeds 10, the effect of improving the development latitude is lost. When the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the film thickness dependency is large, and the development latitude tends to be narrow. If this ratio exceeds 1.4, the stability of the composition deteriorates, and it becomes difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The preferable addition amount of the phenol compound is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the alkali-soluble resin. 50% by weight
If the addition amount exceeds the above range, the development residue becomes worse and a new defect that the pattern is deformed at the time of development occurs, which is not preferable.

Such a phenol compound having a molecular weight of 1,000 or less can be prepared by, for example, referring to the methods described in JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, EP 219294, and the like. ,
It can be easily synthesized by those skilled in the art. Specific examples of the phenol compound are shown below, but the compounds that can be used in the present invention are not limited to these.

Resorcin, phloroglucin, 2, 3, 4
-Trihydroxybenzophenone, 2,3,4,4'-
Tetrahydroxybenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, fluoroglucoside,
4,2 ', 4'-biphenyltetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2',
4,4'-tetrahydroxydiphenyl ether, 2,
2 ', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2', 4,4'-tetrahydroxydiphenylsulfone, 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.

Suitable dyes include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 60
3. Oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B
(CI45170B), malachite green (CI42
000), methylene blue (CI52015) and the like.

Further, a spectral sensitizer as described below is added to sensitize the photosensitive composition of the present invention to a longer wavelength region than far ultraviolet where the photoacid generator used has no absorption. Sensitivity can be given to i or g rays. Suitable spectral sensitizers include, specifically, 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, picramide, 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 (5,7-
Dimethoxycarbonylcoumarin) and coronene, but are not limited thereto. Further, these spectral sensitizers can also be used as a light absorbing agent for far ultraviolet light of a light source. In this case, the light absorbing agent exhibits the effect of improving the standing wave by reducing the reflected light from the substrate and reducing the influence of multiple reflection in the resist film.

The composition of the present invention is dissolved in a solvent capable of dissolving the above-mentioned components, and coated on a support. As the solvent (d) used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monochloride Ethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

It is preferable to add a surfactant to the above solvent. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates and the like, F-top EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173, F17
6, F189, R08 (Dai Nippon Ink Co., Ltd.), Florad FC430, FC431 (Sumitomo 3M Co., Ltd.)
Made), Asahi Guard AG710, Surflon S-38
2, SC101, SC102, SC103, SC10
Fluorinated surfactants such as 4, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP3
No. 41 (manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid-based or methacrylic acid-based (co) polymerized polyflow No. 41 75, N
o. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) and Troysol S-366 (manufactured by Troy Chemical Co., Ltd.). The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. Among these,
Surfactants containing fluorine atoms and / or silicon atoms are preferred. These surfactants may be added alone or in some combination.

The above-mentioned radiation-sensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) to be used in the manufacture of precision integrated circuit devices by an appropriate application method such as a spinner or a coater, and then is coated with a predetermined mask. Through exposure, baking and development, a good resist pattern can be obtained.

Examples of the developer for the radiation-sensitive composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, and n-propylamine. Primary amines such as diethylamine, di-n-
Secondary amines such as butylamine, triethylamine, tertiary amines such as methyldiethylamine, dimethylethanolamine, alcoholamines such as triethanolamine, tetramethylammonium hydroxide, quaternary ammonium salts such as tetraethylammonium hydroxide, An alkaline aqueous solution of a cyclic amine such as pyrrole or pyriidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0138]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. (Synthesis example of resin) p- (1- (cyclohexylethoxy) ethoxy) styrene / p-hydroxystyrene (30/70) (resin P
2) Synthesis of p-hydroxystyrene (VP-8000 manufactured by Nippon Soda)
70 g was heated and dissolved in 320 g of propylene glycol monomethyl ether acetate (PGMEA), dehydrated by distillation under reduced pressure, and then cooled to 20 ° C. To this solution was added 0.35 g of pyridinium-p-toluenesulfonate and 22.4 g of cyclohexaneethanol. To this solution, 17.5 g of t-butyl vinyl ether was slowly added, and reacted at 20 ° C. for 5 hours. 0.28 g of triethylamine and 320 ml of ethyl acetate were added to the reaction solution, which was washed three times with 150 ml of distilled water. The solvent was distilled off and concentrated. The obtained oil was dissolved in 100 ml of acetone, and this was slowly poured into 2 L of distilled water. The precipitated powder was collected by filtration and dried to obtain 54 g of the desired product.

Synthesis of p- (1- (cyclohexylethoxy) ethoxy) styrene / p-acetoxystyrene / p-hydroxystyrene (30/10/60) (resin P3) p-hydroxystyrene (VP-8000 manufactured by Nippon Soda)
70 g was heated and dissolved in 320 g of propylene glycol monomethyl ether acetate (PGMEA), dehydrated by distillation under reduced pressure, and then cooled to 20 ° C. To this solution was added 0.35 g of pyridinium-p-toluenesulfonate and 22.4 g of cyclohexaneethanol. To this solution, 17.5 g of t-butyl vinyl ether was slowly added, and reacted at 20 ° C. for 5 hours. 5.53 g of pyridine was added to the reaction solution, and 5.9 g of acetic anhydride was slowly added thereto. The reaction was carried out at room temperature for 1 hour, and 320 ml of ethyl acetate was added to the solution, which was washed three times with 150 ml of distilled water. The solvent was distilled off and concentrated. The obtained oil was dissolved in 100 ml of acetone, and this was slowly poured into 2 L of distilled water. The precipitated powder is collected by filtration and dried to obtain 5
8 g were obtained. Other resins were synthesized in the same manner as above.

(B-1) Synthesis of Photoacid Generator Synthesis of Compound (PAG-A1) Diphenyl sulfoxide (50 g) was dissolved in benzene (800 ml), and aluminum chloride (200 g) was added thereto, followed by refluxing for 24 hours. The reaction solution was slowly poured into 2 liters of ice, and 400 ml of concentrated hydrochloric acid was added thereto, followed by heating at 70 ° C. for 10 minutes. This aqueous solution is treated with ethyl acetate 50
After washing with 0 ml and filtration, a solution prepared by dissolving 200 g of ammonium iodide in 400 ml of water was added. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate and dried to obtain 70 g of triphenylsulfonium iodide. 50 g of triphenylsulfonium iodide was dissolved in 300 ml of methanol, and 31 g of silver oxide was added thereto, followed by stirring for 4 hours. After filtering the reaction solution, 2,4,6-triisopropylbenzenesulfonic acid tetramethylammonium salt (2,4,6-triisopropylbenzenebenzenesulfonyl chloride is heated and reacted in tetramethylammonium hydroxide, water, and methanol) 45 g).
The solution was concentrated, and the resulting powder was thoroughly washed with water and recrystallized from ethyl acetate / acetone to give the compound (PAG-
A1) was obtained in an amount of 50 g.

Synthesis of Compound (PAG-A2) A mixture of commercially available triarylsulfonium Cl salt (50% aqueous solution of triphenylsulfonium chloride manufactured by Fluka), triphenylsulfonium, 4,4′-bis (diphenylsulfonio) diphenylsulfide and the like 19.9 g (0.030 mol) of an aqueous solution of
Dissolved in ml. 10.5 g of a hard (branched) dodecylbenzenesulfonic acid Na salt having the following structure was added to this solution.
(0.030 mol) of a 400 ml solution of ion-exchanged water was added at room temperature with stirring. The precipitated viscous solid was separated by decanting, and washed with 1 liter of ion-exchanged water. The precipitated viscous solid was dissolved in 100 ml of acetone, and poured into 500 ml of ion-exchanged water with stirring to recrystallize. The precipitate was dried at 50 ° C. under vacuum to obtain a glassy solid 1
5.5 g were obtained. By NMR measurement, it was confirmed that this solid was the target photoacid generator (PAG-A2).

[0142]

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(B-2) Synthesis of photoacid generator (I-1) bis (t-amylphenyliodonium) p-
Synthesis of Tolyl Acetate Bis (t-amylphenyliodonium) iodide 91
g of methanol was dissolved in 2 L of methanol.
0 g was added, and the mixture was stirred at room temperature for 4 hours. After filtering the reaction solution to remove silver compounds, 30 g of p-tolylacetic acid was added to the filtrate.
Was added. The solution was concentrated, and the obtained oil was dissolved in 2 L of ethyl acetate. This solution was washed twice with 500 ml of a 2.38% aqueous solution of tetramethylammonium hydroxide and three times with 500 ml of distilled water. The solution was concentrated and the obtained solid was washed with 500 ml of diisopropyl ether to obtain 63 g of the desired product.

(I-9) Synthesis of bis (t-amylphenyliodonium) acetate Bis (t-amylphenyliodonium) iodide 50
g of silver (I) 2 dissolved in 2 L of methanol.
2 g was added and the mixture was stirred at room temperature for 4 hours. After the reaction solution was filtered to remove the silver compound, 7.5 g of acetic acid was added to the filtrate. The solution was concentrated and the obtained solid was washed with 300 ml of diisopropyl ether to obtain 32 g of the desired product.

(I-2) Synthesis of bis (t-amylphenyliodonium) p-nitrobenzoate Bis (t-amylphenyliodonium) iodide 10
was dissolved in 700 ml of methanol, and 4.44 g of silver (I) oxide was added thereto, followed by stirring at room temperature for 4 hours. After the reaction solution was filtered to remove the silver compound, 4.0 g of p-nitrobenzoic acid was added to the filtrate. The solution was concentrated, and the resulting solid was washed twice with 500 ml of a 2.38% aqueous solution of tetramethylammonium hydroxide and three times with 500 ml of distilled water, and dried to obtain 4.2 g of the desired product.

(II-1) Synthesis of triphenylsulfonium p-tolyl acetate 8.2 g of triphenylsulfonium iodide was dissolved in 500 ml of methanol, and 5.1 g of silver (I) oxide was added thereto.
Was added and stirred at room temperature for 4 hours. After the reaction solution was filtered to remove the silver compound, 3.8 g of p-tolylacetic acid was added to the filtrate. The solution was concentrated, and the resulting oil was extracted with ethyl acetate 2
After washing three times with 00 ml, 5.1 g of the desired product was obtained.

(II-5) Synthesis of Triphenylsulfonium Acetate 20 g of triphenylsulfonium iodide was dissolved in 500 ml of methanol, and 12.5 g of silver (I) oxide was added thereto.
Was added and stirred at room temperature for 4 hours. After the reaction solution was filtered to remove the silver compound, 4.0 g of acetic acid was added to the filtrate. The solution was concentrated, and the obtained oil was washed twice with 300 ml of diisopropyl ether to obtain 11.2 g of the desired product.

(Examples and Comparative Examples) (Preparation and Evaluation of Compositions)
The resist solution was prepared by dissolving in 8 g of A (propylene glycol monomethyl ether acetate) and filtering through a 0.1 μm filter. This resist solution was applied on a silicon wafer using a spin coater,
The film was dried on a vacuum adsorption type hot plate at 60 ° C. for 60 seconds to obtain a resist film having a thickness of 0.4 μm.

[0149]

[Table 1]

[Resin] P1: p- (1- (ethoxy) ethoxy) styrene / p-hydroxystyrene (35/65) P2: p- (1- (cyclohexylethoxy) ethoxy) styrene / p-hydroxystyrene (30 / 70) P3: p- (1- (cyclohexylethoxy) ethoxy) styrene / p-acetoxystyrene / p-hydroxystyrene (30
/ 10/60) P4: p- (1- (cyclohexylethoxy) ethoxy) styrene / pt-butylstyrene / p-hydroxystyrene (30/1
0/60) P5: p- (1- (benzyloxy) ethoxy) styrene / p-hydroxystyrene (30/70) P6: p- (1- (phenethyloxyethoxy) ethoxy) styrene / p-acetoxystyrene / p -Hydroxystyrene (30/10/60) In each of the above resins, the weight-average molecular weight (polystyrene conversion value confirmed by the GPC method) of polyhydroxystyrene before providing a protective group or the like is 8,000 for P1 to P3. , P4 and P5 are 15000 and P6 is 2000
0. [Photoacid generator] PAG-A3: Exemplified compound PAG7-3 described above (manufactured by Midori Kagaku)

Surfactant R08: Megafac R08 W-1: Troysol S-366 Organic basic compound

[0152]

Embedded image

The resist film was exposed using a 248 nm wavelength KrF excimer laser stepper (NA = 0.63). After the exposure, the film was heated on a hot plate at 100 ° C. for 60 seconds, immediately immersed in a 0.26 N tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried. The pattern on the silicon wafer obtained in this way was measured using a scanning scanning electron microscope (CD-SE).
Observed in M), the resist performance (dependency on coarse / dense, exposure latitude) as shown in the table was obtained. (Table 2 below)

The density difference ΔCD is a mask size of 0.17 μm.
At the exposure dose that reproduces the L / S = 1: 1.5 pattern at
It represents a dimensional difference from 0.17 μm when the dimension of the pattern of the same dimension L / S = 1: 5 is measured. Exposure latitude Δexp is, firstly, L / S = 0.15 μm in mask size.
Determine the optimal exposure that reproduces the 1: 1 pattern, and second, determine the range of exposure where the dimensions formed after development are within ± 10% of 150 nm, and determine the optimal exposure Represents the value divided by.

[0155]

[Table 2]

As shown in Table 2 above, the composition of the present invention has excellent dependency on density and has a large exposure latitude.

[0157]

The positive-working radiation-sensitive composition of the present invention is excellent in density dependency and exposure margin.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 504 G03F 7/004 504 H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AA00 AB03 AB15 AB16 AB17 AC08 AD03 BE00 BE07 BE08 BG00 CC03 CC04 CC20 FA03 FA12 FA17 4J002 AA051 BC121 BG021 BG091 BG121 CH052 EB106 EH057 EU186 EU216 EV226 EV296 FD206 FD312 FD317

Claims (5)

[Claims] (A) a resin having an acid-decomposable group represented by the following general formula (I), decomposed by the action of an acid, and having increased solubility in an alkaline developer: (b-1) activity At least one of compounds that generate an acid upon irradiation with light or radiation and contribute to the decomposition reaction of the acid-decomposable group, (b-
2) It is characterized by containing at least one kind of a compound that generates an acid upon irradiation with actinic rays or radiation and does not contribute to the decomposition reaction of the acid-decomposable group, (c) a surfactant, and (d) a solvent. Bodi type radiation-sensitive composition. Embedded image In the general formula (I), R ₁ represents an alkyl group having 1 to 4 carbon atoms. W is at least one selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom.
Represents an organic group, an amino group, an ammonium group, a mercapto group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted cyclic alkyl group containing a species atom and at least one carbon atom. n represents an integer of 1 to 4. 2. In the resin (a), at least a part of the phenolic hydroxyl group in an alkali-soluble resin containing a phenolic hydroxyl group is protected by an acid-decomposable group represented by the general formula (I). The body-type radiation-sensitive composition according to claim 1, which is a resin. 3. The body-type radiation-sensitive material according to claim 1, wherein W in the general formula (I) is at least one substituent selected from the group of substituents shown below. Composition. Embedded image In the above formula: R ₂ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, Alternatively, it represents an unsubstituted aryl group or a substituted or unsubstituted aralkyl group. R ₃ is a hydrogen atom, carbon number 1 to 6
Represents a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, an amino group, a hydroxyl group, or a cyano group. X represents a halogen atom. R ₄ is
Represents a substituted or unsubstituted aryl group or a substituted or unsubstituted cyclic alkyl group having 3 to 15 carbon atoms. m
Is a natural number of 1 to 4. 4. The compound (b-1) is a compound that generates a sulfonic acid upon irradiation with actinic rays or radiation,
2. The bodi-type radiation-sensitive composition according to claim 1, wherein the compound (b-2) is a compound that generates a carboxylic acid upon irradiation with actinic rays or radiation. 5. The radiation-sensitive composition according to claim 1, further comprising an organic basic compound.