JP2000147752A - Negative resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable a chemically amplifying negative resist compsn. containing an alkali soluble resin, radiation-sensitive acid producing agent and crosslinking agent crosslinkable with an acid to satisfy characteristics of sensitivity, resolution and resist profile when electron beams or X-rays are used by satisfying at least one condition of specified conditions. SOLUTION: In the chemically amplifying negative resist compsn. containing an alkali-soluble resin, radiation-sensitive acid producing agent and crosslinking agent with crosslinks with an acid, at least one condition in the following conditions is satisfied. The conditions are that (1) the radiation-sensitive acid producing agent is a compd. expressed by formulae I, II or the like, and that (2) the crosslinking agent is a low mol.wt. phenolic deriv. having <=1000 mol.wt. and a specified structure. In the formulae I and II, each of R1 to R27 may be same or different and represents a hydrogen atom, straight-chain, branched or cyclic alkyl group, straight-chain, branched or cyclic alkoxy group, hydroxy group, halogen atom or the like and X is at least one fluorine atom or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative resist composition suitable for use in ultra microlithography processes such as the production of ultra LSIs and high capacity microchips, and other photofabrication processes. More specifically, X including an excimer laser beam
The present invention relates to a negative-type photoresist composition capable of forming a high-definition pattern using a beam, an electron beam, and the like, and can be suitably used particularly for fine processing of a semiconductor element using a high energy beam such as an electron beam. The present invention relates to a negative resist composition.

[0002]

2. Description of the Related Art The degree of integration of integrated circuits is increasing, and in the manufacture of semiconductor substrates such as VLSI, processing of ultrafine patterns having a line width of less than half a micron is required. Have been. In order to satisfy the need, the wavelength used in an exposure apparatus used for photolithography has become shorter and shorter, and now, far ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) have been studied. . Further, formation of finer patterns by electron beams or X-rays has been studied.

In particular, electron beams or X-rays are positioned as a next-generation or next-next-generation pattern forming technology, and development of a negative resist capable of achieving a high sensitivity, a high resolution and a rectangular profile is desired. In electron beam lithography, accelerated electron beams emit energy in the process of causing collision and scattering with atoms constituting a resist material, thereby exposing the resist material to light. The use of a highly accelerated electron beam increases the straightness, reduces the effects of electron scattering, and makes it possible to form a high-resolution rectangular pattern.On the other hand, the electron beam permeability increases, The sensitivity decreases. As described above, in electron beam lithography, there is a trade-off between sensitivity, resolution, and resist shape, and it has been a problem how to achieve both.

Conventionally, various acid generators have been proposed for chemically amplified negative resists. Japanese Patent Publication No. 8-3635 contains organic halogen compounds, JP-A-2-150848, JP-A-6-19
9770 iodonium salt, sulfonium salt, JP-A-2-52
348, JP-A-4-367864, JP-A-4-367865, an acid generator containing Cl and Br is disclosed in JP-A-4-210960, JP-A-4-217249.
To diazodisulfone, diazosulfone compound,
226454 triazine compound, JP-A-3-87746, JP-A-4-24-2
91259, JP-A-6-236024, and US-5344742 each disclose a sulfonate compound.However, these acid generators can overcome the trade-off between sensitivity and resolution under electron beam irradiation and resolution / resist shape. Did not.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problem of the performance improvement technology inherent in microfabrication using an electron beam. It is the development of a negative type chemically amplified resist composition for electron beam or X-ray which satisfies the characteristics of resolution and resist shape.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that, in a negative-type chemical amplification system, the above objects of the present invention depend on the type of the photosensitive composition and a specific photoacid The present invention was found to be achieved by using a generator and / or a specific crosslinking agent, and led to the present invention. That is, the present invention is achieved by the following configurations. (1) A chemically amplified negative resist composition containing an alkali-soluble resin, a radiation-sensitive acid generator, and a crosslinking agent capable of crosslinking by an acid, characterized by satisfying at least one of the following conditions. Electron beam and X-ray chemically amplified negative resist composition. The radiation-sensitive acid generator is represented by the following general formulas (I) to (II)
It is a compound represented by I). The crosslinking agent that is crosslinked by an acid is a low-molecular-weight phenol derivative represented by the following general formula (IV) and having a molecular weight of 1000 or less.

[0007]

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In the general formulas (I) to (III), R _{1 to} R ₃₇
Are the same or different and are a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, or -S-
Represents an _R38 group. R ₃₈ represents a linear, branched or cyclic alkyl group or aryl group. Further, R _{1 to} R ₁₅ , R
₁₆ Of to R ₂₇ or R ₂₈ to R _37, 2 or more are bonded, a single bond, carbon, oxygen, sulfur, and one or other to form a ring containing two or more selected from nitrogen Is also good. X ⁻ is a linear, branched or cyclic alkyl group substituted with at least one fluorine atom, at least one fluorine atom, a linear, branched or cyclic alkyl group substituted with at least one fluorine atom. Alkoxy group, acyl group substituted with at least one fluorine atom, acyloxy group substituted with at least one fluorine atom, sulfonyl group substituted with at least one fluorine atom, substitution with at least one fluorine atom A sulfonyloxy group, a sulfonylamino group substituted with at least one fluorine atom, an aryl group substituted with at least one fluorine atom, an aralkyl group substituted with at least one fluorine atom, and at least one Having at least one selected from an alkoxycarbonyl group substituted with a fluorine atom Nsuruhon acid, an anion of naphthalenesulfonic acid, or anthracenesulfonic acid.

[0009]

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In the general formula (IV), Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent. R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom or carbon number 1
Shows no more than two hydrocarbon groups. R ^{41 represents a} hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. m: represents an integer of 2 to 4. n: represents an integer of 1 to 3. X ₁ represents a divalent linking group. Y: a divalent to tetravalent linking group having the following partial structure or a monovalent functional group having a hydrogen atom at the terminal.

[0011]

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Z: absent when Y is a terminal group,
Alternatively, it represents a divalent to tetravalent linking group or a monovalent functional group.
Further, Y or Z may be bonded to a carbon atom on Ar ¹ to form a ring.

Embodiments of the negative resist composition of the present invention include the following. A negative resist composition comprising an alkali-soluble resin, a radiation-sensitive acid generator represented by formulas (I) to (III), and a crosslinking agent capable of crosslinking by an acid. A negative resist composition comprising an alkali-soluble resin, a radiation-sensitive acid generator, and a crosslinking agent crosslinked by an acid and having a molecular weight of 1,000 or less and represented by the general formula (IV). It is characterized by containing an alkali-soluble resin, a radiation-sensitive acid generator represented by the general formula (I) to the general formula (III) and a cross-linking agent represented by the general formula (IV) having a molecular weight of 1,000 or less, which is crosslinked with an acid. Negative resist composition In the present invention, among the above-mentioned embodiments, an embodiment in which the effect of the present invention is further improved is preferable.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention will be described below. (1) Alkali-soluble resin used in the present invention The alkali-soluble resin in the present invention is a resin insoluble in water and soluble in an aqueous alkali solution (also referred to as an alkali-soluble resin).
It is. The alkali dissolution rate of the alkali-soluble resin is
Those measured at 23 ° C. with 0.261N tetramethylammonium hydroxide (TMAH) (20 ° C./sec) or more are preferable. It is particularly preferably at least 200 ° / sec (Å is Angstroms).

Examples of the alkali-soluble resin used in the present invention include novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, and hydrogenated polyhydroxy resin. Styrene, halogen or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o /
p- and m / p-hydroxystyrene copolymers, partially O-alkylated compounds based on hydroxyl groups of polyhydroxystyrene (for example, 5 to 30 mol% of O-methylated products, O-
(1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O-
(T-butoxycarbonyl) methylated compound) or O
-Acylated products (e.g., 5 to 30 mol% o-acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene -Hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and derivatives thereof, but are not limited thereto.

Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, and a part of O-polystyrene. Alkylated or O-acylated products, styrene-hydroxystyrene copolymers, and α-methylstyrene-hydroxystyrene copolymers. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

The predetermined monomer is 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., m
Hydroxychloro compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or as a mixture of two or more, but are not limited thereto. It is not something to be done.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, 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 their acetal compounds, such as chloroacetaldehyde diethyl acetal, among which formaldehyde is used Is preferred. These aldehydes are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

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 exposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred are 2,000 to 20,000.
00 range. Further, the weight average molecular weight of the polyhydroxystyrene other than the novolak resin, its derivative, and the copolymer is 2,000 or more, preferably 2,000 to 2,000.
It is 30,000, more preferably 2,000 to 20,000. Here, the weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. In the present invention, these alkali-soluble resins are 2
You may mix and use more than one kind. The amount of the alkali-soluble resin used is usually 30 to 90% by weight, preferably 50 to 90% by weight, based on the total weight of the resist composition (excluding the solvent).
80% by weight.

(2) Radiation-sensitive acid generator (hereinafter also referred to as photoacid generator) The photoacid generator suitably used in the present invention is represented by the above general formulas (I) to (III). . A linear group of R _{1 to} R ₃₈ ,
As the branched alkyl group, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-
Examples thereof include those having 1 to 4 carbon atoms such as -butyl group and t-butyl group. 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. Examples of the linear or branched alkoxy group represented by R _{1 to} R ₃₇ include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, Examples thereof include those having 1 to 8 carbon atoms such as an octyloxy group. Examples of the cyclic alkoxy group include a cyclopentyloxy group, for example, a cyclopentyloxy group and a cyclohexyloxy group. As the halogen atom for R _{1 to} R ₃₇ ,
Examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group for R ₃₈ 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.

R _{1 to} R ₁₅ , R _{16 to} R ₂₇ or R
Of ₂₈ to R _37, or two is formed by bonding a single bond, a carbon, oxygen, sulfur, and the ring containing one or more members selected from nitrogen, for example, furan ring, dihydrofuran Examples include a furan ring, a pyran ring, a trihydropyran ring, a thiophene ring, and a pyrrole ring.

In the general formulas (I) to (III), X ⁻ is an anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from the following groups. At least one fluorine atom, a linear, branched or cyclic alkyl group substituted by at least one fluorine atom; at least one linear, branched or cyclic alkoxy group substituted by at least one fluorine atom Acyl group substituted with a fluorine atom acyloxy group substituted with at least one fluorine atom sulfonyl group substituted with at least one fluorine atom sulfonyloxy group substituted with at least one fluorine atom at least one fluorine A sulfonylamino group substituted with an atom, an aryl group substituted with at least one fluorine atom, an aralkyl group substituted with at least one fluorine atom, and an alkoxycarbonyl group substituted with at least one fluorine atom

The linear, branched or cyclic alkyl group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, trifluoromethyl group, pentafluoroethyl group, 2,
Examples thereof include a 2,2-trifluoroethyl group, a heptafluoropropyl group, a heptafluoroisopropyl group, a perfluorobutyl group, a perfluorooctyl group, a perfluorododecyl group and a perfluorocyclohexyl group. Among them, a perfluoroalkyl group having 1 to 4 carbon atoms, all of which is substituted by fluorine, is preferable.

The above-mentioned linear, branched or cyclic alkoxy group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, a trifluoromethoxy group, a pentafluoroethoxy group,
Examples include a heptafluoroisopropyloxy group, a perfluorobutoxy group, a perfluorooctyloxy group, a perfluorododecyloxy group, a perfluorocyclohexyloxy group, and the like. Among them, a perfluoroalkoxy group having 1 to 4 carbon atoms, all of which is substituted by fluorine, is preferable.

The acyl group has 2 to 12 carbon atoms.
Wherein those substituted with 1 to 23 fluorine atoms are preferred. Specific examples include a trifluoroacetyl group, a fluoroacetyl group, a pentafluoropropionyl group, and a pentafluorobenzoyl group.

The acyloxy group has 2 to 2 carbon atoms.
12 which is substituted with 1 to 23 fluorine atoms is preferred. Specific examples include a trifluoroacetoxy group, a fluoroacetoxy group, a pentafluoropropionyloxy group, and a pentafluorobenzoyloxy group.

The above-mentioned sulfonyl group has a carbon number of 1 to 1.
12 which is substituted with 1 to 25 fluorine atoms is preferred. Specific examples include a trifluoromethanesulfonyl group, a pentafluoroethanesulfonyl group, a perfluorobutanesulfonyl group, a perfluorooctanesulfonyl group, a pentafluorobenzenesulfonyl group, and a 4-trifluoromethylbenzenesulfonyl group.

The sulfonyloxy group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specific examples include a trifluoromethanesulfonyloxy group, a perfluorobutanesulfonyloxy group, and a 4-trifluoromethylbenzenesulfonyloxy group.

The sulfonylamino group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specific examples include a trifluoromethanesulfonylamino group, a perfluorobutanesulfonylamino group, a perfluorooctanesulfonylamino group, and a pentafluorobenzenesulfonylamino group.

The aryl group has 6 to 1 carbon atoms.
4, which is substituted with 1 to 9 fluorine atoms is preferable. Specifically, a pentafluorophenyl group, 4
-Trifluoromethylphenyl, heptafluoronaphthyl, nonafluoroanthranyl, 4-fluorophenyl, 2,4-difluorophenyl, and the like.

The aralkyl group has 7 to 7 carbon atoms.
It is preferably 10 and substituted by 1 to 15 fluorine atoms. Specific examples include a pentafluorophenylmethyl group, a pentafluorophenylethyl group, a perfluorobenzyl group, a perfluorophenethyl group, and the like.

The alkoxycarbonyl group preferably has 2 to 13 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specific examples include a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a pentafluorophenoxycarbonyl group, a perfluorobutoxycarbonyl group, and a perfluorooctyloxycarbonyl group.

[0033] The most preferred X ^- is a fluorine-substituted benzenesulfonic acid anion, among others pentafluorobenzenesulfonic acid anion is particularly preferred.

The benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid having a fluorine-containing substituent further includes a linear, branched or cyclic alkoxy group, an acyl group, an acyloxy group, a sulfonyl group,
It may be substituted with a sulfonyloxy group, a sulfonylamino group, an aryl group, an aralkyl group, an alkoxycarbonyl group (the number of carbon atoms is the same as described above), a halogen (excluding fluorine), a hydroxyl group, a nitro group and the like. Hereinafter, specific examples of the compounds represented by the general formulas (I) to (III) are shown, but the invention is not limited thereto.

[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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The compounds of the general formulas (I) and (II)
For example, a method of reacting a substituted or unsubstituted phenylsulfoxide with an aryl Grignard reagent such as arylmagnesium bromide, and subjecting the obtained triarylsulfonium halide to salt exchange with a corresponding sulfonic acid, or a method corresponding to substituted or unsubstituted phenylsulfoxide A method of condensing and salt-exchanging an aromatic compound using an acid catalyst such as methanesulfonic acid / diphosphorus pentoxide or aluminum chloride, and a method of condensing and salt-exchanging a diaryliodonium salt and a diarylsulfide using a catalyst such as copper acetate. Can be synthesized by The compound of the general formula (III) can be synthesized by reacting an aromatic compound with periodate. The content of the compounds represented by the general formulas (I) to (III) in the composition is preferably 0.1 to 20% by weight, preferably 0 to 20% by weight, based on the solid content of the whole negative resist composition. 0.5 to 10% by weight, more preferably 1 to 7% by weight.

(Other photoacid generators) In the present invention, in addition to the compounds represented by the above general formulas (I) to (III), other compounds which decompose upon irradiation with radiation to generate an acid are used. be able to. In the present invention, when the compounds represented by the above general formulas (I) to (III) are used as essential components, the following other compounds which decompose upon irradiation with radiation to generate an acid may be used in combination. it can. The ratio of the photoacid generator which can be used in combination with the compounds represented by the general formulas (I) to (III) of the present invention is 100/0 in molar ratio.
20/80, preferably 90/10 to 40/60, and more preferably 80/20 to 50/50.

On the other hand, when the crosslinking agent represented by the above general formula (IV) is used as an essential component (as described above), the photoacid generator may be any one of the general formulas (I) to (III). The compound represented by the compound may be used, another photoacid generator described below may be used, or these may be used in combination. In this case, 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, based on the solid content of the whole negative resist composition. More preferably, it is 1 to 7% by weight.

Examples of such other photoacid generators include photoinitiators for cationic photopolymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and microresists. A known compound that generates an acid by light and a mixture thereof can be appropriately selected and used.

For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, Re 27,992, JP-A-3-140140
Salt, DCNecker etal, Macrom
olecules, 17, 2468 (1984), CSwen et al, Teh, Proc. Con
f.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056, etc., phosphonium salts, JVCrivello et al., Macromorecules, 10 (6), 1307
(1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent Nos. 104,143, 339,049, 410,201, JP-A-2-150,848, JP-A-2-296,514, etc. Described iodonium salts, JVCrivello etal, Polymer J. 17, 73 (198
5), JVCrivello et al. J. Org. Chem., 43, 3055 (1978)
, WRWatt et al, J. Polymer Sci., PolymerChem. Ed., 2
2,1789 (1984), JVCrivello etal, Polymer Bull., 14,
279 (1985), JVCrivello etal, Macromorecules, 14 (5),
1141 (1981), JVCrivello et al, J. PolymerSci., Polym
er Chem. Ed., 17, 2877 (1979), EP 370,693,
No. 161,811, No. 410,201, No. 339,049, No. 233,56
7, 297,443, 297,442, U.S. Pat.
No. 114, No. 4,933,377, No. 4,760,013, No. 4,734,
No. 444, No. 2,833,827, Dokoku Patent No. 2,904,626,
Nos. 3,604,580 and 3,604,581, JVCrivello et al., Macromorecules, 10 (6), 1307 (1
977), JVCrivello et al, J. PolymerSci., Polymer Che
m.Ed., 17,1047 (1979), etc.
S.Wen etal, Teh, Proc.Conf.Rad.Curing ASIA, p478 Toky
o, Oct (1988), etc., onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60 -239736
No., JP-A-61-169835, JP-A-61-169837, JP-A-61-169837
No. 62-58241, JP-A-62-212401, JP-A-63-70243,
Organic halogen compounds described in JP-A-63-298339, etc.
Meier et al., J. Rad. Curing, 13 (4), 26 (1986), TPGill
etal, Inorg.Chem., 19, 3007 (1980), D. Astruc, Acc.
Res., 19 (12), 377 (1896), and organic metal / organic halides described in JP-A-2-14145, S. Hayase et al., J. Polym
er Sci., 25, 753 (1987), E. Reichmanis et al., J. Pholimer
Sci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhu et al., J.
Photochem., 36, 85, 39, 317 (1987), B. Amit etal, Tetrahe
dron Lett., (24) 2205 (1973), DHR Barton et al., J. Chem.
Soc., 3571 (1965), PMCollins et al., J. Chem.SoC., Per
kin I, 1695 (1975), M. Rudinstein et al, Tetrahedron Le
tt., (17), 1445 (1975), JWWalker etal J. Am. Chem. So
c., 110, 7170 (1988), SCBusman et al, J. Imaging Techn
ol., 11 (4), 191 (1985), HMHoulihan et al, Macormolecu
les, 21, 2001 (1988), PM Collins et al., J. Chem. Soc., Che
m.Commun., 532 (1972), S.Hayase etal, Macromolecules, 1
8,1799 (1985), E. Reichmanis et al., J. Electrochem. So
c., Solid State Sci. Technol., 130 (6), FMHoulihanet
al, Macromolcules, 21, 2001 (1988), EP 0290,750
Nos. 046,083, 156,535, 271,851, 0,
U.S. Pat.Nos. 3,901,710 and 4,181,531
, A photoacid generator having an o-nitrobenzyl-type protecting group described in JP-A-60-198538, JP-A-53-133022, etc.
TUNOOKA etal, Polymer Preprints Japan, 35 (8), G. Bern
er etal, J.Rad.Curing, 13 (4), WJMijs etal, Coating
Technol., 55 (697), 45 (1983), Akzo, H. Adachi et al, Po
lymer Preprints, Japan, 37 (3), European Patent No. 0199,672,
No. 84515, No. 044,115, No. 618,564, No. 0101,1
No. 22, U.S. Pat.Nos. 4,371,605, 4,431,774, JP-A-64-18143, JP-A-2-245756, JP-A-3-140109, etc. Examples of the compound include sulfonic acid generating compounds and disulfone compounds described in JP-A-61-166544.

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, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas et al, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Ra
pid Commun., 9,625 (1988), Y.Yamada et al., Makromol.C
hem., 152, 153, 163 (1972), JVCrivello etal, J. Polym
erSci., Polymer Chem. Ed., 17,3845 (1979), U.S. Patent No. 3,849,137, Dokoku Patent No. 3,914,407, JP-A-63-266.
No. 53, JP-A-55-164824, JP-A-62-69263, JP-A-Showa
63-146038, JP-A-63-163452, JP-A-62-153853
And the compounds described in JP-A-63-146029 and the like can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, EP 126,712, and the like, can also be used compounds which generate an acid by light.

(3) Crosslinking Agent Used in the Present Invention In the present invention, a compound capable of being crosslinked by an acid (hereinafter referred to as an acid crosslinking agent or simply a crosslinking agent, as appropriate) is represented by the general formula (I)
It is preferable to use a phenol derivative represented by V). In the general formula (IV), Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent. From the availability of raw materials, the aromatic hydrocarbon ring is preferably a benzene ring, a naphthalene ring or an anthracene ring.

Preferred examples of the substituent include a halogen atom, a hydrocarbon group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an alkylthio group having 12 or less carbon atoms, a cyano group, a nitro group and a trifluoro group. And a methyl group. Because of its high sensitivity, Ar ¹
Benzene ring and naphthalene ring having no substituent,
Or a halogen atom, a hydrocarbon group having 6 or less carbon atoms,
A benzene ring and a naphthalene ring having an alkoxy group having 6 or less carbon atoms, an alkylthio group having 6 or less carbon atoms, or a nitro group as a substituent are particularly preferable.

R³⁹And R⁴⁰Are the same but different
Hydrogen atom or carbon with 12 or less carbon atoms
Shows a hydride group. Because of the ease of synthesis, R
³⁹And R⁴⁰Is a hydrogen atom or a methyl group
Particularly preferred. R⁴¹Is a hydrogen atom or 12 or more carbon atoms
Shows the lower hydrocarbon group. Because of the high sensitivity, R ⁴¹
Represents, for example, a methyl group, an ethyl group, a propyl group,
Hydrocarbons with 7 or less carbon atoms, such as xyl and benzyl groups
Is particularly preferred. m represents an integer of 2 to 4
You. n shows the integer of 1-3.

Also, X₁Represents a divalent linking group. Y is before
The divalent to tetravalent linking group or terminal having the partial structure
It represents a monovalent functional group that is a hydrogen atom. Z is divalent to tetravalent
Or a monovalent functional group, wherein Y is a terminal group
Does not exist in the case. Z depends on the valence of the linking group of Y
To change the valence or number. Further, when Y or Z is Ar
¹Bond to at least one of the above carbon atoms to form a ring
Is also good.

Next, X _{1 in the} general formula (IV) will be described in detail.
X ₁ is a divalent linking group, and preferably represents a single bond or a hydrocarbon linking group which may have a substituent. As the hydrocarbon linking group, a linear alkylene having 1 to 18 carbon atoms,
Branched alkylene and cyclic alkylene, having 2 to 18 carbon atoms
Linear, branched, cyclic alkenylene, alkynylene having 2 to 8 carbon atoms and arylene having 6 to 20 carbon atoms are preferable. More preferred examples of the hydrocarbon linking group for X ₁ include methylene, ethylene, propylene, butylene, isopropylene, cyclohexylene, phenylene, tolylene,
Examples include biphenylene and groups represented by the following structures.

[0053]

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When these linking groups have a substituent, preferred substituents include an alkoxy group having 12 or less carbon atoms, a halogen atom and a hydroxyl group.

Next, Y in the general formula (IV) will be described in detail. Y
Is a divalent to tetravalent linking group or a monovalent functional group, and as described above, may be monovalent, divalent, trivalent or tetravalent, and particularly has an interaction with a phenolic hydroxyl group. A group known to be strong. Specifically, it has the above-mentioned partial structure.

Here, that the exemplified structure is a partial structure of Y means that the linking group or the functional group Y whose terminal is a hydrogen atom has at least one exemplified partial structure. Accordingly, Y includes a group in which a plurality of the exemplified partial structures are linked, or a group in which the exemplified partial structure is linked to a normal hydrocarbon group or the like. Y
Is formed by bonding a plurality of partial structures or linking the exemplified partial structure and a normal hydrocarbon group to form a ring, which becomes a divalent to tetravalent linking group or a monovalent functional group. Is also good. Particularly, preferred structures having these partial structures include, for example, amides, sulfonamides, imides, ureas, urethanes, thioureas, carboxylic acids, carboxylic esters, and sulfonic esters.

Next, Z in the general formula (IV) will be described in detail. Z
Is not present when Y is a terminal group, and represents a divalent to tetravalent linking group or a monovalent functional group. Z is preferably a divalent to tetravalent hydrocarbon linking group which may have a substituent or 1
Is a monovalent hydrocarbon group. Examples of the divalent to tetravalent hydrocarbon linking group or monovalent hydrocarbon group include divalent to tetravalent carbon atoms having 1 to 4 carbon atoms.
18 straight-chain alkylene, or alkyl, divalent to tetravalent branched alkylene, or alkyl, divalent to tetravalent cyclic alkylene, or alkyl, divalent to tetravalent arylene having 6 to 20 carbon atoms, or Aryl, divalent to tetravalent carbon number 2-1
A straight-chain, branched, cyclic alkenylene or alkenyl of 8 or divalent to tetravalent alkynylene having 2 to 18 carbon atoms or alkynyl is preferable.

As more preferred specific examples of Z, when monovalent, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, secondary butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, octyl, benzyl, phenyl , Naphthyl,
Anthracenyl, allyl, vinyl and the like. In the case of divalent or higher valence, it is preferable to remove a hydrogen atom from these monovalent groups according to the valence to form a linking group.
When Z has a substituent, preferred substituents include alkoxy having 12 or less carbon atoms, a halogen atom, and a hydroxyl group. In the general formula (IV), when Z is absent and Y represents a divalent to tetravalent linking group, the residue other than Y in the general formula (IV) bonded to Y is 2 Up to four may be combined. In addition, when Z is present in the general formula (IV) and Z represents a divalent to tetravalent linking group, a residue other than Z in the general formula (IV) bonded to Z around the Z, May be bonded to 2 to 4.

Specific examples of the cross-linking agent (phenol derivative) preferably used in the present invention are shown below in some patterns for convenience, for example, with functional groups, but the present invention is not limited to these. It is not something to be done.

[0060]

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[0061]

[Table 1]

[0062]

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[0063]

[Table 2]

[0064]

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[0065]

[Table 3]

[0066]

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[0067]

[Table 4]

[0068]

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[0069]

[Table 5]

[0070]

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[0071]

[Table 6]

[0072]

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[0073]

[Table 7]

[0074]

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[0075]

[Table 8]

[0076]

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[0077]

[Table 9]

[0078]

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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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[0084]

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[0085]

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[0086]

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[0087]

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[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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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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In the above specific examples, ⁱ Pr is an isopropyl group, ⁿ Bu is an n-butyl group, ^t Bu is a t-butyl group, Ph is a phenyl group, and cyclo-C ₆ H
₁₁ represents a cyclohexyl group. Among these specific examples, a low-molecular-weight phenol derivative having an amide structure or a urea structure is not known as a crosslinking agent, and is preferable from the viewpoint of effects.

Formula (IV) useful as these crosslinking agents
Can be synthesized by a conventionally known method. A general synthetic method is shown in the following Schemes I and II.

[0103]

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In the formula, base represents a strong alkali, for example, KOH, NaOH, (CH ₃ ) ₄ N ⁺ OH and the like.

[0105]

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That is, the compound of the general formula (IV) can be synthesized from the corresponding phenol derivative by hydroxyalkylation and alkoxylation with a carbonyl compound.

The low molecular weight phenol derivative represented by the above general formula (IV) has a molecular weight of 1,000 or less, preferably 150 to 800, more preferably 250 to 750.
It is. These phenol derivatives may be used alone or in combination of two or more. In addition, when synthesizing these phenol derivatives, the phenol derivatives may be condensed with each other to produce by-products such as dimers and trimers, but the phenol derivatives may be used while containing these impurities. In this case as well, the impurity is preferably at most 30%, more preferably at most 20%.

In the present invention, the phenol derivative represented by the general formula (IV) accounts for 5 to 7
It is used in an amount of 0% by weight, preferably 10 to 50% by weight. Here, when the addition amount of the phenol derivative as a cross-linking agent is less than 5% by weight, the residual film ratio decreases, and
If it exceeds 70% by weight, the resolving power is reduced, and furthermore, the stability of the resist solution during storage is not preferred.

In the present invention, the following other crosslinking agents (i) and (ii) can be used in addition to the crosslinking agent represented by the above general formula (IV). In the present invention, when the crosslinking agent represented by the above general formula (IV) is used as an essential component, the following other crosslinking agents can be used in combination. In this case, the ratio of the other crosslinking agent that can be used in combination with the crosslinking agent represented by the general formula (IV) of the present invention is 100/0 to 20/80, preferably 90/10 to 40/60, and Preferably 80 /
20 to 50/50.

On the other hand, when the compounds represented by the general formulas (I) to (III) are used as essential components as the photoacid generator (the above-mentioned embodiment), the crosslinking agent is represented by the above general formula (IV) Or a cross-linking agent described below or a combination thereof. In this case,
The crosslinking agent (i) to (ii) which can be used in the present invention is used in an amount of 2 to 80% by weight, preferably 5 to 75% by weight, particularly preferably 10 to 70% by weight based on the total solid content. is there.
If the amount of the crosslinking agent is less than 2% by weight, the film loss during development is large, and if it exceeds 80% by weight, it is not preferable from the viewpoint of storage stability.

(I) Compound having N-hydroxymethyl group, N-alkoxymethyl group or N-acyloxymethyl group (ii) Epoxy compound These crosslinking agents will be described in detail below. (i) As a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group, European Patent Publication (hereinafter referred to as “EP-A”) No. 0,133,216; West German Patent 3,634,
No. 671, No. 3,711,264, monomer and oligomer-melamine-formaldehyde condensate and urea-formaldehyde condensate, EP-A 0,0
Benzoguanamine-formaldehyde condensate disclosed in the alkoxy-substituted compound disclosed in U.S. Pat. No. 212,482, and the like. More preferred examples include, for example,
A melamine-formaldehyde derivative having at least two free N-hydroxymethyl groups, N-alkoxymethyl groups, or N-acyloxymethyl groups is exemplified, and among them, an N-alkoxymethyl derivative is particularly preferred.

(Ii) Examples of the epoxy compound include monomers, dimers, oligomers, and the like containing one or more epoxy groups.
Polymeric epoxy compounds can be mentioned. For example, a reaction product of bisphenol A with epichlorohydrin, a reaction product of a low molecular weight phenol-formaldehyde resin with epichlorohydrin and the like can be mentioned. Other examples include epoxy resins described and used in U.S. Pat. No. 4,026,705 and British Patent 1,539,192.

(4) Other Components Used in the Composition of the Present Invention The negative resist composition of the present invention may further contain, if necessary, an organic basic compound, a dye, a surfactant and the like. it can.

(4) -1 Dye 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.

(4) -2 Organic Basic Compound 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 is preferable. Preferred chemical environments include the structures of the following formulas (A) to (E).

[0116]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and include a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, Represents 6 to 6 hydroxyalkyl groups or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R
²⁵¹ and R ²⁵² may combine with each other to form a ring.
R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ may be the same or different and represent an alkyl group having 1 to 6 carbon atoms.

Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group.

Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, imidazole, 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 aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. 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.

Particularly preferred compounds are guanidine and
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, , 4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine,
-(Aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, -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-amino Ethyl) 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, and the like, but are not limited thereto.

These nitrogen-containing basic compounds may be used alone or in combination of two or more. The ratio of the photoacid generator and the organic basic compound used in the composition is (photoacid generator) / (organic basic compound) (molar ratio) =
It is preferably 2.5 to 300. If the molar ratio is less than 2.5, the sensitivity becomes low and the resolving power may decrease.
Exceeding the limit may result in an increase in the thickness of the resist pattern over time from the exposure to the heat treatment, and the resolution may be reduced.
(Photoacid generator) / (organic basic compound) (molar ratio)
Preferably 5.0 to 200, more preferably 7.0 to 1
50. (4) -3 Solvents The photosensitive composition of the present invention is dissolved in a solvent that dissolves each of the above components, and is applied on a support. As the solvent 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 monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl pyruvate, methyl pyruvate , Pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like, and these solvents are used alone or as a mixture.

(4) -4 Surfactants A surfactant may be added 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 nonyl phenol ether and the like Sorbitan such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Te - DOO, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, Eftop EF301, E
F303, EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), Megafac F171, F173 (Dainippon Ink Co., Ltd.)
), Florad FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, S
C104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.)
Fluorinated surfactants such as organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and acrylic or methacrylic acid (co) polymerized polyflow Nos. 7
5, No. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these surfactants is usually 2 parts by weight per 100 parts by weight of the solid content in the composition of the present invention.
It is at most 1 part by weight, preferably at most 1 part by weight. These surfactants may be added alone or in some combination.

In the production of precision integrated circuit elements, the pattern formation step on a resist film is performed by forming the negative of the present invention on a substrate (eg, a transparent substrate such as a silicon / silicon dioxide cover, a glass substrate, an ITO substrate, etc.). A good resist pattern can be formed by applying a mold photoresist composition, then irradiating with an electron beam lithography apparatus, heating, developing, rinsing and drying.

Examples of the developer for the negative photoresist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; ethylamine;
primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, Aqueous solutions of alkalis such as quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, and cyclic amines such as pyrrole and piperidine can be used. Further, an appropriate amount of an alcohol such as isopropyl alcohol or a surfactant such as a nonionic surfactant may be added to an aqueous solution of the above alkalis.

Among these developers, quaternary ammonium salts are preferred, and tetramethylammonium hydroxide and choline are more preferred.

[0126]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto. 1. Example of synthesis of constituent materials (1) Photoacid generator 1) Synthesis of tetramethylammonium pentafluorobenzenesulfonate 25 g of pentafluorobenzenesulfonyl chloride was dissolved in 100 ml of methanol under ice cooling, and 25% tetramethylammonium hydroxide was added thereto. 100 g of the aqueous solution was slowly added. After stirring at room temperature for 3 hours, a solution of tetramethylammonium pentafluorobenzenesulfonate was obtained. This solution was used for salt exchange with sulfonium salt and iodonium salt.

2) Synthesis of triphenylsulfonium pentafluorobenzenesulfonate 50 g of diphenylsulfoxide was dissolved in 800 ml of benzene, and 200 g of aluminum chloride was added thereto.
Refluxed for 4 hours. The reaction solution was slowly poured into 2 L of ice, and 400 ml of concentrated hydrochloric acid was added thereto, followed by heating at 70 ° C. for 10 minutes. This aqueous solution was washed with 500 ml of ethyl acetate, filtered, and then 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. Triphenylsulfonium iodide (30.5 g) was dissolved in methanol (1000 ml), and silver oxide (19.1 g) was added to the solution.
Stirred for hours. The solution was filtered, and an excess amount of a solution of tetramethylammonium pentafluorobenzenesulfonate was added thereto. The reaction solution was concentrated and dissolved in 500 ml of dichloromethane, and the solution was washed with a 5% aqueous solution of tetramethylammonium hydroxide and water. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain triphenylsulfonium pentafluorobenzenesulfonate (I-1).

3) Synthesis of di (4-t-amylphenyl) iodonium pentafluorobenzenesulfonate 60 g of t-amylbenzene and 39.5 potassium iodate.
g, 81 g of acetic anhydride, and 170 ml of dichloromethane were mixed, and 66.8 g of concentrated sulfuric acid was slowly added dropwise thereto under ice cooling. After stirring for 2 hours under ice cooling, the mixture was stirred at room temperature for 10 hours. 500 ml of water was added to the reaction solution under ice-cooling, and the mixture was extracted with dichloromethane. The organic phase was washed with sodium hydrogen carbonate and water, and then concentrated to obtain di (4-t-amylphenyl) iodonium sulfate. This sulfate was added to a solution of an excess amount of tetramethylammonium pentafluorobenzenesulfonate. To this solution was added 500 ml of water, and the mixture was extracted with dichloromethane. The organic phase was washed with a 5% aqueous solution of tetramethylammonium hydroxide and water, and concentrated to obtain di (4-t-amylphenyl) iodonium pentafluorobenzenesulfonate (III). -1) was obtained. Other compounds can be synthesized using the same method as described above.

(2) Synthesis of Crosslinking Agent 1) Synthesis of Crosslinking Agent A-4 p-Aminophenol (1 mol) and sodium acetate (1 mol) were put into a flask together with acetone (1 liter), and isobutyric acid chloride (1 mol) was added. Add dropwise under ice-cooling. Five hours later, the mixture was poured into ice water to precipitate crystals, and the crystals were collected by filtration to obtain A-4-X in a yield of 80%. This A-4
-X (0.8 mol), KOH (0.8 mol), water 5
00ml, a 37% formalin aqueous solution (4.8 mol) was placed in a flask, heated at 50 ° C for 5 hours, and then neutralized with acetic acid.
The solvent was concentrated under reduced pressure, and the obtained oil was dissolved in ethyl acetate / methanol = 1/1 and separated by SiO ₂ column chromatography to obtain the target product A-4 as colorless crystals in a total yield of 50%. The synthesis scheme is as follows.

[0130]

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The structure of the obtained target product A-4 was ¹ H NM
It was confirmed by R, IR and MASS.

2) Synthesis of Crosslinking Agent D-3 A flask was charged with tyramine (1 mol) and acetone (1 liter), and phenyl isocyanate (1 mol) was added.
At room temperature. After 3 hours, the mixture was poured into ice water to precipitate crystals, and the crystals were collected by filtration to obtain D-3-X in a yield of 85%. This D-3-X (0.85 mol) and KOH
(0.85 mol), 500 ml of water and a 37% formalin aqueous solution (5.0 mol) were placed in a flask,
After heating for an hour, neutralize with acetic acid and concentrate under reduced pressure to precipitate crystals. The obtained crystals are recrystallized with methanol / water = 5/5,
The target product D-3 was obtained as a colorless powder in a total yield of 33%. The synthesis scheme is as follows.

[0133]

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The structure of the obtained target compound D-3 is represented by ¹ H NM
It was confirmed by R, IR and MASS.

3) Synthesis of Crosslinking Agent J-3 B-5 (1 mol), isopropyl alcohol (1 liter), sulfuric acid (1 mol) obtained by the same method as described above.
Is stirred in a flask at 70 ° C. for 1 day, neutralized with barium carbonate, filtered, and the filtrate is concentrated under reduced pressure. The resulting oil was dissolved in ethyl acetate / methanol = 9/1 and separated by SiO ₂ cam chromatography to obtain the desired product J-3 as a colorless oil in a yield of 70% from B-5. The synthesis scheme is as follows.

[0136]

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The structure of the obtained target product J-3 was ¹ H NM
It was confirmed by R, IR and MASS.

4) Synthesis of Crosslinking Agent S-33 p- (4-Hydroxyphenyl) benzoic acid (1 mo
l), KOH (2 mol), water (500 ml), 37%
A formalin aqueous solution (6.0 mol) is placed in a flask,
After heating at 50 ° C. for 10 hours, the mixture was neutralized with acetic acid, cooled on ice, and precipitated as crystals. The obtained crystals were recrystallized from methanol / water = 5/5 to obtain the desired product S-33 in a colorless powder yield of 70%. The synthesis scheme is as follows.

[0139]

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The structure of the obtained target product is represented by ¹ HNMR,
R, MASS confirmed. Similarly, other crosslinking agents could be easily synthesized.

[0141] 2. Examples [Examples and Comparative Examples] (1) Coating of resist A solution of a photoresist composition having a composition shown in Table 10 below using a compound constituting the present invention and a comparative compound selected from the above synthesis examples. Was adjusted. 0.2 μm for each sample solution
And then applied on a silicon wafer using a spin coater and dried on a vacuum adsorption type hot plate at 120 ° C. for 90 seconds to obtain a film thickness of 0.83
A μm resist film was obtained.

[0142]

[Table 10]

The abbreviations used in Table 10 indicate the following. <Resin> P-1: poly- (p-hydroxystyrene) Mw 10,000 Mw / Mn = 1.4 P-2: novolak resin m-cresol / p-cresol = 45/55 (molar ratio) Mw 6,500

[0144]

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[0145]

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(2) Preparation of resist pattern An electron beam lithography system (acceleration voltage 50 Ke
Irradiation was performed using V). 110 ° C each after irradiation
Heating for 60 seconds with a vacuum adsorption type hot plate,
It was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The cross-sectional shape of the obtained pattern was observed with a scanning electron microscope. The sensitivity is 0.2
The irradiation energy at the time of resolving a 0 μm line (line: space = 1: 1) was defined as the sensitivity, and the limiting resolution at the irradiation amount (line and space were separated and resolved) was defined as the resolution. 0.20 μm line (line: space = 1: 1)
For those that do not resolve, the maximum resolution is defined as the resolution,
The irradiation energy at that time was defined as sensitivity. Table 11 shows the performance evaluation results.

[0147]

[Table 11]

[Explanation of Evaluation Results] The results in Table 11 show that the resist composition [Example 8] using the photoacid generator of the present invention and a crosslinking agent other than the general formula (IV) was different from the acid generator other than the present invention. The composition shows higher sensitivity, higher resolution and a rectangular profile than the composition using the agent [Comparative Examples 1 to 4], indicating that the composition has excellent performance. These effects are achieved by the general formulas (I) to (II) of the present invention.
The negative resist composition having the acid generator (I) is particularly effective under electron beam and X-ray irradiation conditions, an effect which has not been known at all. The compositions (Examples 1 to 7) further containing the crosslinking agent represented by the general formula (IV) of the present invention in addition to the photoacid generator of the present invention show much higher sensitivity, resolution and profile. From these, it is clear that the composition containing both the acid generator and the crosslinking agent of the present invention is particularly suitable for electron beam irradiation and shows extremely excellent performance.

The composition of the present invention containing the crosslinking agent represented by the general formula (IV) and an acid generator other than the general formulas (I) to (III) (Example 9) is a cross-linking agent other than the present invention. Comparative Examples 1 to 3 containing the agent
4 shows an excellent performance as compared with No. 4 of the present invention.
It is clear that the crosslinking agent represented by (IV) is particularly suitable for electron beam lithography.

[0150]

According to the present invention, a negative photosensitive composition having excellent sensitivity and resolution and a rectangular profile can be provided by the chemically amplified negative resist composition for electron beam and X-ray.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuto Kunida 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Pref.

Claims (1)

[Claims] 1. A chemically amplified negative resist composition containing an alkali-soluble resin, a radiation-sensitive acid generator, and a crosslinking agent capable of crosslinking by an acid, satisfying at least one of the following conditions. A chemically amplified negative resist composition for electron beams and X-rays. The radiation-sensitive acid generator is represented by the following general formulas (I) to (II)
It is a compound represented by I). The crosslinking agent that is crosslinked by an acid is a low-molecular-weight phenol derivative represented by the following general formula (IV) and having a molecular weight of 1000 or less. Embedded image In the general formulas (I) to (III), R _{1 to} R ₃₇ are the same or different and each represent a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group. represents a halogen atom, or an -S-R ₃₈ group. R ₃₈ represents a linear, branched or cyclic alkyl group or aryl group. Further, two or more of R _{1 to} R ₁₅ , R _{16 to} R ₂₇ or R _{28 to} R ₃₇ are bonded to form one or two types selected from a single bond, carbon, oxygen, sulfur, and nitrogen. A ring including the above may be formed. X ^- is a linear, branched or cyclic alkyl group substituted with at least one fluorine atom, at least one fluorine atom, a linear, branched or cyclic alkyl group substituted with at least one fluorine atom Alkoxy group, acyl group substituted with at least one fluorine atom, acyloxy group substituted with at least one fluorine atom, sulfonyl group substituted with at least one fluorine atom, substitution with at least one fluorine atom A sulfonyloxy group, a sulfonylamino group substituted with at least one fluorine atom, an aryl group substituted with at least one fluorine atom, an aralkyl group substituted with at least one fluorine atom, and at least one Having at least one selected from an alkoxycarbonyl group substituted with a fluorine atom Benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid. Embedded image In the general formula (IV), Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent. R ³⁹ and R ⁴⁰ each independently represent a hydrogen atom or carbon number 1
Shows no more than two hydrocarbon groups. R ^{41 represents a} hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. m: represents an integer of 2 to 4. n: represents an integer of 1 to 3. X ₁ represents a divalent linking group. Y: a divalent to tetravalent linking group having the following partial structure or a monovalent functional group having a hydrogen atom at the terminal. Embedded image Z: absent when Y is a terminal group, or a divalent to tetravalent linking group or a monovalent functional group. Further, Y or Z may be bonded to a carbon atom on Ar ¹ to form a ring.