JP2002372783A - Negative type resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative type resist composition which satisfies such characteristics as sensitivity, resolution, a rectangular pattern shape and good edge roughness all at once in microfabrication of a semiconductor device using active light or radiation, particularly an electron beam or X-ray. SOLUTION: The negative type resist composition contains (A) a compound which generates an acid when irradiated with active light or radiation, (B) an alkali-soluble resin, (C) a crosslinker which causes crosslinking with the resin (B) under the action of the acid and (D) a compound containing both at least one amino group selected from secondary to tertiary alicyclic amino groups and at least one carboxyl group in one molecule.

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 photo publication processes. More specifically, the present invention relates to a negative photoresist composition capable of forming a pattern with high definition using an electron beam, an X-ray or the like, and is particularly suitable 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 which can be used for a resist composition.

[0002]

2. Description of the Related Art The degree of integration of integrated circuits is increasing, and the fabrication of semiconductor substrates such as VLSIs requires the processing of ultrafine patterns having a line width of less than half a micron. Was. In order to meet this need, the wavelength of exposure equipment used in photolithography has become increasingly shorter, and now far ultraviolet light and excimer laser light (XeCl, KrF, ArF, F2, etc.) have been studied. Is coming. Further, the formation of finer patterns using electron beams or X-rays has been studied. In particular, electron beam lithography is positioned as a next-generation or next-generation pattern formation technology,
There is a strong demand for a negative resist having high sensitivity, high resolution, a rectangular profile shape, and good edge roughness.

In electron beam lithography, energy is supplied to a compound in a process in which an accelerated electron beam causes collision and scattering with atoms constituting a resist material to cause a reaction of the resist material to form an image. The use of a highly accelerated electron beam increases the straightness, reduces the effects of electron scattering, and enables the formation of a high-resolution rectangular pattern with good edge roughness. And the sensitivity is reduced. in this way,
In electron beam lithography, there is a trade-off between sensitivity and resolution / resist shape and edge roughness, and there has been a problem how to achieve both.

For the purpose of improving sensitivity, chemically amplified resists mainly utilizing an acid catalyzed reaction are used as resist materials for these resists. Among them, alkali-soluble resists are mainly used for negative resists. A chemically amplified composition comprising a resin, an acid generator, and a crosslinking agent has been effectively used.

The acid generator is disclosed in Japanese Patent Publication No. 8-36.
No. 35 discloses an organic halogen compound, JP-A-2-52348.
Nos. 4 and 5 include aromatic compounds substituted with Br and Cl.
No. 368864 and JP-A-4-366865 describe Br,
Cl-substituted aromatic compounds having alkyl or alkoxy groups, JP-A-2-150848, JP-A-6-19
No. 9770, iodonium and sulfonium compounds, JP-A-3-87746, haloalkanesulfonate compounds, JP-A-4-210960, JP-A-4-2172
No. 49, a diazodisulfone compound or a diazosulfone compound; JP-A-4-336454, Br and I-substituted alkyltriazine compounds; JP-A-4-291258, a sulfonamide, sulfonimide compound;
JP-A-291259 discloses a sulfonic acid compound of a polyhydric phenol, JP-A-4-291260 and JP-A-4-29126.
No. 1 and JP-A-6-202320 disclose a naphthoquinonediazide-4-sulfonate compound.
No. 9 discloses a disulfone compound, JP-A-6-236024 discloses an N-oxyimidosulfonate compound, and U.S. Pat. No. 5,344,742 discloses a benzylsulfonate compound.

Further, with respect to acid crosslinking agents, see JP-A-3-75.
652, JP-A-5-181277, JP-A-7-14
No. 6556, a methoxymethylmelamine compound, JP-A-4-281455, JP-A-5-232702, JP-A-6-83055, a compound having an alkoxymethyl ether group, JP-A-5-281715, an oxazine compound, JP-A-5-134412, JP-A-6-38
No. 25 discloses an aromatic compound having an alkoxyalkyl group, and JP-A-6-194838 discloses, in addition to a trioxane compound, an alkoxymethyluryl compound described in JP-A-1-293339. Also, Japanese Patent Application Laid-Open
No. 186660 discloses a negative resist using an organic carboxylic acid compound and an organic amine as an additive, and JP-A-5-289340 discloses a negative resist using an amino acid type compound as an additive. However, also in these, high sensitivity and high resolution, a rectangular profile, and good edge roughness cannot be simultaneously satisfied.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the problem of a technique for improving the performance in the fine processing of a semiconductor device using actinic rays or radiation, particularly electron beams or X-rays. An object of the present invention is to provide an electron beam or X-ray negative type chemically amplified resist which simultaneously satisfies the characteristics of sensitivity and resolution, rectangular pattern shape, and good edge roughness for the use of a line or X-ray.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a chemically amplified negative resist using a compound which generates an acid upon irradiation with actinic rays or radiation, an alkali-soluble resin, and a crosslinking agent is used. It is further achieved by adding a compound containing an amino group and a carboxyl group in the molecule. That is, the present invention is achieved by the following configurations.

(1) (A) a compound which generates an acid upon irradiation with actinic rays or radiation, (B) an alkali-soluble resin, (C) a crosslinking agent which crosslinks with the resin of (B) by the action of an acid, (D) A negative resist composition comprising a compound containing at least one amino group selected from secondary and tertiary alicyclic amino groups and at least one carboxyl group in the molecule.

(2) The negative resist composition according to the above (1), further comprising (E) an organic basic compound.

(3) The resin (B) is a resin containing a repeating unit represented by the following general formula (b) (hereinafter referred to as a resin).
(1)
Or the negative resist composition according to (2).

[0012]

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In the formula, R ₁ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group which may have a substituent. R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an acyl group which may have a substituent. R ₃ , R ₄
May be the same or different and represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group which may have a substituent. A is a single bond, which may have a substituent, an alkylene group, an alkenylene group, a cycloalkylene group, or an arylene group, or -O-,-
SO _2- , -O-CO-R _5- , -CO-OR ₆ -,-
_{CO-N (R 7) -R} 8 - represents a. R ₅ , R ₆ , and R ₈ may be the same or different and may have a single bond, a substituent, an alkylene group, an alkenylene group, a cycloalkylene group, or an arylene group alone, or At least one selected from the group consisting of an ether structure, an ester structure, an amide structure, a urethane structure and a ureido structure
Represents a divalent group formed by the species together. R ₇ may be the same or different and represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent. n represents an integer of 1 to 3.
Further, a plurality of R ₂ , or a combination of R ₂ and R ₃ or R ₄ may form a ring.

(4) The resin as the component (B) contains at least one resin selected from the repeating units represented by the following formulas (b-2) and (b-3) (hereinafter referred to as resin B2).
(1) or (2).

[0015]

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[0016] In the formula, R ₁ and A are respectively R _1, A of the general formula (b) synonymous. R _{101 to} R ₁₀₆ are each independently
Hydroxy group, linear, branched, or cyclic alkyl group, alkoxy group, alkylcarbonyloxy group, alkylsulfonyloxy group, alkenyl group, aryl group, aralkyl group, carboxy group, amino group, N-alkylamino group, Represents an N-dialkylamino group. a to f
Each independently represents an integer of 0 to 3.

(5) The negative resist composition as described in any of (1) to (4) above, wherein the exposure light source is an electron beam or an X-ray.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail. [1] Alkali-soluble resin of the present invention (B) In the present invention, the alkali-soluble resin is a phenol novolak resin, a polyvinyl phenol resin, or a copolymer having a structural unit derived from vinyl phenol, which has been disclosed as a negative chemically amplified resist. , And a resin obtained by partially protecting or modifying the polyvinylphenol resin,
A polymer having a phenol skeleton can be widely used. Preferable examples include a phenol resin containing a repeating structural unit represented by the general formula (b).

In the general formula (b), R ₁ represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group or a haloalkyl group which may have a substituent. R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an acyl group which may have a substituent. R ₃ and R ₄ may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group. Represents A may have a single bond, a substituent, a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group, or _{-O -, - SO 2 -,} - O-CO-R 5 -, −
_{CO-O-R 6 -,} - CO-N (R 7) -R 8 - represents a.

R ₅ , R ₆ and R ₈ may be the same or different, and may have a single bond, a substituent, an alkylene group,
Alkenylene group, cycloalkylene group or arylene group alone or divalent formed by combining these groups with at least one selected from the group consisting of ether structure, ester structure, amide structure, urethane structure and ureido structure Represents a group. R ₇ may be the same or different and represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent. n represents an integer of 1 to 3. Further, a plurality of R ₂ , or a combination of R ₂ and R ₃ or R ₄ may form a ring.

The alkyl group of R _{1 to} R ₄ and R ₇ is, for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group. , A sec-butyl group, a hexyl group, a 2-ethylhexyl group, and an octyl group. R ₂ ~
The cycloalkyl groups of R ₄ and R ₇ may be monocyclic or polycyclic. Preferred examples of the monocyclic type include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group each having 3 to 8 carbon atoms. Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a dicyclopentyl group, an a-pinel group, and a tricyclodecanyl group. The alkenyl group for R ₃ and R ₄ is, for example, an alkenyl group having 2 to 8 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The aryl group of R _{2 to} R ₄ and R ₇ is, for example, an aryl group having 6 to 15 carbon atoms, and specifically, a phenyl group, a tolyl group, a dimethylphenyl group,
Preferred are 4,6-trimethylphenyl group, naphthyl group, anthryl group and the like. R _{2 to} R ₄ , R ₇
The aralkyl group is, for example, an aralkyl group having 7 to 12 carbon atoms, and specific examples thereof preferably include a benzyl group, a phenethyl group, and a naphthylmethyl group.

The haloalkyl group for R ₁ is, for example, a haloalkyl group having 1 to 4 carbon atoms, and specifically includes chloromethyl, chloroethyl, chloropropyl, chlorobutyl, bromomethyl, bromoethyl and the like. Preferred examples are given.

The acyl group for R ₂ is, for example, one having 1 carbon atom.
To 8 acyl groups, specifically, a formyl group,
Preferable examples include an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, and a benzoyl group.

The alkylene group represented by A, R ₅ , R ₆ and R ₈ is preferably an alkylene group which may have a substituent, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group. Those having 1 to 8 carbon atoms are exemplified. Examples of the alkenylene group for A, R ₅ , R ₆ and R ₈ include:
Preferably an ethenylene group which may have a substituent,
Those having 2 to 6 carbon atoms such as a propenylene group and a butenylene group are exemplified.

The cycloalkylene group represented by A, R ₅ , R ₆ and R ₈ is preferably an optionally substituted cycloalkylene group having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group.
Individual ones. The arylene group for A, R ₅ , R ₆ and R ₈ is preferably a phenylene group, a tolylene group,
Those having 6 to 12 carbon atoms such as a naphthylene group are exemplified.

The substituents substituted on these groups include:
Those having active hydrogen such as amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group, and halogen atom (fluorine atom, chlorine atom, bromine atom,
Iodine atom), alkoxy group (methoxy group, ethoxy group,
Propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, Ethoxycarbonyl group, propoxycarbonyl group, etc.), cyano group, nitro group and the like. Particularly, those having active hydrogen such as an amino group, a hydroxyl group and a carboxyl group are preferable.

The ring formed by combining a plurality of R ₂ , or R ₂ and R ₃ or R ₄ is a benzofuran ring,
Examples thereof include a 4- to 7-membered ring containing an oxygen atom such as a benzodioxonol ring and a benzopyran ring.

The alkali-soluble resin of the component (B) used in the present invention is represented by the general formula (b-2) or (b-3):
Those having any of the repeating units represented by

In the general formulas (b-2) and (b-3),
R ₁ has the same meaning as R ₁ in the general formula (b). A has the same meaning as A in the general formula (b). R _{101 to} R ₁₀₆ each independently represent a hydrogen atom, a hydroxy group, a linear, branched, or cyclic alkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkenyl group, an aryl group, an aralkyl group. Represents a group, a carboxy group, an amino group, an N-alkylamino group, or an N-dialkylamino group, but is preferably a hydrogen atom, a hydroxy group, a linear or branched alkyl group having 1 to 6 carbon atoms, 1
To 6 alkoxy groups, C1 to C6 alkylcarbonyloxy groups, and phenyl groups, particularly preferably a hydrogen atom, a hydroxy group, or a C1 to C4 linear or branched alkyl group (methyl group, Ethyl group, n-propyl group, n
-Butyl group, t-butyl group, etc.), C1-C3 alkoxy groups (methoxy group, ethoxy group, etc.) and phenyl group. a to f each independently represent an integer of 0 to 3, preferably 0 to 2. On the aromatic ring represented by Y, the position of the bond bonded to the main chain or the position of the bond bonded to the substituent may be any position on the aromatic ring.

The resin of the present invention (B) may be copolymerized with another polymerizable monomer for the purpose of further improving the performance of the negative resist of the present invention.

The copolymerizable monomers that can be used include those shown below. For example, acrylates other than the above, acrylamides, methacrylates, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, addition polymerizable unsaturated bonds selected from crotonates and the like. It is a compound having one.

Specifically, for example, acrylates such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (eg, methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate) , Chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2
-Dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) aryl acrylate (for example, phenyl acrylate);

Methacrylic acid esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate,
Amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Chlorbenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate , Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.),
Aryl methacrylates (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, (where the alkyl group has 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl) Group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide (aryl group includes, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group,
Examples include a cyanophenyl group, a hydroxyphenyl group, and a carboxyphenyl group. ), N, N-dialkylacrylamide (an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group, a cyclohexyl group, etc.), N-diarylacrylamide (an aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like ;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl groups having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl Group, cyclohexyl group, etc.), N
-Aryl methacrylamide (an aryl group includes a phenyl group and the like), N, N-dialkyl methacrylamide (an alkyl group includes an ethyl group, a propyl group and a butyl group), N, N-diaryl Methacrylamide (an aryl group includes a phenyl group and the like), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide and the like;
Allyl compounds, for example, allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol Such;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether,
Ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, Tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ethers (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-
2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate , Vinylphenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-
Phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, and the like;

Styrenes, for example, styrene, alkyl styrene (eg, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc., alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene) , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluors Ren, trifluoromethyl styrene, 2
-Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), carboxystyrene;

Crotonic esters, for example, alkyl crotonates (for example, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.); dialkyl itaconates (for example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.) ); Dialkyl esters of maleic acid or fumaric acid (eg,
Dimethyl maleate, dibutyl fumarate, etc.), maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilenitrile and the like. In addition, generally, any addition-polymerizable unsaturated compound that can be copolymerized may be used.

Among these, monomers having a carboxyl group such as carboxystyrene, N- (carboxyphenyl) acrylamide, N- (carboxyphenyl) methacrylamide, and monomers improving the alkali solubility such as maleimide are copolymerization components. Is preferred. The content of the other polymerizable monomer in the resin in the present invention is preferably 50 mol% or less, more preferably 30 mol% or less, based on all repeating units.

Specific examples of the alkali-soluble resin (B) used in the present invention are shown below, but the present invention is not limited thereto.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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In the above specific examples, n represents a positive integer. x,
y and z represent the molar ratio of the resin composition, and for a resin consisting of two components, x = 10 to 95, y = 5 to 90, preferably x = 10
It is used in the range of 40 to 90, y = 10 to 60. In a resin consisting of three components, x = 10 to 90, y = 5 to 8
5, z = 5-85, preferably x = 40-80, y = 1
It is used in the range of 0 to 50 and z = 10 to 50.

The preferred molecular weight of the alkali-soluble resin (B) is from 1,000 to 200,000 by weight, more preferably from 3,000 to 50,000. The molecular weight distribution is from 1 to 10, preferably from 1 to 3, and more preferably from 1 to 1.5. The smaller the molecular weight distribution, the smoother the resolution, the resist shape, and the side wall of the resist pattern, and the better the roughness.

The alkali-soluble resin (B) used in the present invention is described in Macromolecules (1995), 28 (11), 3787-3789,
Polym. Bull. (Berlin) (1990), 24 (4), 385-389, and JP-A-8-286375. That is, the desired alkali-soluble resin can be obtained by radical polymerization or living anion polymerization. These resins may be used alone or in combination of two or more.

Here, the weight average molecular weight is defined as the value in terms of polystyrene by gel permeation chromatography. The alkali dissolving rate of the alkali-soluble resin is preferably 20 ° / sec or more as measured (23 ° C.) using 0.261N tetramethylammonium hydroxide (TMAH). Particularly preferably, it is 200 ° / sec or more.

In the resin B1, the content of the resin containing the repeating structural unit represented by the general formula (b) is 5 to 100 mol%, preferably 10 to 90 mol%, based on the whole resin. Mol%. In the resin B2, the content of at least one selected from the repeating structural units represented by general formulas (b-2) and (b-3) is 3 to 95 mol based on the entire resin. %, Preferably 5 to 90
Mol%.

The alkali-soluble resin of the present invention may be used alone or in combination with other alkali-soluble resins. The proportion of the alkali-soluble resin of the present invention is 10
Other alkali-soluble resins other than the present invention can be used up to 100 parts by weight with respect to 0 parts by weight. The following are examples of alkali-soluble resins that can be used together.

Examples include, but are not limited to, novolak resins, hydrogenated novolak resins, acetone-pyrogallol resins, styrene-maleic anhydride copolymers, carboxyl group-containing methacrylic resins and derivatives thereof. .

The amount of the resin (B) to be added is in the range of 30 to 95% by weight, preferably 40 to 90% by weight, more preferably 50 to 85% by weight based on the total solid content of the composition.

[2] The compound of the present invention (A) which generates an acid upon irradiation with actinic rays or radiation The component (A) used in the present invention is a compound which generates an acid upon irradiation with actinic rays or radiation. Any compound can be used if it exists.

Compounds that generate an acid upon irradiation with actinic rays or radiation include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, Alternatively, a known compound that generates an acid by light and a mixture thereof, which is used for a micro resist or the like, can be appropriately selected and used.

Further, a compound in which a group or a compound capable of generating an acid upon irradiation with these actinic rays or radiation is introduced into a main chain or a side chain of a polymer, for example, as disclosed in
3-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038,
JP-A-63-163452, JP-A-62-15385
No. 3, JP-A-63-146029 and the like. Further, U.S. Pat. No. 3,779,7
No. 78, EP 126,712 and the like, compounds which generate an acid by light can also be used.

Also, known onium salts such as diazonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, organic halogen compounds, o-nitrobenzylsulfonate compounds, N-iminosulfonate compounds, N-imidosulfonate compounds, diazonium salts Examples thereof include a sulfone compound, a diazodisulfone compound, and a disulfone compound.

Preferred are sulfonium or iodonium sulfonate compounds, N-hydroxyimide sulfonic acid ester compounds, and disulfonyldiazomethane compounds. Among them, particularly preferred are N-imidosulfonate compounds described in JP-A-10-7653 and JP-A-11-2901, and JP-A-4-21096.
No. 0, diazodisulfone compounds described in European Patent No. 417557, etc., and sulfonium salts and iodonium salts represented by the following general formulas (I) to (III). Sulfonium salts and iodonium salts represented by (III) are most preferred.

[0068]

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R _{1 to} R in the general formulas (I) to (III)
₃₇ is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, or a group which can be represented by -S-R _38. The alkyl group represented by R _{1 to} R ₃₇ may be linear, branched, or cyclic. Examples of the linear or branched alkyl group include an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group. be able to. As the cyclic alkyl group,
Examples thereof include an alkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

The alkoxy group represented by R _{1 to} R ₃₇ may be linear, branched or cyclic. Examples of the linear or branched alkoxy group include those having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group,
Examples thereof include an isobutoxy group, a sec-butoxy group, a t-butoxy group, and an octyloxy group. Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group.

Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group. Examples of the halogen atom represented by R _{1 to} R ₃₇ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R ₃₈ in -S-R ₃₈ in which R ₁ to R ₃₇ represents is an alkyl group, or an aryl group. The scope of the alkyl group R ₃₈ is represented can also include any example in the alkyl groups already listed as an alkyl group represented by R ₁ to R _37. The aryl group represented by R ₃₈ has a carbon number of 6 to 6, such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group.
There may be mentioned 14 aryl groups.

From the alkyl group represented by R _{1 to} R ₃₈ to the aryl group, any of the groups may further have a substituent bonded to a part of the group to increase the number of carbon atoms. Is also good. Further, the substituent which may be bonded is preferably an alkoxy group having 1 to 4 carbon atoms,
Examples include zero aryl groups and alkenyl groups having 2 to 6 carbon atoms, and examples include cyano groups, hydroxy groups, carboxy groups, alkoxycarbonyl groups, and nitro groups. In addition, a halogen atom may be used. For example,
Examples include a fluorine atom, a chlorine atom and an iodine atom.

The groups represented by R _{1 to} R ₁₅ in the general formula (I) are
Two or more of them may combine to form a ring. The ring may be formed by directly bonding the terminals of the groups represented by R _{1 to} R ₁₅ . They may be indirectly linked via one or more elements selected from carbon, oxygen, sulfur and nitrogen to form a ring. The ring structure formed by combining two or more of R _{1 to} R ₁₅ is the same as the ring structure found in a furan ring, dihydrofuran ring, pyran ring, trihydropyran ring, thiophene ring, pyrrole ring, and the like. Can be mentioned. R _{16 to} R in the general formula (II)
_{The same} can be said for ₂₇ . Two or more may be directly or indirectly linked to form a ring. The same applies to R _{28 to} R ₃₇ in the general formula (III).

The general formulas (I) to (III) have X ⁻ . X ⁻ in the general formulas (I) to (III) is an anion of an acid. The acid forming the anion is an acid selected from benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid. The acid is substituted by one or more fluorine atoms. Or the acid is, together with or in place of the fluorine atom, an alkyl group, an alkoxyl group, an acyl group, an acyloxyl group, a sulfonyl group,
It has at least one organic group selected from the group consisting of a sulfonyloxy group, a sulfonylamino group, an aryl group, an aralkyl group, and an alkoxycarbonyl group, and the organic group further substitutes at least one fluorine atom. are doing. Further, the above benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid may be substituted with a halogen atom other than fluorine, a hydroxyl group, a nitro group, or the like.

[0075] X ^- alkyl group bonding such as benzenesulfonic acid to form the anion of, for example, a carbon number 1 to 1
2 alkyl groups. The alkyl group may be linear, branched, or cyclic. At least one fluorine atom, preferably 25 or less, is substituted. Specifically, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, a heptafluoroisopropyl group, a perfluorobutyl group, a perfluorooctyl group, a perfluorododecyl group, Perfluorocyclohexyl group and the like can be mentioned. Among them, carbon atoms all substituted with fluorine 1
~ 4 perfluoroalkyl groups are preferred.

The alkoxy group bonded to benzenesulfonic acid or the like together with the alkyl group or alone is an alkoxy group having 1 to 12 carbon atoms. The alkoxy group may be linear, branched, or cyclic.
At least one fluorine atom, preferably 25 or less, is substituted. Specific examples include a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoroisopropyloxy group, a perfluorobutoxy group, a perfluorooctyloxy group, a perfluorododecyloxy group, and a perfluorocyclohexyloxy group.
Among them, a perfluoroalkoxy group having 1 to 4 carbon atoms, all of which is substituted by fluorine, is preferable.

The acyl group bonded to benzenesulfonic acid or the like together with the alkyl group or alone is preferably substituted with a fluorine atom having 2 to 12 or 1 to 23 carbon atoms. Specific examples include a trifluoroacetyl group, a fluoroacetyl group, a pentafluoropropionyl group, and a pentafluorobenzoyl group.

The acyloxy group bonded to benzenesulfonic acid or the like together with the alkyl group or alone is preferably substituted with a fluorine atom having 2 to 12 or 1 to 23 carbon atoms. Specific examples include a trifluoroacetoxy group, a fluoroacetoxy group, a pentafluoropropionyloxy group, and a pentafluorobenzoyloxy group. As the sulfonyl group bonded to benzenesulfonic acid or the like together with the alkyl group or alone, a sulfonyl group having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms is preferable. Specific examples include a trifluoromethanesulfonyl group, a pentafluoroethanesulfonyl group, a perfluorobutanesulfonyl group, a perfluorooctanesulfonyl group, a pentafluorobenzenesulfonyl group, and a 4-trifluoromethylbenzenesulfonyl group.

The above-mentioned sulfonyloxy group bonded to the above-mentioned benzenesulfonic acid or the like together with the alkyl group or alone is preferably a group substituted by a fluorine atom having 1 to 12 or 1 to 25 carbon atoms. Specific examples include a trifluoromethanesulfonyloxy group, a perfluorobutanesulfonyloxy group, and a 4-trifluoromethylbenzenesulfonyloxy group. The sulfonylamino group bonded to the above-mentioned benzenesulfonic acid or the like together with the alkyl group or alone has a carbon number of 1 to
12 which is substituted with 1 to 25 fluorine atoms is preferred. Specifically, a trifluoromethanesulfonylamino group, a perfluorobutanesulfonylamino group,
Examples thereof include a perfluorooctanesulfonylamino group and a pentafluorobenzenesulfonylamino group.

The aryl group bonded to the above-mentioned benzenesulfonic acid or the like together with the alkyl group or alone is preferably a group substituted by a fluorine atom having 6 to 14 or 1 to 9 carbon atoms. Specific examples include a pentafluorophenyl group, a 4-trifluoromethylphenyl group, a heptafluoronaphthyl group, a nonafluoroanthranyl group, a 4-fluorophenyl group, and a 2,4-difluorophenyl group. The aralkyl group bonded to the above-mentioned benzenesulfonic acid or the like together with the alkyl group or alone is preferably a group substituted by a fluorine atom having 7 to 10 or 1 to 15 carbon atoms. Specific examples include a pentafluorophenylmethyl group, a pentafluorophenylethyl group, a perfluorobenzyl group, a perfluorophenethyl group, and the like. The alkoxycarbonyl group bonded to the benzenesulfonic acid or the like alone or together with the alkyl group may have 2 to 13, 1 to 1 carbon atoms.
Those substituted with 25 fluorine atoms are preferred.
Specific examples include a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a pentafluorophenoxycarbonyl group, a perfluorobutoxycarbonyl group, and a perfluorooctyloxycarbonyl group.

Among these anions, the most preferred X ^- is a fluorine-substituted benzenesulfonic acid anion,
Among them, pentafluorobenzenesulfonic acid anion is particularly preferred. Further, the benzene sulfonic acid, naphthalene sulfonic acid, or anthracene sulfonic acid having the fluorine-containing substituent further has 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.

The following formulas (I) to (III)
Specific examples of the compound represented by are shown below, but it should not be construed that the invention is limited thereto.

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[0086]

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[0087]

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[0088]

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The compounds of the general formulas (I) and (II)
It can be synthesized by the following method. For example, an aryl Grignard reagent such as aryl magnesium bromide is reacted with phenylsulfoxide, and the resulting triarylsulfonium halide is subjected to salt exchange with the corresponding sulfonic acid. There is another way. For example, there is a method in which phenyl sulfoxide and an aromatic compound corresponding thereto are condensed and salt-exchanged using an acid catalyst such as methanesulfonic acid / diphosphorus pentoxide or aluminum chloride. Further, the diaryl iodonium salt and the diaryl sulfide can be synthesized by a method of condensation or salt exchange using a catalyst such as copper acetate. In any of the above methods, the phenylsulfoxide may have a substituent substituted on the benzene ring, or may not have such a substituent. The compound of the general formula (III) can be synthesized by reacting an aromatic compound with periodate.

The content of the component (A) used in the present invention is as follows:
0.1 to 20 with respect to the solid content of the whole negative resist composition
% Is suitable, preferably 0.5 to 10% by weight,
More preferably, it is 1 to 7% by weight.

In the present invention, other than the compounds represented by the above general formulas (I) to (III), or together with them, other compounds capable of generating an acid upon irradiation with actinic rays or radiation can be used. . When other compounds that generate an acid upon irradiation with actinic rays or radiation are used together with the compounds represented by the general formulas (I) to (III), they are represented by the above general formulas (I) to (III). The ratio of the compound to be generated and the other compound that generates an acid by irradiation with actinic rays or radiation is 100/0 to 20/8 in molar ratio.
0, preferably 90/10 to 40/60, more preferably 80/20 to 50/50.

[3] Acid Crosslinking Agent of the Invention (C) In the present invention, a compound capable of being crosslinked by an acid (hereinafter referred to as an acid crosslinking agent or simply as a crosslinking agent) together with an alkali-soluble resin and an acid generator. use. Here, a known acid crosslinking agent can be effectively used. Preferably,
A compound or resin having two or more hydroxymethyl groups, alkoxymethyl groups, acyloxymethyl groups, or alkoxymethyl ether groups, or an epoxy compound.

More preferably, alkoxymethylated, acyloxymethylated melamine compounds or resins, alkoxymethylated, acyloxymethylated urea compounds or resins, hydroxymethylated or alkoxymethylated phenol compounds or resins, and alkoxymethyl etherified phenol compounds Alternatively, a resin or the like can be used.

Specifically, a phenol derivative can be used as the crosslinking agent. Preferably, the molecular weight is 120
0 or less, containing 3 to 5 benzene rings in the molecule, and further having 2 or more hydroxymethyl groups or alkoxymethyl groups in total, and concentrating the hydroxymethyl group or alkoxymethyl group on at least one of the benzene rings. ,
Alternatively, a phenol derivative formed by distributing and binding can be used. By using such a phenol derivative, the effects of the present invention can be made more remarkable. The alkoxymethyl group bonded to the benzene ring preferably has 6 or less carbon atoms. Specifically, methoxymethyl, ethoxymethyl, n-propoxymethyl, i-propoxymethyl, n-butoxymethyl, i-butoxymethyl, sec-butoxymethyl and t-butoxymethyl are preferred. Further, an alkoxy-substituted alkoxy group such as a 2-methoxyethoxy group and a 2-methoxy-1-propyl group is also preferable. Among these phenol derivatives, particularly preferred ones are listed below.

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[0096]

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[0099]

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(Wherein L ^{1 to} L ⁸ may be the same or different and represent a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group.) A phenol derivative having a hydroxymethyl group A phenol compound having no hydroxymethyl group (L ^{1 in the} above formula)
~L ⁸ is a compound) with formaldehyde is a hydrogen atom can be obtained by reacting in the presence of a basic catalyst. At this time, the reaction is preferably performed at a reaction temperature of 60 ° C. or lower in order to prevent resinification and gelation. Specifically, it can be synthesized by a method described in JP-A-6-28067, JP-A-7-64285, or the like.

The phenol derivative having an alkoxymethyl group can be obtained by reacting the corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, the reaction is preferably performed at a reaction temperature of 100 ° C. or less in order to prevent resinification and gelation. Specifically, it can be synthesized by a method described in European Patent EP632003A1 or the like. A phenol derivative having a hydroxymethyl group or an alkoxymethyl group synthesized as described above is preferable in terms of stability during storage, but a phenol derivative having an alkoxymethyl group is particularly preferable from the viewpoint of stability during storage.
Such a phenol derivative having two or more hydroxymethyl groups or alkoxymethyl groups in total and concentrated or linked to any benzene ring may be used alone. A combination of the above may be used.

In addition to the above phenol derivatives, the following compounds (i) and (ii) can be used as crosslinking agents. (I) Compound having N-hydroxymethyl group, N-alkoxymethyl group, or N-acyloxymethyl group (ii) Epoxy compound

The cross-linking agent is 3% of the total solid content of the resist composition.
It is used in an addition amount of up to 65% by weight, preferably 5 to 50% by weight. If the amount of the cross-linking agent is less than 3% by weight, the residual film ratio decreases, and if it exceeds 65% by weight, the resolving power decreases, and the stability of the resist solution during storage is not so preferable.

In the present invention, in addition to the above-mentioned phenol derivatives, for example, other crosslinking agents (i) and (i) as described above
i) can be used in combination. The ratio of other crosslinking agents that can be used in combination in addition to the above-mentioned phenol derivative is 10 mol%.
0 / 0-20 / 80, preferably 90 / 10-40 / 6
0, more preferably 80/20 to 50/50.

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 No. 3,63
Monomer and oligomer-melamine-formaldehyde condensate and urea-formaldehyde condensate disclosed in U.S. Pat. Nos. 4,671 and 3,711,264; Benzoguanamine-formaldehyde condensates disclosed in substituted compounds and the like can be mentioned. More preferred examples include, for example, at least two free N-hydroxymethyl groups,
A melamine-formaldehyde derivative having an -alkoxymethyl group or an N-acyloxymethyl group, among which an N-alkoxymethyl derivative is particularly preferred.

(Ii) Examples of the epoxy compound include monomer, dimer, oligomer, and polymer epoxy compounds containing one or more epoxy groups. 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] At least one amino group selected from secondary to tertiary alicyclic amino groups and at least one carboxyl group in the molecule of component (D) used in the present invention. Compounds containing both

The compound of the component (D) has the following general formula (d)
Preferably, the structure is represented by

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In the above formula (d),

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Represents a 4- to 8-membered alicyclic amino group structure, which may have a substituent. Particularly preferably 5
Represents a 6-membered alicyclic amino group structure. Examples of the substituent include a halogen atom (such as Cl and Br), a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 4 to 8 carbon atoms, and 6 carbon atoms.
And aralkyl groups having 7 to 14 carbon atoms. R ₅₁ is a hydrogen atom, carbon number 1 to
An alkyl group of 8, a cycloalkyl group having 4 to 12 carbon atoms,
It represents an aryl group having 6 to 18 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. Also,
R ₅₁ may form a ring together with part of the alicyclic cyclic amino group. Particularly preferably, R ₅₁ is a hydrogen atom,
It is an alkyl group having 1 to 4 carbon atoms. R ₅₂ represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, or an arylene group having 6 to 18 carbon atoms, particularly preferably a single bond or an alkylene group having 1 to 4 carbon atoms. It is. a and b each represent an integer of 1 to 3.

R₅₁, R₅₂May have a substituent,
As the substituent, a halogen atom (Cl, Br, F
Etc.), -CN group, -OH group, -NH_TwoGroup, -NH (R₅₃)
Group (where R₅₃Represents an alkyl group having 1 to 4 carbon atoms),
−N (R₅₃) (R₅₄) Group (where R ₅₄Is R₅₃Synonymous with
), An alkyl group having 1 to 4 carbon atoms, and a cycle having 4 to 8 carbon atoms.
Loalkyl group, aryl group having 6 to 12 carbon atoms, 7 carbon atoms
-14 aralkyl groups, C 1-4 alkoxy groups,
Examples include a carboxyl group and a formyl group. these
The amine group contains 1 to 3 amine groups in the molecule of component (D).
And more preferably 1 or 2. Also
When two or more amino groups are contained, an amine group having the same structure is contained.
Or an amino group having a different structure.

The compound of component (D) preferably contains 1 to 3 carboxyl groups in the molecule of component (D), more preferably 1 to 2 carboxyl groups.

The compound of component (D) is preferably nipecotic acid, isonipecotic acid, pipecolic acid, N-methyl pipecolic acid, N-methyl nipecotic acid, N-ethyl isonipecotic acid, N-propyl pipecolic acid, 3-
Hydroxypipecolic acid, 4-hydroxypipecolic acid, 4-hydroxynipecotic acid, 2-hydroxyisonipecotic acid, proline, N-methylproline, 3-hydroxyproline, 4-hydroxyproline, N-methyl- 3-hydroxyproline, 2-carboxypiperazine, 2,6-dicarboxypiperazine, N-methyl-2
-Carboxypiperazine, 2-carboxymethylpiperidine, 2-carboxymethylpyrrolidine, 2-carboxyethylpiperidine, and the like, but are not limited thereto.

As the component (D) used in the present invention, one type may be used, or two or more types may be used as a mixture. The content of the component (D) used in the present invention is suitably 0.01 to 20% by weight, preferably 0.02 to 10% by weight, particularly preferably 0.02 to 10% by weight, based on the solid content of the whole negative resist composition. Preferably it is 0.03 to 5% by weight.

[5] Other components used in the composition of the present invention The negative resist composition of the present invention may further contain, if necessary, a radical generator, an organic basic compound, a dye, a surfactant and the like. It can be contained.

[5] -1 Dyes 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.

[5] -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).

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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 are both substituted or unsubstituted amino groups and ring structures containing nitrogen atoms. 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, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, a cyano group It is.

Particularly preferred compounds are guanidine,
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-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, and the like, but are not limited thereto. These nitrogen-containing basic compounds are used alone or in combination of two or more.

The ratio of the acid generator and the organic basic compound used in the composition is preferably (acid generator) / (organic basic compound) (molar ratio) = 2.5 to 300. If the molar ratio is less than 2.5, the sensitivity becomes low and the resolving power may decrease. If the molar ratio exceeds 300, the resist pattern becomes thicker and the resolving power may decrease over time until the heat treatment after exposure. . (Acid generator) / (organic basic compound) (molar ratio) is preferably from 5.0 to 200, more preferably from 7.0 to 150.

[5] -3 Solvents The composition of the present invention is dissolved in a solvent capable of dissolving the above-mentioned components, and 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, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methyl Pyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

[5] -4 Surfactants Surfactants can be added to the above solvents. 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 - door,

Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate; EFTOP EF301 and EF3
03, EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Florade FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-
382, SC101, SC102, SC103, SC1
04, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), fluorinated surfactant such as Troysol S-366 (manufactured by Troy Chemical 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 KK) and the like. 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. 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 photoresist pattern is formed by applying a photoresist composition and then irradiating with an electron beam (under an acceleration voltage of 75 keV or more) or an X-ray lithography apparatus, and heating, developing, rinsing, and drying to form a good resist pattern. can do.

Examples of the developer for the negative resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, and n-propylamine. Primary amines such as diethylamine, di-
Secondary amines such as n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, and tertiary amines such as tetramethylammonium hydroxide, Aqueous solutions of alkalis such as quaternary ammonium salts, 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. Of these developers, quaternary ammonium salts are preferred, and tetramethylammonium hydroxide and choline are more preferred.

[0131]

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.

[0132] 1. Synthesis Examples of Constituent Materials (1) Alkali-Soluble Resin Synthesis Example 1 (Synthesis of Resin Example (29)) 3.9 g (0.024 mol) of 4-acetoxystyrene,
0.8 g (0.006 mol) of 4-methoxystyrene was added to 1
-Methoxy-2-propanol dissolved in 30 ml and a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) at 70 ° C under a nitrogen stream and stirring. V-65) 50 mg, 4-acetoxystyrene 9.1 g (0.056 mol), 4-methoxystyrene 1.9 g (0.014 mol) 1-methoxy-
A 70 ml solution of 2-propanol was added dropwise over 2 hours. After 2 hours, 50 mg of an initiator was added, and the reaction was further performed for 2 hours. Thereafter, the temperature was raised to 90 ° C., and stirring was continued for 1 hour.
After allowing the reaction solution to cool, it was poured into 1 L of ion exchanged water with vigorous stirring to precipitate a white resin. After drying the obtained resin, it was dissolved in 100 mL of methanol,
% Tetramethylammonium hydroxide was added to hydrolyze the acetoxy group in the resin, and then neutralized with an aqueous hydrochloric acid solution to precipitate a white resin. Rinse with deionized water,
After drying under reduced pressure, 11.6 g of the resin (29) of the present invention was obtained. When the molecular weight was measured by GPC, the weight average (M
w: 9,200 in terms of polystyrene and the degree of dispersion (Mw /
Mn) was 2.2.

Synthesis Example 2 (Synthesis of Resin Example (39)) 12.0 g of poly (4-hydroxystyrene) (Mw = 1
0,500, Mw / Mn = 1.2) in acetone 100m
pyridine, 2.0 g of pyridine was added, and 1.3 g of acetic anhydride was added.
g was added and reacted at 50 ° C. for 3 hours with stirring. The reaction solution was poured into 1 L of ion-exchanged water with vigorous stirring to precipitate a white resin. After drying the obtained resin under reduced pressure, 12.2 g of resin (39) of the present invention was obtained.
When the molecular weight was measured by GPC, the weight average (M
w: 11,400 in terms of polystyrene; dispersity (Mw)
/ Mn) was 1.2. Further, when the composition ratio was calculated by NMR measurement, the molar ratio was x / y (4-hydroxystyrene / 4-acetoxystyrene) = 88/12.

Synthesis Example 3 (Synthesis of Resin Example (91)) 3.8 g (0.015 mol) of 2-[(4'-hydroxyphenyl) carbonyloxy] ethyl methacrylate, 1.0 g of 2-hydroxyethyl acrylate
(0.009 mol), 0.3 g of acrylonitrile (0.
006 mol) in 30 m of 1-methoxy-2-propanol
1 and polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd .; trade name: V-65) at 70 ° C under a nitrogen stream and stirring.
g, 2-[(4'-hydroxyphenyl) carbonyloxy] ethyl methacrylate 8.8 g (0.035 mol), 2-hydroxyethyl acrylate 2.4 g
(0.021 mol), 0.7 g of acrylonitrile (0.
014 mol) of 1-methoxy-2-propanol 70 m
The solution was added dropwise over 2 hours. After 2 hours, initiator 50m
g was added, and the reaction was further performed for 2 hours. Thereafter, the temperature was raised to 90 ° C., and stirring was continued for 1 hour. After allowing the reaction solution to cool, it was poured into 1 L of ion exchanged water with vigorous stirring to precipitate a white resin. After drying the obtained resin under reduced pressure,
15.8 g of the resin (91) of the present invention was obtained. When the molecular weight was measured by GPC, the weight average (Mw: in terms of polystyrene) was 15,200, and the dispersity (Mw / Mn) was 2.2.
Met. Hereinafter, the resin of the present invention (B) was synthesized in the same manner.

(2) Acid generator 1) Synthesis of tetramethylammonium pentafluorobenzenesulfonate 25 g of pentafluorobenzenesulfonyl chloride was dissolved in 100 ml of methanol under ice cooling, and 100 g of a 25% aqueous solution of tetramethylammonium hydroxide was added thereto. Added slowly. 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, 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. To the reaction mixture was added 500 ml of water under ice-cooling, and the mixture was extracted with dichloromethane. The organic phase was washed with sodium hydrogen carbonate and water, and concentrated to obtain di (4-t-amylphenyl) iodonium sulfate. This sulfate was added to a solution of an excess amount of tetramethylammonium pentafluorobenzenesulfonate. 500 ml of water was added to this solution, and this 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.

(3) Crosslinking agent Synthesis of crosslinking agent [HM-1] 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl 20 g of benzene (Honshu Chemical Industry Co., Ltd. T
risp-PA) was added to a 10% aqueous potassium hydroxide solution, and the mixture was stirred and dissolved. Then, while stirring this solution, 3
60 ml of a 7% aqueous formalin solution was gradually added at room temperature over 1 hour. After stirring at room temperature for 6 hours, the mixture was thrown into a dilute sulfuric acid aqueous solution. The precipitate was filtered, washed sufficiently with water, and recrystallized from 30 ml of methanol to obtain 20 g of a white powder of a phenol derivative having a hydroxymethyl group [HM-1] having the following structure. The purity was 92% (liquid chromatography method).

[0139]

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Synthesis of Crosslinking Agent [MM-1] 20 g of the phenol derivative having a hydroxymethyl group [HM-1] obtained in the above synthesis example was added to 1 liter of methanol, and the mixture was heated and stirred to dissolve. Next, 1 ml of concentrated sulfuric acid was added to this solution, and the mixture was heated under reflux for 12 hours. After the completion of the reaction, the reaction solution was cooled, and 2 g of potassium carbonate was added. After sufficiently concentrating this mixture, 300 ml of ethyl acetate was added. This solution was washed with water and concentrated to dryness to obtain 22 g of a white solid of a phenol derivative having a methoxymethyl group [MM-1] having the following structure. 90 purity
% (Liquid chromatography method).

[0141]

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Further, the following phenol derivatives were synthesized in the same manner.

[0143]

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[0144]

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[0145]

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[0146] 2. Examples [Examples and Comparative Examples] (1) Coating of Resist A solution of a compound constituting the present invention described in the detailed description of the invention and a photoresist composition having a composition shown in Table 1 below was prepared. All of the compounds of component (D) are commercially available products (Aldric
h) was used. Further, as comparative examples, resist compositions were used in which the compound of the component (D) used in the present invention was not used and in which salicylic acid was used as the organic carboxylic acid instead of the component (D). Further, as a comparative example,
A resist composition using L-phenylalanine instead of the component (D) was used. After filtering each sample solution with a 0.1 μm filter, using a spin coater,
It was applied on a silicon wafer and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 0.3 μm.

[0147]

[Table 1]

The structures of CL-1 and CL-2 are shown below.

[0149]

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The organic basic compounds used in Table 1 include OE-1: 4-dimethylaminopyridine OE-2: benzimidazole OE-3: 2,4,5-triphenylimidazole OE-4: 1,4 -Diazabicyclo [5.4.0] undecene.

As the solvent, PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether is represented.

(2) Preparation of resist pattern An electron beam writer (Hitachi HL750,
Irradiation was performed using an acceleration voltage of 50 KeV). After the irradiation, each was heated for 60 seconds on a vacuum adsorption type hot plate at 110 ° C., immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The obtained pattern, by the following method, sensitivity, resolution, pattern shape,
The edge roughness was evaluated.

(2-1) Sensitivity The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope. 0.20 μm line (line: space =
The minimum irradiation energy when resolving 1: 1) was taken as the sensitivity. (2-2) Resolving power The limiting resolving power (line and space are separated and resolved) at the irradiation dose exhibiting the above sensitivity was defined as the resolving power.

(2-3) Pattern Shape The cross-sectional shape of the obtained pattern (pattern size = 0.14 μm) was observed using a scanning electron microscope. Rectangle,
The evaluation was made in three stages of slightly taper and taper. (2-4) Edge Roughness The line width was measured at arbitrary 30 points in the length direction of 50 μm in the 0.14 μm line pattern at the irradiation dose exhibiting the above sensitivity, and the variation was evaluated by 3σ. Table 2 shows the performance evaluation results.

[0155]

[Table 2]

From the results shown in Table 2, the component (D) contains at least one amino group selected from secondary to tertiary alicyclic amino groups and at least one carboxyl group in the molecule. The negative resist composition of the present invention using a compound does not contain this component, or a compound containing an organic carboxylic acid, or a comparative example using a compound containing both an acyclic amino group and a carboxyl group, It can be seen that both the resolving power and the pattern shape are excellent, and particularly the edge roughness is greatly improved.

[0157]

According to the negative resist composition of the present invention,
It is possible to provide a negative resist composition which is excellent in sensitivity, resolution and pattern shape and edge roughness.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yutaka Adekawa 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd.

Claims (5)

[Claims] (A) a compound which generates an acid upon irradiation with actinic rays or radiation; (B) an alkali-soluble resin; (C) a crosslinking agent which crosslinks with the resin of (B) by the action of an acid; and (D) a molecule. A negative resist composition comprising a compound containing therein at least one kind of amino group selected from secondary and tertiary alicyclic amino groups and at least one kind of carboxyl group. 2. The negative resist composition according to claim 1, further comprising (E) an organic basic compound. 3. The resin of the component (B) is represented by the following general formula (b):
The negative resist composition according to claim 1, which is a resin containing a repeating unit represented by the formula: Embedded image In the formula, R ₁ represents a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group or haloalkyl group. R ₂ may have a hydrogen atom or a substituent;
Represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an acyl group. R ₃ and R ₄ may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, or an optionally substituted alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group. Represents A may have a single bond, a substituent, an alkylene group, an alkenylene group, cycloalkylene group or arylene group, or -O -, - SO ₂ -,
_{-O-CO-R 5 -,} - CO-O-R 6 -, - CO-N
(R ₇ ) represents —R ₈ —. R ₅ , R ₆ , and R ₈ may be the same or different and may have a single bond, a substituent, an alkylene group, an alkenylene group, a cycloalkylene group, or an arylene group alone, or It represents a divalent group formed by at least one selected from the group consisting of an ether structure, an ester structure, an amide structure, a urethane structure and a ureide structure. R ₇ may be the same or different and represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group which may have a substituent. n represents an integer of 1 to 3. Further, a plurality of R ₂ , or a combination of R ₂ and R ₃ or R ₄ may form a ring. 4. The resin of the component (B) has the following general formula (b-
The negative resist composition according to claim 1 or 2, wherein the resin is a resin containing at least one selected from the repeating units represented by (2) and (b-3). Embedded image In the formula, R ₁ and A are respectively R _1, A of the general formula (b) synonymous. R _{101 to} R ₁₀₆ each independently represent a hydroxy group, a linear, branched, or cyclic alkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkenyl group, an aryl group, an aralkyl group, and a carboxy group. , An amino group, an N-alkylamino group, or an N-dialkylamino group. a to f each independently represent an integer of 0 to 3; 5. The method according to claim 1, wherein the actinic ray or radiation is an electron beam or X-ray.
The negative resist composition according to claim 1, wherein the composition is a line.