JP2003005355A - Negative type resist composition for electron beam or x-ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem of a performance enhancing technique in microfabrication of a semiconductor device using an electron beam or X-ray and to provide a negative type resist composition for an electron beam or X-ray satisfying such characteristics as sensitivity and resist shape when an electron beam or X-ray is used. SOLUTION: The negative type resist composition contains (A) a compound which generates an acid when irradiated with an electron beam or X-ray, (B) a resin soluble in an aqueous alkali solution and (D) at least one compound represented by a specified structure.

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 which is suitable for use in ultra-microlithography processes such as production of ultra-LSIs and high-capacity microchips and other photofabrication processes. More specifically, the present invention relates to a negative photoresist composition capable of forming a highly precise pattern using X-rays, electron beams, etc., and is particularly suitable for fine processing of semiconductor elements using high-energy rays such as electron beams. The present invention relates to a negative resist composition that can be used for. The present invention relates to a high sensitivity and high resolution electron beam or X-ray negative resist composition.

[0002]

2. Description of the Related Art In recent years, various electron beam negative resist compositions have been proposed (JP-A-5-249676,
JP-A-9-34112, JP-A-10-90901
No. The pattern formation process that uses an electron beam as a light source is said to be capable of higher resolution than a process that uses radiation such as i-rays and excimer lasers as a light source. Next-generation 256 mega, 1 giga, 4 giga, etc. Its application is being considered for the manufacture of the ultra-high integration semiconductor device. However, pattern formation using an electron beam is different from the collective exposure method in pattern formation using a light source such as an i-line or an excimer laser, and a mask pattern is drawn. The larger the number, the longer the exposure (drawing) time, and the more time it takes to form a pattern, which is a drawback. Therefore, 256 mega,
As the degree of integration increases dramatically, from 1 giga to 4 giga, the pattern formation time will increase dramatically.
There is concern that the throughput will be significantly inferior. From the above, in order to put a pattern forming process using an electron beam into practical use, it is essential to shorten the exposure time as much as possible, and for that purpose, it is necessary to increase the sensitivity of the resist composition as a pattern forming material. It was strongly desired. However, with the increase in sensitivity, there is a problem that the profile deteriorates. Therefore, it has been a problem to achieve both high sensitivity and a rectangular profile.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the problem of the performance improving technique in the fine processing of semiconductor devices using electron beams or X-rays. On the other hand, it is to provide a negative resist composition for electron beam or X-ray which satisfies the sensitivity and the characteristics of the resist shape.

[0004]

Means for Solving the Problems As a result of intensive studies by the inventors of the present invention, it was found that the object of the present invention can be achieved by adding the compound (D). Heading, arrived at the present invention. That is, the present invention has the following configuration.

(1) (A) A compound that generates an acid upon irradiation with an electron beam or X-ray, (B) a resin soluble in an alkaline aqueous solution (D) represented by the following general formulas (1) to (8) Electron beam or X containing at least one compound
Negative resist composition for lines.

[Chemical 2]

In the above general formulas (1) to (8), R ₁₁
Is a hydrogen atom or a primary, secondary or tertiary aliphatic amine substituent, mixed amine substituent, aromatic amine substituent, heterocyclic amine substituent, amide group, imide group, Ester group, halogen group, halogen-substituted alkyl group, halogen-substituted aryl group, hydroxyl group, carboxyl group, thiol group, cyano group, nitro group, formyl group, sulfonyl group, sulfonamide group, acyl group, aroyl group, alkyl group , An alkyloxy group, an alkenyloxy group, a heterocyclic group, an aryl group, an alkenyl group, and an aralkyl group. R ₁₂ represents a hydrogen atom, an aromatic amine substituent, a heterocyclic amine substituent, a halogen-substituted alkyl group, a halogen-substituted aryl group, a hydroxyl group, an acyl group, an aroyl group, an alkyl group, an alkyloxy group, an alkenyloxy group, A heterocyclic group, an aryl group, an alkenyl group, an aralkyl group, an ester group, and a carbonic acid ester group are shown.

(2) Further, by the action of (C) acid, (B)
The negative resist composition for electron beams or X-rays according to (1) above, which contains a compound that undergoes an addition reaction with a resin. (3) The negative resist composition for electron beam or X-ray according to the above (1) or (2), which further comprises (E) a nitrogen-containing basic compound. (4) The negative resist composition for electron beam or X-ray according to any one of (1) to (3) above, which further contains (F) a surfactant.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention are described in detail below. [1] (B) Resin soluble in alkaline aqueous solution (hereinafter, also referred to as alkali-soluble resin) In the present invention, the alkali-soluble resin is a phenol novolac resin, a polyvinylphenol resin, or a vinyl disclosed in negative chemically amplified resists. A copolymer having a structural unit derived from phenol, and a resin obtained by partially protecting or modifying a polyvinylphenol resin,
Polymers having a phenol skeleton can be widely used. The resin as the component (B) is preferably a resin containing the repeating unit of the general formula (a).

[0009]

[Chemical 3]

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 represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, an aryl group, an aralkyl group, or an acyl group. R ₃ and R ₄
Are the same or different and represent 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, a divalent alkylene group, an alkenylene group, a cycloalkylene group, or an 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 each may have a single bond or a substituent, which may be an alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or these groups. It represents a divalent group formed by a combination of 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. R _{7 s} may be the same or different and each represents a hydrogen atom or an alkyl group, cycloalkyl group, aralkyl group or aryl group which may have a substituent. n represents an integer of 1 to 3. A plurality of R ₂ , or R ₂ and R ₃ or R ₄ may combine to form a ring. More preferred is a phenol resin containing a repeating structural unit represented by the above general formula (a).

The alkyl group represented by 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 or an n-butyl group. , Sec-butyl group, hexyl group, 2-ethylhexyl group,
An octyl group can be preferably mentioned. R ₂ ~
The cycloalkyl group of R ₄ and R ₇ may be monocyclic or polycyclic. As the monocyclic type, for example, a cyclopropyl group, a cyclopentyl group and a cyclohexyl group having 3 to 8 carbon atoms can be preferably mentioned. Preferable 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 of R ₃ and R ₄ is, for example, an alkenyl group having 2 to 8 carbon atoms, and specifically, a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group can be preferably exemplified.

The aryl group represented by R _{2 to} R ₄ and R ₇ is, for example, an aryl group having 6 to 15 carbon atoms, specifically, phenyl group, tolyl group, dimethylphenyl group, 2,
Preferred examples include 4,6-trimethylphenyl group, naphthyl group and anthryl group. R ₂ ~R _4, R ₇
The aralkyl group of is an aralkyl group having a carbon number of 7 to 12, and specific examples thereof 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 group, chloroethyl group, chloropropyl group, chlorobutyl group, bromomethyl group, bromoethyl group and the like. It can be preferably mentioned.

The acyl group of R ₂ has, for example, 1 carbon atom.
~ 8 acyl groups, specifically, a formyl group,
Preferred examples thereof include an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, a benzoyl group and the like.

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

The cycloalkylene group of A, R ₅ , R ₆ and R ₈ preferably has a carbon number of 5 to 8 such as a cyclopentylene group and a cyclohexylene group which may have a substituent.
There are individual ones. The arylene group for A, R ₅ , R ₆ and R ₈ is preferably a phenylene group, a tolylene group,
Examples thereof include those having 6 to 12 carbon atoms such as a naphthylene group.

Substituents substituted with these groups include
Those having active hydrogen such as amino group, amide group, ureido group, urethane group, hydroxyl group, and carboxyl group, and halogen atoms (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 and the like), cyano group, nitro group and the like. Those having active hydrogen such as amino group, hydroxyl group and carboxyl group are particularly 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 resin of the present invention (B) may be a resin consisting only of the repeating structural unit represented by the general formula (a), but for the purpose of further improving the performance of the negative resist of the present invention, Other polymerizable monomers may be copolymerized.

Copolymerizable monomers that can be used include those shown below. For example, addition-polymerizable unsaturated bonds selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, etc. other than the above It is a compound having one.

Specifically, for example, acrylic acid esters such as alkyl (wherein the alkyl group has 1 to 1 carbon atoms).
0 acrylate) (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 (eg phenyl acrylate etc.);

Methacrylic acid esters, for example, alkyl (alkyl groups preferably having 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 methacrylate (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.);

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

Methacrylamides such as methacrylamide and N-alkylmethacrylamide (wherein the alkyl group has 1 to 10 carbon atoms, such as methyl group, ethyl group, t-butyl group, ethylhexyl group and hydroxyethyl group). Group, cyclohexyl group, etc.), N
-Aryl methacrylamide (an aryl group includes a phenyl group, etc.), N, N-dialkyl methacrylamide (an alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N, N-diaryl. Methacrylamide (such as a phenyl group as an aryl group), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide, etc .;
Allyl compounds, such as allyl esters (eg, 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 ether (eg 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 barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate. , Vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl-β-
Phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .;

Styrenes such as styrene, alkylstyrenes (eg methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethyl). Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene). , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromstyrene, dibromostyrene, iodostyrene, fluoros Ren, trifluoromethyl styrene, 2
-Brom-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), carboxystyrene;

Crotonic acid esters, for example, alkyl crotonic acid (for example, butyl crotonic acid, hexyl crotonic acid, glycerin monocrotonate, etc.); Dialkyl itaconic acids (for example, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc.) ); Dialkyl esters of maleic acid or fumaric acid (eg,
Dimethyl maleate, dibutyl fumarate, etc.), maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleironitrile and the like. In addition, any addition-polymerizable unsaturated compound that is generally copolymerizable may be used.

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

Specific examples of the resin having the repeating structural unit represented by the general formula (a) are shown below, but the invention is not limited thereto.

[0032]

[Chemical 4]

[0033]

[Chemical 5]

[0034]

[Chemical 6]

[0035]

[Chemical 7]

[0036]

[Chemical 8]

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

[0041]

[Chemical 13]

[0042]

[Chemical 14]

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

The resin having a repeating structural unit represented by the above (B), preferably the general formula (a), has a weight average molecular weight of 1,000 to 200,000, more preferably 3,000 to 50. Used in the range of 1,000. The molecular weight distribution is 1-10, preferably 1-3,
More preferably, those having a range of 1 to 1.5 are used.
The smaller the molecular weight distribution, the resolution, resist shape,
Also, the side wall of the resist pattern is smooth, and the roughness is excellent. The content of the repeating structural unit represented by the general formula (a) is 5 to 100 mol%, preferably 10 to 90 mol% based on the entire resin.

The alkali-soluble resin containing the structural unit represented by the general formula (a) used in the present invention is Macrom
olecules (1995), 28 (11), 3787-3789, Polym. Bull.
(Berlin) (1990), 24 (4), 385-389, JP-A-8-2863.
It can be synthesized by the method described in 75. That is, the target 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 by the polystyrene conversion value of gel permeation chromatography. The alkali dissolution rate of the alkali-soluble resin is preferably 20Å / sec or more as measured by 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.). It is particularly preferably 200 Å / sec or more. In the present invention, the alkali-soluble resin having the repeating unit represented by the general formula (a) may be used alone, or may be used in combination with another alkali-soluble resin. Regarding the usage ratio, up to 100 parts by weight of other alkali-soluble resin can be used together with 100 parts by weight of the alkali-soluble resin having the repeating unit represented by the general formula (a). Examples of alkali-soluble resins that can be used in combination are shown below. For example, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, styrene-maleic anhydride copolymer, carboxyl group-containing methacrylic resin and derivatives thereof can be mentioned, but not limited thereto.

The resin (B) is used in an amount of 30 to 95% by weight, preferably 40 to 90% by weight, more preferably 50 to 80% by weight, based on the total solid content of the composition.

[2] A compound (photoacid generator) which generates an acid upon irradiation with an electron beam or an X-ray, which is the component (A), will be described. As the photo-acid generator used in the present invention, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization,
Known light used for photo-decoloring agents of dyes, photo-discoloring agents, micro resists, etc. (ultraviolet rays of 400 to 200 nm, deep ultraviolet rays, particularly preferably g-line, h-line, i-line)
Ray, KrF excimer laser light), ArF excimer laser light, an electron beam, an X-ray, a molecular beam or an ion beam to generate an acid, and a mixture thereof can be appropriately selected and used.

Other photoacid generators used in the present invention include, for example, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and other onium salts,
Organic halogen compounds, organic metal / organic halides, o
Examples thereof include a photoacid generator having a nitrobenzyl-type protecting group, a compound represented by iminosulfonate and the like, which photolyzes to generate a sulfonic acid, a disulfone compound, a diazoketosulfone, a diazodisulfone compound.
Further, a group in which an acid-generating group or a compound is introduced into the main chain or side chain of a polymer can be used.

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

Among the above photo-acid generators, one effectively used is a photo-acid generator whose anion has a fluorine atom. For example, the cation part is composed of iodonium or sulfonium and the anion part is R ^F
A photo-acid generator selected from a sulfonate composed of an anion represented by SO ₃ ^— (wherein, R ^F represents a C 1-10 fluorine-substituted alkyl group) is used. . The fluorine-substituted alkyl group represented by R ^F may be linear, branched or cyclic. Preferred R ^F is represented by CF ₃ (CF ₂ ) y, and y is 0.
It is a fluorine-substituted linear alkyl group which is an integer of -9.
The cation part of the photoacid generator is preferably represented by the following general formulas (I) to (III).

[0052]

[Chemical 15]

In the above general formulas (I) to (III), R ₁
To R ₃₇ are the same or different and each is 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.
It represents a -R ₃₈ group. R ₃₈ represents a linear, branched or cyclic alkyl group or aryl group. R ₁ ~ R ₁₅ , R ₁₆ ~
Two or more of R ₂₇ and R _{28 to} R ₃₇ are combined to form a ring containing one or more selected from a single bond, a carbon atom, an oxygen atom, a sulfur atom and a nitrogen atom. Good.

In the general formulas (I) to (III), R _{1 to} R
_As the linear or branched alkyl group of ₃₈ , a carbon number such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, or a t-butyl group, which may have a substituent. One to four can be mentioned. Examples of the cyclic alkyl group include those having a carbon number of 3 to 8, such as cyclopropyl group, cyclopentyl group and cyclohexyl group, which may have a substituent. Examples of the linear or branched alkoxy group for R _{1 to} R ₃₇ include a methoxy group, an ethoxy group,
Examples thereof include those having 1 to 4 carbon atoms such as hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group. Examples of the cyclic alkoxy group include a cyclopentyloxy group, for example, 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. Examples of the aryl group of 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. These substituents preferably have 1 to 1 carbon atoms.
4 alkoxy groups, halogen atom (fluorine atom, chlorine atom, iodine atom), aryl group having 6 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, cyano group, hydroxy group, carboxy group, alkoxycarbonyl Group, nitro group and the like.

Further, R _{1 to} R ₁₅ , R _{16 to} R ₂₇ , R _{28 to} R
Of ₃₇ , one or two selected from a single bond, carbon, oxygen, sulfur, and nitrogen, which is formed by combining two or more.
Examples of the ring containing at least one kind include a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, and a pyrrole ring. Specific examples (A1-1) to (A1-1) of the photo-acid generator that can be used in the present invention
1-64) is shown below.

[0057]

[Chemical 16]

[0058]

[Chemical 17]

[0059]

[Chemical 18]

[0060]

[Chemical 19]

[0061]

[Chemical 20]

[0062]

[Chemical 21]

[0063]

[Chemical formula 22]

[0064]

[Chemical formula 23]

Further, the following photoacid generators can also be preferably used. (1) The following general formula (P
AG1) or an oxazole derivative represented by the general formula (P
An S-triazine derivative represented by AG2).

[0066]

[Chemical formula 24]

In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y)
₃ is shown. Y represents a chlorine atom or a bromine atom. The following compounds can be specifically mentioned, but the compounds are not limited to these.

[0068]

[Chemical 25]

[0069]

[Chemical formula 26]

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

[0071]

[Chemical 27]

In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ ,
^R204 and ^R205 each independently represent a substituted or unsubstituted alkyl group or aryl group. Z ⁻ represents a counter anion, for example, BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , Si.
Condensed polynuclear aromatic sulfonate anion such as perfluoroalkane sulfonate anion such as F ₆ ²⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , pentafluorobenzene sulfonate anion, naphthalene-1-sulfonate anion, anthraquinone sulfonate Examples thereof include anion dyes and sulfonic acid group-containing dyes, but are not limited thereto.

Two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded to each other via a single bond or a substituent. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0074]

[Chemical 28]

[0075]

[Chemical 29]

[0076]

[Chemical 30]

[0077]

[Chemical 31]

[0078]

[Chemical 32]

[0079]

[Chemical 33]

[0080]

[Chemical 34]

[0081]

[Chemical 35]

The above-mentioned onium salts represented by the general formulas (PAG3) and (PAG4) are known, and are described in, for example, US Pat.
It can be synthesized by the methods described in 2,807,648 and 4,247,473, and JP-A-53-101,331.

(3) A disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6).

[0084]

[Chemical 36]

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0086]

[Chemical 37]

[0087]

[Chemical 38]

[0088]

[Chemical Formula 39]

[0089]

[Chemical 40]

[0090]

[Chemical 41]

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

[0092]

[Chemical 42]

Here, R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0094]

[Chemical 43]

The amount of these photo-acid generators added is usually in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, and more preferably, based on the solid content in the composition. Is used in the range of 0.1 to 10% by weight.
If the addition amount of the photo-acid generator is less than 0.001% by weight, the sensitivity will be low, and if the addition amount is more than 40% by weight, the light absorption of the resist will be too high, and the deterioration of the profile or the process (especially baking). ) It is not preferable because the margin becomes narrow.

[3] The compound of the present invention (C) which undergoes an addition reaction with the resin (B) by the action of an acid. In the present invention, the compound which undergoes an addition reaction with a resin by the action of an acid together with an alkali-soluble resin and an acid generator ( Hereinafter, the component (C) or the compound (C) will be used. Here, a known acid crosslinking agent can be effectively used. Preferably, one or more hydroxymethyl groups, alkoxymethyl groups, acyloxymethyl groups, or alkoxymethyl ether groups, more preferably 2 to 16 groups,
More preferably, a compound or resin having 4 to 10 units,
Alternatively, it is an epoxy compound.

More preferably, alkoxymethylated, acyloxymethylated melamine compounds or resins, alkoxymethylated, acyloxymethylated urea compounds or resins, hydroxymethylated, alkoxymethylated, acyloxymethylated phenol compounds or resins, and alkoxymethyl. Examples thereof include etherified phenol compounds and resins.

(I) As the above-mentioned phenol compound,
Preferably, it has a molecular weight of 1200 or less, contains 3 to 5 benzene rings in the molecule, and further has two or more hydroxymethyl groups or alkoxymethyl groups in total, and has at least one of the hydroxymethyl groups and alkoxymethyl groups. Examples thereof include a phenol derivative formed by concentrating on the benzene ring or by allocating and distributing the benzene ring. By using such a phenol derivative, the effect 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 group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group,
A sec-butoxymethyl group and a t-butoxymethyl group 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 preferable ones are listed below.

[0099]

[Chemical 44]

[0100]

[Chemical formula 45]

[0101]

[Chemical formula 46]

[0102]

[Chemical 47]

[0103]

[Chemical 48]

[0104]

[Chemical 49]

[0105]

[Chemical 50]

[0106]

[Chemical 51]

(In the formula, L ^{1 to} L ⁸ may be the same or different and each represents a hydroxymethyl group, a methoxymethyl group or an ethoxymethyl group.) The phenol derivative having a hydroxymethyl group corresponds to It can be obtained by reacting a phenol compound having no hydroxymethyl group (a compound in which L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde under a base catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, JP-A-6-282067 and JP-A-7-64
It can be synthesized by the method described in No. 285 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 under an acid catalyst. At this time, in order to prevent resinification and gelation, it is preferable to carry out the reaction at a temperature of 100 ° C. or lower. Specifically, it can be synthesized by the method described in European Patent EP632003A1 and the like. The phenol derivative having a hydroxymethyl group or an alkoxymethyl group thus synthesized is preferable from the viewpoint of stability during storage, but the 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, which are concentrated in any benzene ring or are distributed by being distributed may be used alone or in combination with two kinds. The above may be used in combination.

(Ii) N-hydroxymethyl group, N-
As a compound having an alkoxymethyl group or an N-acyloxymethyl group, European Patent Publication (hereinafter, referred to as “E
No. 0,133,216, West German Patent Nos. 3,634,671 and 3,711,264, and the monomer and oligomer-melamine-formaldehyde condensate, and Examples thereof include urea-formaldehyde condensate and benzoguanamine-formaldehyde condensate disclosed in the alkoxy-substituted compounds disclosed in EP-A No. 212212. More preferable examples include, for example, melamine-formaldehyde derivatives having at least two free N-hydroxymethyl groups, N-alkoxymethyl groups, or N-acyloxymethyl groups, and among them, N-alkoxymethyl derivatives are particularly preferable. .

(Iii) Examples of epoxy compounds include monomer, dimer, oligomer and polymer epoxy compounds containing one or more epoxy groups. Examples thereof include a reaction product of bisphenol A and epichlorohydrin, a reaction product of low molecular weight phenol-formaldehyde resin and epichlorohydrin, and the like. In addition, US Pat. No. 4,026,705,
The epoxy resin described and used in British Patent 1,539,192 can be mentioned.

The component (C) is used in an amount of generally 3 to 65% by weight, preferably 5 to 50% by weight, based on the total solid content of the resist composition. If the addition amount of the component (C) is less than 3% by weight, the residual film rate is lowered, and if it exceeds 65% by weight, the resolution is lowered, and further it is not preferable in terms of stability during storage of the resist solution. .

In the present invention, the above-mentioned (i) phenol compound is added to the above-mentioned other crosslinking agent (ii), for example,
(Iii) can also be used in combination. The ratio of other cross-linking agent that can be used in combination with the above phenol derivative is 100/0 to 20/80, preferably 90/10 to 4 in terms of molar ratio.
It is 0/60, more preferably 80/20 to 50/50.

[4] (D) Compound Represented by General Formulas (1) to (8) The resist composition of the present invention comprises (D) the general formula (1) to
It contains the compound represented by (8). As a result, the resolution becomes high and the obtained resist pattern has a good profile.

R ₁₁ in the above general formulas (1) to (8) is a hydrogen atom, a primary, secondary, or tertiary aliphatic amine substituent, a hybrid amine substituent, an aromatic amine. Group substituent, heterocyclic amine group substituent, amide group, imide group, ester group, halogen group, halogen substituted alkyl group, halogen substituted aryl group, hydroxyl group, carboxyl group, thiol group, cyano group, nitro group, formyl Examples thereof include groups, sulfonyl groups, sulfonamide groups, acyl groups, aroyl groups, alkyl groups, alkyloxy groups, alkenyloxy groups, heterocyclic groups, aryl groups, alkenyl groups, and aralkyl groups.

When R ₁₁ represents an aromatic amine substituent, a heterocyclic amine substituent, an alkyl group, a heterocyclic group, an aryl group, or an alkenyl group, R ₁₁ is a general formula via a linking group. It may be bonded to the skeletons of (1) to (8).
Examples of such a linking group include a divalent linking group of an aromatic amine substituent, a heterocyclic amine substituent, an alkyl group, a heterocyclic group, and an aryl group, or a double bond, 3
Heavy bond, oxygen atom, nitrogen atom, sulfur atom, -C (= O)
-Or groups in which two or more of these are combined are included. As such an example, R ₁₁ :-( phenylene group)-(divalent heterocyclic amine substituent)-(phenyl group) can be mentioned. Such divalent linking groups further include primary, secondary, and tertiary aliphatic amine substituents, hybrid amine substituents, amide groups, imide groups, ester groups, halogen groups, and hydroxyl groups. , Carboxyl group, thiol group, cyano group, nitro group, formyl group, sulfonyl group,
A sulfonamide group, an acyl group, an aroyl group, an alkyl group, an aryl group, —COO ⁻ , or —SO ₃ ^— may be substituted. However, the total number of carbon atoms in the substituent R ₁₁ including the linked substituent and the further substituent is 70 or less.

Specifically, as a primary aliphatic amine substituent, amino group, methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n
-Butylamino group, isobutylamino group, sec-butylamino group, tert-butylamino group, pentylamino group, tert-amylamino group, cyclopentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, Nonylamino group,
Decylamino group, dodecylamino group, cetylamino group,
Examples include methylenediamino group, ethylenediamino group, tetraethylenepentamino group, and the like. As secondary aliphatic amine substituents, dimethylamino group, diethylamino group,
Di-n-propylamino group, diisopropylamino group,
Di-n-butylamino group, diisobutylamino group, di-
sec-butylamino group, dipentylamino group, dicyclopentylamino group, dicyclohexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, dicetylamino group, etc. As the aliphatic amine substituent, a trimethylamino group, a triethylamino group, a tri-n-propylamino group, a triisopropylamino group, a tri-n-butylamino group, a triisobutylamino group, a tri-sec-butylamino group, Examples thereof include a tripentylamino group, a tricyclopentylamino group, a tricyclohexylamino group, a triheptylamino group, a trioctylamino group, a trinonylamino group, a tridecylamino group, a tridodecylamino group and a tricetylamino group. Examples of the mixed amine substituents include methylethylamino group, benzylamino group, phenethylamino group and benzylmethylamino group.

Specific examples of the aromatic amine and heterocyclic amine substituents (substituted on a carbon atom or a nitrogen atom) include aniline derivatives (eg, aniline, N-methylaniline, N-ethylaniline, N, N'-dimethylaniline, N, N'-diethylaniline, N-propylaniline, 2-methylaniline, 3-methylaniline, 4
-Methylaniline, 2,6-dinitroaniline, etc.), diphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivative (for example, pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4
-Dimethylpyrrole, 2,4-dimethylpyrrole, 2,
5-dimethylpyrrole etc.), oxazole derivative (eg oxazole, isoxazole etc.), thiazole derivative (eg thiazole, isothiazole etc.), imidazole derivative (eg imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole etc.) ,
Thiadiazole, triazole, benzoxazole,
Benzotriazole, pyrazole derivatives, furazan derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1
-Pyrroline etc.), pyrrolidine derivative (e.g. pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.), imidazoline derivative, imidazolidine derivative, pyridine derivative (e.g. pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine,
Phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4. -Phenyl pyridine, 2-
(1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivative, pyrimidine derivative, pyrazine derivative, pyrazolone derivative, pyrazolidine derivative, piperidine derivative, piperazine derivative, morpholine derivative, indole derivative, isoindole derivative, 1H- Indazole derivative, indoline derivative, guanidine derivative, quinoline derivative (eg, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoxaline derivative, phthalazine derivative, purine derivative, pteridine derivative, carbazole derivative, phenanthridine derivative Derivative, acridine derivative, phenazine derivative, phenanthroline derivative, adenine derivative, adenosine derivative, guanine derivative, Anoshin derivatives, uracil derivatives, uridine derivatives, and the like.

Examples of the amide group include a carbamoyl group and N-
Examples include methylcarbamoyl group, N, N-dimethylcarbamoyl group, acetamide group, N-methylacetamide group, propionamide group, benzamide group, methacrylamide group, decanylamide group, laurylamide group, palmitylamide group, stearylamide group, etc. To be done. Examples of the imido group include a phthalimido group, a succinimido group, and a maleimido group. Examples of the ester group include carbamate group, methyl ester group, ethyl ester group, propyl ester group, isopropyl ester group, n-butyl ester group, sec-butyl ester group, tert-butyl ester group, pentyl ester group, isopentyl ester group. , Tert-amyl ester group, hexyl ester group, heptyl ester group, octyl ester group, cyclopentyl ester group, cyclohexyl ester group,
Cycloheptyl ester group, norbornyl ester group,
Examples thereof include an adamantyl ester group.

As the halogen-substituted alkyl group, a trifluoromethyl group, a 1,1,1-trifluoroethyl group,
1,1,1-Trichloroethyl group, nonafluorobutyl group and the like are shown. As the halogen-substituted aryl group,
Fluorobenzene group, chlorobenzene group, 1, 2, 3,
Examples include 4,5-pentafluorobenzene group and the like.

Examples of the alkyloxy group and alkenyloxy group are methoxy group, ethoxy group, propyloxy group,
Isopropyloxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, tert-amyloxy group, hexyloxy group, heptyloxy group, octyloxy group,
Examples thereof include a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a norbornyloxy group, an adamantyloxy group, an acryloxy group and a methacryloxy group. As the heterocyclic group, thiophene,
Furan, tetrahydrofuran, morpholine, pyran, tetrahydropyran, dioxane, thiocarbazole, xanthene group, and thioxanthene group are exemplified.

As the alkyl group, those having 1 to 20 carbon atoms are preferable, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Pentyl group, isopentyl group, tert-amyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group , Decanyl group, lauryl group, palmityl group, stearyl group and the like.

The aryl group is preferably one having 6 to 20 carbon atoms, specifically, a phenyl group, a naphthyl group,
Biphenyl group, phenanthrenyl group, anthranyl group,
Fluorenyl group, pyrene group and the like, and alkoxyphenyl groups such as p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group and m-tert-butoxyphenyl group. , 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group,
Alkylphenyl group such as 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group, alkylnaphthyl group such as methylnaphthyl group and ethylnaphthyl group, alkoxynaphthyl group such as methoxynaphthyl group and ethoxynaphthyl group, dimethyl Examples thereof include dialkylnaphthyl groups such as naphthyl group and diethylnaphthyl group, dialkoxynaphthyl groups such as dimethoxynaphthyl group and diethoxynaphthyl group.

The alkenyl group preferably has 2 to 10 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group and a cyclohexenyl group. The aralkyl group is preferably one having 7 to 15 carbon atoms, specifically, a benzyl group,
Examples thereof include a phenylethyl group and a phenethyl group.

R ₁₂ is a hydrogen atom, an aromatic amine substituent, a heterocyclic amine substituent, a halogen-substituted alkyl group, a halogen-substituted aryl group, a hydroxyl group, an acyl group, an aroyl group, an alkyl group, an alkyloxy group, Examples thereof include an alkenyloxy group, a heterocyclic group, an aryl group, an alkenyl group, an aralkyl group, an ester group and a carbonic acid ester.

Further, when R ₁₂ represents an aromatic amine substituent, a heterocyclic amine substituent, an alkyl group, a heterocyclic group, an aryl group or an alkenyl group, R ₁₂ is a general formula via a linking group. It may be bonded to the skeletons of (1) to (9).
Examples of such a linking group include a divalent linking group of an aromatic amine substituent, a heterocyclic amine substituent, an alkyl group, a heterocyclic group, and an aryl group, or a double bond, 3
Heavy bond, oxygen atom, nitrogen atom, sulfur atom, -C (= O)
-Or groups in which two or more of these are combined are included. As such an example, R ₁₂ :-( phenylene group)-(divalent heterocyclic amine substituent)-(phenyl group) can be mentioned. Such divalent linking groups further include primary, secondary, and tertiary aliphatic amine substituents, hybrid amine substituents, amide groups, imide groups, ester groups, halogen groups, and hydroxyl groups. , Carboxyl group, thiol group, cyano group, nitro group, formyl group, sulfonyl group,
A sulfonamide group, an acyl group, an aroyl group, an alkyl group, an aryl group, —COO ⁻ , or —SO ₃ ^— may be substituted. However, the total number of carbon atoms in the substituent R ₁₂ including the linked substituent and the further substituent is 70 or less.

Specific examples of the aromatic amine and heterocyclic amine substituents (substituted on the carbon atom or the nitrogen atom) include aniline derivatives (eg, aniline, N-methylaniline, N-ethylaniline, N, N'-dimethylaniline, N, N'-diethylaniline, N-propylaniline, 2-methylaniline, 3-methylaniline, 4
-Methylaniline, 2,6-dinitroaniline, etc.), diphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g. pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-
Dimethylpyrrole, 2,5-dimethylpyrrole, etc.), oxazole derivative (eg, oxazole, isoxazole, etc.), thiazole derivative (eg, thiazole, isothiazole, etc.), imidazole derivative (eg, imidazole, 4-methylimidazole, 4-methyl-2) -Phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-
1-pyrroline etc.), pyrrolidine derivative (eg virolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.), imidazoline derivative, imidazolidine derivative, pyridine derivative (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine) , 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine,
Phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1-methyl-4. -Phenyl pyridine, 2-
(1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivative, pyrimidine derivative, pyrazine derivative, pyrazolone derivative, pyrazolidine derivative, piperidine derivative, piperazine derivative, morpholine derivative, indole derivative, isoindole derivative, 1H- Indazole derivative, indoline derivative, guanidine derivative, quinoline derivative (eg, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivative, cinnoline derivative, quinazoline derivative, quinoxaline derivative, phthalazine derivative, purine derivative, pteridine derivative, carbazole derivative, phenanthridine derivative Derivative, acridine derivative, phenazine derivative, phenanthroline derivative, adenine derivative, adenosine derivative, guanine derivative, Anoshin derivatives, uracil derivatives, uridine derivatives, pyridinium derivatives, and the like.

As the halogen-substituted alkyl group, trifluoromethyl group, 1,1,1-trifluoroethyl group,
Examples include 1,1,1-trichloroethyl group and nonafluorobutyl group. As the halogen-substituted aryl group,
Fluorobenzene group, chlorobenzene group, 1, 2, 3,
Examples include 4,5-pentafluorobenzene group and the like.

Examples of the alkyloxy group and alkenyloxy group include methoxy group, ethoxy group, propyloxy group,
Isopropyloxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, tert-amyloxy group, hexyloxy group, heptyloxy group, octyloxy group,
Examples thereof include a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a norbornyloxy group, an adamantyloxy group, an acryloxy group and a methacryloxy group. As the heterocyclic group, thiophene,
Furan, tetrahydrofuran, morpholine, pyran, tetrahydropyran, dioxane, thiocarbazole, xanthene group, and thioxanthene group are exemplified.

The alkyl group is preferably one having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Pentyl group, isopentyl group, tert-amyl group, hexyl group, heptyl group, octyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclopropylmethyl group, 4-methylcyclohexyl group, cyclohexylmethyl group, norbornyl group, adamantyl group , Decanyl group, lauryl group, palmityl group, stearyl group and the like.

The aryl group is preferably one having 6 to 20 carbon atoms, specifically, a phenyl group, a naphthyl group,
Biphenyl group, phenanthrenyl group, anthranyl group,
Fluorenyl group, pyrene group and the like, and alkoxyphenyl groups such as p-methoxyphenyl group, m-methoxyphenyl group, o-methoxyphenyl group, ethoxyphenyl group, p-tert-butoxyphenyl group and m-tert-butoxyphenyl group. , 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, ethylphenyl group,
Alkylphenyl group such as 4-tert-butylphenyl group, 4-butylphenyl group and dimethylphenyl group, alkylnaphthyl group such as methylnaphthyl group and ethylnaphthyl group, alkoxynaphthyl group such as methoxynaphthyl group and ethoxynaphthyl group, dimethyl Examples thereof include dialkylnaphthyl groups such as naphthyl group and diethylnaphthyl group, dialkoxynaphthyl groups such as dimethoxynaphthyl group and diethoxynaphthyl group.

The alkenyl group preferably has 2 to 10 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group and a cyclohexenyl group. The aralkyl group is preferably one having 7 to 15 carbon atoms, specifically, a benzyl group,
Examples thereof include a phenylethyl group and a phenethyl group. As the ester group, a methyl ester group, an ethyl ester group, an isopropyl ester group, an n-propyl ester group, a t-butyl ester group, an n-butyl ester group, s
Examples include ec-butyl ester group, pentyl ester group, t-pentyl ester group, isopentyl group, cyclohexyl ester group and the like. As the carbonic acid ester group, a methyl carbonic acid ester group, an ethyl carbonic acid ester group, an isopropyl carbonic acid ester group, an n-propyl carbonic acid ester group, t
-Butyl carbonate ester group, n-butyl carbonate group,
Examples thereof include a cyclohexyl carbonate group, a vinylmethyl carbonate group, a fluorenylmethyl carbonate group and the like.

In the compounds represented by the general formulas (5) to (8)
Examples of the counter anion include OH^-, MeO^-, E
tO^-, N-BuO^-, T-BuO^-, I-PrO^-, TsO^-,
Cl^-, Br^-, I^-, I₃ ^-, CH₃COO^-, CF₃COO
^-, C_FourF₉COO^-, CH₃SO ₃ ^-, CF₃SO₃ ^-, C_FourF₉
SO₃ ^-, ClO_Four ^-, BF_Four ^-, HSO_Four ^-, SO_Four ^2-, Citra
te, etc. However, Ts is the following structure
Is.

[0133]

[Chemical 52]

Of the above, the counter anion in the compounds represented by the general formulas (5) to (8) is preferably O.
H ⁻ , MeO ⁻ , TsO ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , CH ₃ C
OO ⁻ , CH ₃ SO ₃ ⁻ , and BF ₄ ⁻ can be mentioned.

Specific examples of the compounds represented by the above general formulas (1) to (8) are shown below, but the invention is not limited thereto.

[0136]

[Chemical 53]

[0137]

[Chemical 54]

[0138]

[Chemical 55]

[0139]

[Chemical 56]

[0140]

[Chemical 57]

Commercially available compounds can be used as the compounds represented by the above general formulas (1) to (8). For example, The
SynTec GmbH, SYNTHON AcMaRi Chemie GmbH & Co.KG.,
It can be purchased from ALDRICH. The above general formula (1)
The amount of the compound represented by (8) to be added is usually 0.01% by weight to 30% by weight, preferably 0.02% by weight to 20% by weight, based on the solid content in the composition of the present invention. Furthermore, it is 0.05 to 15% by weight. These may be added alone or in some combinations.

[5] (E) Nitrogen-containing basic compound The resist composition of the present invention preferably contains, as the component (E), a nitrogen-containing basic compound having no acidic group. This has the effect of improving the PED stability (resist performance does not change with the lapse of time from the exposure to the subsequent heating). The preferred organic basic compound having no acidic group that can be used in the present invention is a compound having a stronger basicity than phenol. The acidic group which this organic basic compound does not have is a phenolic hydroxyl group, a sulfonic acid group, or a phosphoric acid group. A nitrogen-containing basic compound having no acidic group is particularly preferable, and examples thereof include those having the following structures.

[0143]

[Chemical 58]

R ²⁵⁰ , R ^251, and R ²⁵² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl having 1 to 6 carbon atoms. A group 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.

[0145]

[Chemical 59]

(In the formula, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R
²⁵⁶ each independently represents an alkyl group having 1 to 6 carbon atoms) A more preferable compound is a nitrogen-containing basic compound having two or more nitrogen atoms of different chemical environments in one molecule,
Particularly preferred is a compound containing both a substituted or unsubstituted amino group and a ring structure containing 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, 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 amino An alkyl morpholine etc. are mentioned. Preferred substituents are amino groups, aminoalkyl groups, alkylamino groups, aminoaryl groups, arylamino groups, alkyl groups, alkoxy groups, acyl groups, acyloxy groups, aryl groups, aryloxy groups, nitro groups,
A hydroxyl group and a cyano group.

Preferred specific examples of the nitrogen-containing basic compound include guanidine, 1,1-dimethylguanidine, 1,
1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2
-Dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-
Amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-amino Ethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) Pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-
3-methyl-1-p-tolylpyrazole, pyrazine, 2
-(Aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-
Aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] nona
5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2]
Octane, 2,4,5-triphenylimidazole, N
-Methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMET
U) and other tertiary morpholine derivatives, JP-A-11-5257
Examples thereof include hindered amines described in JP-A No. 5 (for example, those described in the above-mentioned JP-A No. 2005-2000), but are not limited thereto.

A particularly preferred specific example is 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo. [2.2.2] Octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, tertiary morpholines such as CHMETU, bis Examples thereof include hindered amines such as (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

Among them, 1,5-diazabicyclo [4.
3.0] Nona-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylene Tetramine, CHMETU, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate are preferred.

These basic compounds having no acidic group may be used alone or in combination of two or more kinds.
The amount used is usually 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content in the composition of the present invention.
% By weight. If it is less than 0.001% by weight, the effect of adding the basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed area tends to deteriorate.

[6] (F) Surfactant In the resist composition of the present invention, the component (F) is a fluorine-containing surfactant, a silicon-containing surfactant, and a surfactant containing both a fluorine atom and a silicon atom. Either, or 2
It is preferable to contain one or more species. This is effective in reducing the initial value of particles when the resist component is dissolved in the solvent.

Examples of these surfactants include those disclosed in JP-A-
62-36663, JP-A-61-226746, JP-A-61-226745,
JP 62-170950 A, JP 63-34540 A, JP 7-23016 A
5, JP 8-62834A, JP 9-54432A, JP 9-598A
8, U.S. Pat.Nos. 5,405,720, 5,360,692, 5,528,981,
5296330, 5436098, 5576143, 5294511
No. 5824451, etc., and the following commercially available surfactants can be used as they are. Examples of commercially available surfactants include F-top EF301, EF303, (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC43.
0, 431 (Sumitomo 3M Limited), Megafac F171, F1
73, F176, F189, R08 (manufactured by Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.) )) Or a fluorine-based surfactant or a silicon-based surfactant. Further, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

The content of the fluorine-based and / or silicon-based surfactant is usually 0.001% by weight to 2% by weight, preferably 0.1% by weight, based on the solid content in the composition of the present invention.
It is from 01% to 1% by weight. These surfactants may be added alone or in some combinations.

Specific examples of the surfactant that can be used in addition to the above include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether and the like. Polyoxyethylene alkyl allyl ethers such as ethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostea Sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and other sorbitan fatty acid esters, polyoxyethylene Nonionics such as polyoxyethylene sorbitan fatty acid esters such as rubitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Examples thereof include system surfactants.

The content of these other surfactants is usually 2% by weight or less, preferably 1% by weight or less, more preferably 0.01% by weight, based on the solid content in the composition of the present invention.
~ 1% by weight.

[7] Other components that may be used in the composition of the present invention The negative resist composition of the present invention may further contain a dye or the like, if necessary.

[7] -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 Industry Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170).
B), malachite green (CI42000), methylene blue (CI52015) and the like.

The composition of the present invention is dissolved in a solvent which dissolves each of the above components and coated 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-dimethyl Formamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used as simple substances. Or mixed to use.

In the process of forming a pattern on the resist film in the production of precision integrated circuit devices, etc., the negative of the present invention is formed on the substrate (eg, silicon / silicon dioxide covering, glass substrate, transparent substrate such as ITO substrate). Type photoresist composition is applied, and then an electron beam (under an accelerating voltage of 75 keV or higher) or an X-ray drawing device is used for irradiation, and a good resist pattern is formed by heating, developing, rinsing and drying. can do.

As a developer for the negative resist composition of the present invention, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine Primary amines such as diethylamine, di-
Secondary amines such as n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and primary amines such as choline. An aqueous solution of alkali such as quaternary ammonium salt, cyclic amines such as pyrrole and piperidine, and the like can be used. Furthermore, alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants may be added to the aqueous solution of the above alkalis in appropriate amounts. Of these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are more preferable.

[0161]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the contents of the present invention are not limited thereto.

(1) Alkali-Soluble Resin Synthesis Example 1 (Synthesis of Resin Example a- (29)) 4-acetoxystyrene 3.9 g (0.024 mol),
4-methoxystyrene 0.8g (0.006mol) 1
-Dissolved in 30 ml of methoxy-2-propanol, 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. Name 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. Then, 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 is dissolved in 100 mL of methanol,
% Tetramethylammonium hydroxide was added to hydrolyze the acetoxy group in the resin, which was then neutralized with an aqueous hydrochloric acid solution to precipitate a white resin. Rinse with ion-exchanged water,
After drying under reduced pressure, 11.6 g of the resin a- (29) of the present invention
Got When the molecular weight was measured by GPC, the weight average (Mw: polystyrene conversion) was 9,200, and the dispersity (M
w / Mn) was 2.2. When the composition ratio was calculated by NMR measurement, the molar ratio was x / y = 80/20.

Synthesis Example 2 (Synthesis of Resin Example a- (39)) 12.0 g of poly (4-hydroxystyrene) (Mw = 1)
0,500, Mw / Mn = 1.2) with 100 m of acetone
1 g, pyridine 2.0 g was added, and acetic anhydride 1.3
g was added, and the mixture was reacted under stirring at 50 ° C. for 3 hours. A white resin was deposited by pouring the reaction solution into 1 L of ion-exchanged water with vigorous stirring. The obtained resin was dried under reduced pressure to obtain 12.2 g of Resin a- (39) of the present invention. 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. 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 a- (91)) 3.8 g (0.015 mol) of 2-[(4'-hydroxyphenyl) carbonyloxy] ethyl methacrylate, 1.0 g of 2-hydroxyethyl acrylate
(0.009 mol), acrylonitrile 0.3 g (0.
006 mol) to 1-methoxy-2-propanol 30 m
1, 2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd .; trade name V-65) 50 m 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), acrylonitrile 0.7 g (0.
014 mol) 1-methoxy-2-propanol 70 m
1 solution was added dropwise over 2 hours. Initiator 50m after 2 hours
g was added, and the reaction was further performed for 2 hours. Then, 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 Resin a- (91) of the present invention was obtained. When the molecular weight was measured by GPC, the weight average (Mw: polystyrene conversion) was 11,000, and the dispersity (Mw / Mn) was 1.5. When the composition ratio was calculated by NMR measurement, the molar ratio was x / y / z = 60/30/10. Hereinafter, the resin of the present invention (B) was synthesized in the same manner.

(2) Synthesis of compound that undergoes addition reaction with resin Synthesis of cross-linking agent [HM-1] 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis ( 4-hydroxyphenyl) ethyl] benzene 20 g (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 7% formalin aqueous solution was gradually added at room temperature over 1 hour. After further stirring at room temperature for 6 hours, the mixture was poured into a dilute sulfuric acid aqueous solution. The precipitate was filtered, washed thoroughly with water, and then recrystallized from 30 ml of methanol to obtain 20 g of a white powder of a phenol derivative [HM-1] having a hydroxymethyl group having the following structure. The purity was 92% (liquid chromatography method).

[0166]

[Chemical 60]

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

[0168]

[Chemical formula 61]

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

[0170]

[Chemical formula 62]

Examples 1 to 18 and Comparative Examples 1 to 8 (1) Coating of Resist The components shown in Table 1 below were mixed and dissolved in the following amounts to prepare resist compositions of the present invention. . (A) Photoacid generator 0.8 g (B) Resin component 15 g (C) Compound that undergoes addition reaction with resin 5 g (D) Compound 0.1 g (E) Basic compound 0.02 g (F) Surfactant 0. 01g

Each sample solution was filtered through a 0.1 μm Teflon (registered trademark) filter, and then applied on a hexamethyldisilazane-treated silicon wafer by a spin coater, and vacuum contact type hot at 110 ° C. for 90 seconds. It was heated and dried on the plate to obtain a resist film having a film thickness of 0.3 μm.

[0173]

[Table 1]

In Table 1, resins (1), (2),
(3), (25), (27), (31), (35),
The composition (molar ratio) and molecular weight of (39), (57), (91) and (93) are as follows.

[0175] (1): Mw = 15,000, Mw / Mn = 1.1 (2): Mw = 9000, Mw / Mn = 1.2 (3): Mw = 8,000, Mw / Mn = 1.3 (25): x / y = 70: 30 Mw = 16,000, Mw / Mn = 1.5 (27): x / y = 80: 20 Mw = 9,500, Mw / Mn = 1.1 (31): x / y = 90: 10 Mw = 8,500, Mw / Mn = 1.3 (35): x / y = 75: 25 Mw = 20,000, Mw / Mn = 2.1 (39): x / y = 88: 12 Mw = 1,400, Mw / Mn = 1.2 (57): x / y = 95: 5 Mw = 5,000, Mw / Mn = 1.2 (91): x / y / z = 60: 30: 10, Mw = 11,000, Mw / M n = 1.5 (93): x / y = 85: 15 Mw = 9,300, Mw / Mn = 1.1

The ratio in the case of using two kinds of acid generators in Table 1 is a weight ratio. Further, the cross-linking agents CL-1 and CL-2
Is the following.

[0177]

[Chemical formula 63]

(2) Preparation of resist pattern An electron beam drawing device (accelerating voltage 50 Ke is applied to this resist film.
V) was used for irradiation. 110 ° C after irradiation
Heating for 60 seconds on the vacuum adsorption hot plate of
It was immersed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution 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. Sensitivity, resolution, PED
The stability and initial value of particles were evaluated as follows.

[Sensitivity] The sensitivity was defined as the minimum irradiation energy when resolving a 0.15 μm line (line: space = 1: 1). [Resolution] 0.15 μm line (line: space =
The limiting resolution (the line and space are separated and resolved) at the minimum irradiation energy when resolving 1: 1) was defined as the resolution. However, 0.15 μm line (line: space =
For those in which 1: 1) did not resolve, the limit resolution was defined as the resolution, and the irradiation energy at that time was defined as the sensitivity.

[PED stability]: 0.15 μm on a resist film formed by applying a resist composition solution and baking it.
Radiation dose that allows the line and space pattern to be formed as designed (for example, ArF excimer laser: 14 mJ / cm ² or EB: 10 μC / c
m ² ), and the wafer which has been subjected to the radiation irradiation step was left in a clean room for 2 hours. Then, after baking after irradiation with radiation, development was carried out, and the deviation from the design dimension of the 0.15 μm line and space pattern was measured.

[0181] ｜ Design Dimension-Actual Dimension ｜ / Design Dimension × 100 (%) The smaller the value, the better.

[Initial value of particles] For the negative resist composition solution (coating solution) prepared as described above, the number of particles in the liquid immediately after preparation (initial value of particles) is
The particle initial value was evaluated by counting with a particle counter manufactured by Rion. The performance evaluation results are shown in Table 2.

[0183]

[Table 2]

From the results shown in Table 2, the negative resist composition in which the composition of the present invention was combined was compared with the composition of Comparative Example.
It can be seen that the sensitivity is excellent and the resolution and profile are also improved.

[Examples 19 to 23 and Comparative Example 9] Ten resist films were prepared in the same manner as above using the compositions of Examples 2, 7, 8, 10, and 11 and Comparative Example 2 described above.
Irradiation was performed using an electron beam drawing apparatus under the condition of an acceleration voltage of 0 KeV. After the irradiation, heating, development and rinsing were performed in the same manner as in the above-mentioned example, and the obtained pattern was observed with a scanning electron microscope. Table 3 shows the results of evaluations performed in the same manner as in the above example.

[0186]

[Table 3]

From the results shown in Table 3, it can be seen that the negative resist composition of the present invention exhibits a good resolution and a rectangular profile even when irradiated with an electron beam at a high acceleration voltage, as compared with the composition of Comparative Example 9. .

[0188]

The negative resist composition for electron beams and X-rays of the present invention can provide a negative resist composition having excellent resolution and a rectangular profile even under a condition of high accelerating voltage.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yutaka Adegawa             Fuji-Sha, 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture             Shin Film Co., Ltd. F-term (reference) 2H025 AA01 AA03 AB16 AC05 AC06                       AD01 BE00 CB42 CB43 CC04                       CC17 CC20

Claims (4)

[Claims] 1. A compound (A) which generates an acid upon irradiation with an electron beam or an X-ray, and (B) a resin soluble in an alkaline aqueous solution (D) represented by the following general formulas (1) to (8). Electron beam or X containing at least one compound
Negative resist composition for lines. [Chemical 1] In the above general formulas (1) to (8), R ₁₁ is a hydrogen atom, or a primary, secondary or tertiary aliphatic amine substituent, mixed amine substituent, aromatic amine substituent , Heterocyclic amine substituents, amide groups, imide groups, ester groups, halogen groups, halogen substituted alkyl groups, halogen substituted aryl groups, hydroxyl groups, carboxyl groups, thiol groups,
A cyano group, a nitro group, a formyl group, a sulfonyl group, a sulfonamide group, an acyl group, an aroyl group, an alkyl group, an alkyloxy group, an alkenyloxy group, a heterocyclic group, an aryl group, an alkenyl group and an aralkyl group. R ₁₂ represents a hydrogen atom, an aromatic amine substituent, a heterocyclic amine substituent, a halogen-substituted alkyl group, a halogen-substituted aryl group, a hydroxyl group, an acyl group, an aroyl group, an alkyl group, an alkyloxy group, an alkenyloxy group, A heterocyclic group, an aryl group, an alkenyl group, an aralkyl group, an ester group, and a carbonic acid ester group are shown. 2. The negative resist composition for electron beam or X-ray according to claim 1, further comprising (C) a compound which undergoes an addition reaction with a resin by the action of an acid. 3. The negative resist composition for electron beam or X-ray according to claim 1, further comprising (E) a nitrogen-containing basic compound. 4. The negative resist composition for electron beam or X-ray according to claim 1, further comprising (F) a surfactant.