JP2008112186A - Negative resist composition for electron beam, euv or x-ray and pattern forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a negative resist composition for an electron beam, EUV or X-ray that excels in sensitivity and resolution and satisfies even a rectangular pattern form, and a pattern forming method using the same. <P>SOLUTION: The negative resist composition for an electron beam, EUV or X-ray comprises (A1) a compound that has a specific cationic structure having a reduction potential higher than -0.78 V and generates an acid upon irradiation with an actinic ray or radiation, (BN) an alkali-soluble resin and (C) a crosslinking agent that causes crosslinking under an acid. The pattern forming method using the same is also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resist composition suitably used in an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips and other photo-publishing processes, and a pattern forming method using the resist composition. More specifically, the present invention relates to a negative resist composition capable of forming a highly refined pattern using an electron beam, EUV or X-ray, and a pattern forming method using the same.

  Integrated circuits have been increasingly integrated, and in the manufacture of semiconductor substrates such as VLSI, processing of ultra-fine patterns having a line width of less than half a micron is required. In order to satisfy this need, the wavelength used by exposure apparatuses used in photolithography has become shorter, and now far ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) have been studied. . Further, formation of a finer pattern by an electron beam or X-ray has been studied.

Electron beam lithography is positioned as the next-generation or next-generation pattern formation technology, and development of positive and negative resists having high sensitivity, high resolution, and a rectangular profile shape is strongly desired.
In electron beam lithography, energy is supplied to a compound in the process in which an accelerated electron beam collides and scatters with atoms constituting the resist material, causing a reaction of the resist material to form an image. By using a highly accelerated electron beam, straightness increases, the influence of electron scattering is reduced, and a pattern with high resolution and rectangular shape and good edge roughness can be formed. The sensitivity increases and the sensitivity decreases. Thus, in electron beam lithography, sensitivity and resolution / resist shape, dissolution contrast, and edge roughness are in a trade-off relationship, and how to achieve both is a problem. EUV and X-ray lithography have the same problem.

With regard to positive resists for electron beams or X-rays, the resist technology for KrF excimer laser has been mainly used so far. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 2000-181065), a combination of a compound that generates an acid upon irradiation with an electron beam and an amine compound having a boiling point of 250 ° C. or lower is further disclosed in Patent Document 2 (European Patent No. 0919867). Is a combination of a polymer having an acid-decomposable group, an acid generator and an electron beam sensitizer. Further, Patent Document 3 (Japanese Patent Publication No. 7-508840) discloses a polymer having an acid-decomposable group and an amide compound. Each of these combinations is disclosed. Further, Patent Document 4 (JP-A-3-200968) uses maleimide compounds, Patent Document 5 (JP-A-7-92680) uses sulfonamide compounds, and Patent Document 6 (JP-A-11-44950). ) Discloses sulfoneimide compounds containing a —SO ₂ —NH—SO ₂ — partial structure, and in these attempts to improve, both have high sensitivity and high resolution, rectangular resist shape, It did not achieve both good dissolution contrast and good edge roughness.

On the other hand, various alkali-soluble resins have been proposed for negative resists. Patent Document 7 (Japanese Patent Laid-Open No. 8-127717) discloses partially alkyl etherified polyvinylphenols in Patent Document 8 (Japanese Patent Laid-Open No. 6-67431) and Patent Document 9 (Japanese Patent Laid-Open No. 10-10733). Is a copolymer of vinylphenol and styrene, Patent Document 10 (Japanese Patent No. 2505033) is a novolak resin, Patent Document 11 (Japanese Patent Laid-Open No. 7-311463), Patent Document 12 (Japanese Patent Laid-Open No. 8-292559). Monodispersed polyvinylphenols are disclosed in Japanese Patent Publication Nos.), But these alkali-soluble resins have characteristics of sensitivity and resolution, resist shape, dissolution contrast, and edge roughness under electron beam or X-ray irradiation. It was not compatible.
Conventionally, for negative resists, compounds that generate acid by various electron beams or X-rays have been proposed. Patent Document 13 (JP-B-8-3635) discloses an organic halogen compound, Patent Document 14 (JP-A-2-150848), and Patent Document 15 (JP-A-6-199770) disclose iodonium salts and sulfonium salts. Patent Document 16 (JP-A-2-52348), Patent Document 17 (JP-A-4-367864), and Patent Document 18 (JP-A-4-367865) disclose an acid generator containing Cl and Br. Patent Document 19 (Japanese Patent Laid-Open No. 4-210960), Patent Document 20 (Japanese Patent Laid-Open No. 4-217249) disclose diazodisulfone and diazosulfone compounds, and Patent Document 21 (Japanese Patent Laid-Open No. 4-226454) discloses triazine compounds. Patent Document 22 (JP-A-3-87746), Patent Document 23 (JP-A-4-291259), Patent Document 24 (JP-A-636024), Patent Document 25 (US Pat. No. 5,434,472) Sulfonate compounds are disclosed respectively in Sensitivity and resolution of resist shape under electron beam or X-ray irradiation at Namazai, dissolution contrast, was not able to overcome the trade-off of the edge roughness.
Furthermore, methylol melamine, resol resin, epoxidized novolak resin, urea resin, and the like have been conventionally used for the crosslinking agent, but these crosslinking agents are unstable to heat and used as a resist solution. There was a problem in storage stability at the time.
In Patent Document 26 (Japanese Patent No. 3000740), Patent Document 27 (Japanese Patent Laid-Open No. 9-1667070), Patent Document 28 (Japanese Patent Laid-Open No. 2-15270) and Patent Document 29 (US Patent No. 5863699) The proposed resist composition also does not sufficiently satisfy the required characteristics of high sensitivity, high resolution, rectangular resist shape, dissolution contrast, and edge roughness under electron beam or X-ray irradiation.

  Thus, it is difficult for conventionally known resists to have both high sensitivity and high resolution sufficiently under electron beam or X-ray irradiation, as well as a rectangular resist shape, dissolution contrast, and edge roughness. Both of these are strongly desired.

JP 2000-181065 A European Patent No. 0919867 JP 7-508840 Publication Japanese Unexamined Patent Publication No. 3-200968 JP-A-7-92680 JP 11-44950 A Japanese Patent Laid-Open No. 8-127717 JP-A-6-67431 Japanese Patent Laid-Open No. 10-10733 Japanese Patent No. 2505033 JP 7-311463 A JP-A-8-292559 Japanese Patent Publication No.8-3635 JP-A-2-150848 JP-A-6-199770 JP-A-2-52348 Japanese Unexamined Patent Publication No. 4-367864 Japanese Unexamined Patent Publication No. 4-367865 JP-A-4-210960 JP-A-4-217249 JP-A-4-226454 JP-A-3-87746 JP-A-4-291259 Japanese Laid-Open Patent Publication No.6-236024 U.S. Pat. Japanese Patent No. 3000740 Japanese Patent Laid-Open No. 9-1667070 Japanese Patent Laid-Open No. 2-15270 U.S. Pat. No. 5,863,699

The objective of this invention is providing the resist composition which solved the subject of the performance improvement technique in the microfabrication of the semiconductor element which uses an electron beam, EUV, or X-ray, and a pattern formation method using the same.
Furthermore, it is to provide a negative resist composition that satisfies sensitivity, resolution, and resist shape characteristics with respect to the use of electron beam, EUV or X-ray, and a pattern forming method using the same.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a negative resist composition containing a specific acid generator, and have reached the present invention.
That is, the present invention is achieved by the following configuration.

(1) (A1) A reduction potential is higher than −0.78 V, and has a structure represented by the following general formula (1), (2) or (3), and generates an acid upon irradiation with actinic rays or radiation. A negative resist composition for an electron beam, EUV or X-ray, comprising a compound, (BN) an alkali-soluble resin, and (C) a crosslinking agent that is crosslinked with an acid.

In general formula (1),
Y represents an aryl group which may have a substituent or an alkyl group which may have a substituent.
R _{1a to} R _8a each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxyl group, an optionally substituted alkyl group or an optionally substituted cycloalkyl group. Represents.

In general formulas (2) and (3),
R _{1 to} R ₁₅ each independently represents a hydrogen atom, a nitro group, a cyano group, or a trifluoromethyl group. However, at least two of R _{1 to} R ₁₅ are selected from a nitro group, a cyano group, and a trifluoromethyl group.
R _{16 to} R ₁₉ and R _{22 to} R ₂₇ each independently represent a hydrogen atom, a nitro group, a cyano group, a trifluoromethyl group, or a halogen atom.
X ^- it is,
At least one fluorine atom,
An alkyl group substituted with at least one fluorine atom,
An alkoxy group substituted with at least one fluorine atom,
An acyl group substituted with at least one fluorine atom,
An acyloxy group substituted with at least one fluorine atom,
A sulfonyl group substituted with at least one fluorine atom,
A sulfonyloxy group substituted with at least one fluorine atom,
A sulfonylamino group substituted with at least one fluorine atom,
An aryl group substituted with at least one fluorine atom,
An aralkyl group substituted with at least one fluorine atom, and an alkoxycarbonyl group substituted with at least one fluorine atom;
An anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from

  (2) Further, (A2) is characterized by containing a compound that has a structure represented by the following general formula (I) to general formula (III) and generates an acid upon irradiation with actinic rays or radiation (1 ) Negative resist composition for electron beam, EUV or X-ray.

In the general formulas (I) to (III), R _{1 to} R ₃₇ are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, or a —S—R ₃₈ group. _R38 represents an alkyl group or an aryl group.
X ^- it is,
At least one fluorine atom,
An alkyl group substituted with at least one fluorine atom,
An alkoxy group substituted with at least one fluorine atom,
An acyl group substituted with at least one fluorine atom,
An acyloxy group substituted with at least one fluorine atom,
C ₄ F ₉ -SO ₂ - group,
C ₄ F ₉ -SO ₂ -NH- group,
An aryl group substituted with at least one fluorine atom,
An aralkyl group substituted with at least one fluorine atom, and an alkoxycarbonyl group substituted with at least one fluorine atom;
An anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from

  (3) Further, (A3) contains at least one of a compound that generates fluorine-containing carboxylic acid upon irradiation with actinic rays or radiation and (A4) a compound that generates fluorine-free carboxylic acid upon irradiation with actinic rays or radiation. The negative resist composition for electron beam, EUV or X-ray according to (1) or (2), wherein

  (4) The electron beam, EUV or X-ray according to any one of (1) to (3), wherein the resin of the (BN) component has a repeating unit represented by the following general formula (a): Negative resist composition for use.

Where
R ₁ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or 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 have a hydrogen atom, a halogen atom, a cyano group, or a substituent, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl Represents a group.
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 —O—R ₆ — and —CO—N (R ₇ ) —R ₈ — are represented.
R ₅ , R ₆ and R ₈ may be the same or different and each may have a single bond or a substituent, an alkylene group, an alkenylene group, a cycloalkylene group, or an arylene group alone, or these groups And a divalent group formed by combining 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 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.
A plurality of R _{2 s} or R ₂ and R ₃ or R ₄ may combine to form a ring.

  (5) (C) The crosslinking agent crosslinked with an acid is at least one selected from compounds represented by the following general formulas (4) to (6) and alkoxymethylated melamine compounds ( A negative resist composition for electron beam, EUV or X-ray according to any one of 1) to (4).

R _5b in the general formulas (4) to (6) each independently represents a hydrogen atom, an alkyl group or an acyl group.
R _{< 6b} > -R < _9b > in General formula (4) represents a hydrogen atom, a hydroxyl group, an alkyl group, or an alkoxyl group each independently.
X represents a single bond, a methylene group or an oxygen atom.

  (6) (C) The crosslinking agent that crosslinks with an acid is a phenol derivative having 1 to 6 benzene rings in the molecule, and has at least two hydroxymethyl groups and / or alkoxymethyl groups in the molecule, A negative resist composition for electron beam, EUV or X-ray according to any one of (1) to (5), which is a compound in which these groups are bonded to any benzene ring atomic group .

(7) including a step of forming a resist film from the negative resist composition according to any one of (1) to (6), and exposing and developing the resist film with an electron beam, EUV, or X-ray. A characteristic pattern forming method.

  According to the present invention, it is possible to provide an electron beam, EUV or X-ray negative resist composition excellent in sensitivity and resolving power and forming a rectangular profile, and a pattern forming method using the same.

  The present invention will be described below.

(A1) A compound having a structure represented by the general formula (1), (2) or (3) having a reduction potential higher than −0.78 V and generating an acid upon irradiation with actinic rays or radiation (( A1) component, also referred to as (A1) compound)
In the present invention, the compound (A1) is used as the acid generator. The reduction potential can be measured by cyclic voltammetry.

In general formula (1), Y represents an aryl group which may have a substituent or an alkyl group which may have a substituent. R _{1a to} R _8a each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxyl group, an optionally substituted alkyl group or an optionally substituted cycloalkyl group. Represents.

The alkyl group for Y may be linear or branched, and preferably has 1 to 8 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group and the like. These may further have a substituent.
The aryl group for Y is preferably one having 6 to 16 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthranyl group, a phenanthrenyl group, and a birenyl group.
Examples of the substituent that Y may have include an aryl group, an alkyl group, a cycloalkyl group, an alkoxyl group, a carboxyl group, a hydroxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a cyano group, A nitro group, an arylcarbonyl group, an alkylcarbonyl group, etc. are mentioned. Y may have a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, aryl, which is an electron-withdrawing substituent from the viewpoint of reduction potential. A carbonyl group and an alkylcarbonyl group are preferred.

The alkyl group for R _{1a to} R _8a may be linear or branched, and preferably has 1 to 8 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group and the like. These may further have a substituent.
As a cycloalkyl group of R _{< 1a} > -R < _8a >, a C3-C8 cycloalkyl group is preferable, For example, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group are mentioned, Furthermore, you may have a substituent.
Examples of the halogen atom represented by R _{1a to} R _8a include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the substituent that R _{1a to} R _8a may have include an alkyl group (methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-amyl group). , T-amyl group), cycloalkyl group, phenyl group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group and the like. As the substituents that R _{1a to} R _8a may have, an alkyl group (methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t, -Butyl group, n-amyl group, t-amyl group), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group which are electron-withdrawing substituents from the viewpoint of reduction potential A nitro group is preferred.

  When the compound (1) has a counter anion, the counter anion preferably generates an organic sulfonic acid, such as an alkyl sulfonic acid, an aromatic sulfonic acid, a fluorinated alkyl sulfonic acid, or a fluorinated aromatic sulfonic acid. Those that generate are more preferred. Among these organic sulfonic acids, those having a large number of carbon atoms have moderately controlled diffusibility of the generated acid and have good resolution. Specifically, the alkyl sulfonic acid preferably has 4 to 20 carbon atoms in the alkyl group, the aromatic sulfonic acid preferably has a benzene ring or a naphthalene ring, and the fluorinated alkyl sulfonic acid has an alkyl group. Having 4 to 12 carbon atoms is preferable, and the fluorinated aromatic sulfonic acid preferably has a benzene ring or a naphthalene ring.

In general formulas (2) and (3),
R _{1 to} R ₁₅ each independently represents a hydrogen atom, a nitro group, a cyano group, or a trifluoromethyl group. However, at least two of R _{1 to} R ₁₅ are selected from a nitro group, a cyano group, and a trifluoromethyl group.
R _{16 to} R ₁₉ and R _{22 to} R ₂₇ each independently represent a hydrogen atom, a nitro group, a cyano group, a trifluoromethyl group, or a halogen atom.
X ^- it is,
At least one fluorine atom,
An alkyl group substituted with at least one fluorine atom,
An alkoxy group substituted with at least one fluorine atom,
An acyl group substituted with at least one fluorine atom,
An acyloxy group substituted with at least one fluorine atom,
A sulfonyl group substituted with at least one fluorine atom,
A sulfonyloxy group substituted with at least one fluorine atom,
A sulfonylamino group substituted with at least one fluorine atom,
An aryl group substituted with at least one fluorine atom,
An aralkyl group substituted with at least one fluorine atom, and an alkoxycarbonyl group substituted with at least one fluorine atom;
An anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from

Examples of the halogen atom represented by R _{16 to} R ₂₇ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group in X ⁻ may be linear, branched or cyclic, and preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms.
Specifically, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, heptafluoroisopropyl group, perfluorobutyl group, perfluorooctyl group, perfluorododecyl group, A perfluorocyclohexyl group can be exemplified. Especially, the C1-C4 perfluoroalkyl group substituted by the fluorine is preferable. Particularly preferred is a perfluorobutyl group (C ₈ F ₉ group).

The alkoxy group in X ⁻ may be linear, branched or cyclic, and preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms.
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. Especially, the C1-C4 perfluoro alkoxy group substituted with the fluorine is preferable.

The acyl group in X ⁻ is preferably an acyl group having 2 to 12 carbon atoms and substituted with 1 to 23 fluorine atoms. Specific examples include a trifluoroacetyl group, a fluoroacetyl group, a pentafluoropropionyl group, and a pentafluorobenzoyl group.

The acyloxy group in X ⁻ is preferably an acyloxy group having 2 to 12 carbon atoms and substituted with 1 to 23 fluorine atoms. Specific examples include a trifluoroacetoxy group, a fluoroacetoxy group, a pentafluoropropionyloxy group, a pentafluorobenzoyloxy group, and the like.

The sulfonyl group in X ⁻ is preferably a sulfonyl group having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms. Specific examples include a trifluoromethanesulfonyl group, a pentafluoroethanesulfonyl group, a perfluorobutanesulfonyl group, a perfluorooctanesulfonyl group, a pentafluorobenzenesulfonyl group, and a 4-trifluoromethylbenzenesulfonyl group.

The sulfonyloxy group in X ⁻ is preferably a sulfonyloxy group having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms. Specific examples include trifluoromethanesulfonyloxy, perfluorobutanesulfonyloxy group, 4-trifluoromethylbenzenesulfonyloxy group, and the like.

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

The aryl group in X ⁻ is preferably an aryl group having 6 to 14 carbon atoms and substituted with 1 to 9 fluorine 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 in X ⁻ is preferably an aralkyl group having 7 to 10 carbon atoms and substituted with 1 to 15 fluorine atoms. Specific examples include a pentafluorophenylmethyl group, a pentafluorophenylethyl group, a perfluorobenzyl group, and a perfluorophenethyl group.

The alkoxycarbonyl group in X ⁻ is preferably an alkoxycarbonyl group having 2 to 13 carbon atoms and substituted with 1 to 25 fluorine atoms. Specific examples include trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, pentafluorophenoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorooctyloxycarbonyl group, and the like.

X ⁻ is preferably a fluorine-substituted benzenesulfonate anion, and more preferably a pentafluorobenzenesulfonate anion.

Further, the alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid or anthracene sulfonic acid having the above-mentioned fluorine-containing substituent is further linear, branched or cyclic alkoxy group, acyl group, acyloxy group, sulfonyl group, sulfonyloxy A group, a sulfonylamino group, an aryl group, an aralkyl group, an alkoxycarbonyl group (these carbon numbers are the same as those described above), a halogen (excluding fluorine), a hydroxyl group, a nitro group, and the like.

  In the present invention, an acid generator having a reduction potential higher than −0.78 V, which is the reduction potential of diphenyliodonium salt, is used. From the viewpoint of stability, the reduction potential is up to −0.5 V. Are preferably used.

  Specific examples of the compound (A1) of the present invention are shown below, but the present invention is not limited thereto.

  The content of the compound (A1) of the present invention in the composition is suitably from 0.1 to 40% by weight, preferably from 0.5 to 30% by weight, based on the solid content of the total resist composition. Preferably it is 1.0-25 mass%.

(A2) A compound having a structure represented by general formula (I) to general formula (III) that generates an acid upon irradiation with actinic rays or radiation (also referred to as component (A2) or compound (A2)).
The resist composition according to the present invention may further contain the compound (A2) as an acid generator.

In the general formulas (I) to (III), R _{1 to} R ₃₇ are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, or a —S—R ₃₈ group. _R38 represents an alkyl group or an aryl group.

The alkyl group for R _{1 to} R ₃₈ may be linear, branched or cyclic, and the linear or branched alkyl group may be a methyl group or ethyl group which may have a substituent. , Propyl group, n-butyl group, sec-butyl group, t-butyl group and the like having 1 to 4 carbon atoms. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
The alkoxy group for R _{1 to} R ₃₇ may be linear, branched, or cyclic. Examples of the linear and branched alkoxy groups include methoxy, ethoxy, hydroxyethoxy, and propoxy groups. , N-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, octyloxy group and the like, and those having a substituent may be further included. . Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group, which may further have a substituent.
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 for R ₃₈ include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group.

  These substituents are preferably an alkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, iodine atom), an aryl group having 6 to 10 carbon atoms, or 2 to 6 carbon atoms. Alkenyl group, cyano group, hydroxy group, carboxy group, alkoxycarbonyl group, nitro group and the like.

In the general formulas (I) to (III), X ⁻ is an anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid having at least one selected from the following groups.
At least one fluorine atom Alkyl group substituted with at least one fluorine atom Alkoxy group substituted with at least one fluorine atom Acyl group substituted with at least one fluorine atom Substituted with at least one fluorine atom An acyloxy group C ₄ F ₉ —SO ₂ — group,
C ₄ F ₉ -SO ₂ -NH- group,
An aryl group substituted with at least one fluorine atom, an aralkyl group substituted with at least one fluorine atom, and an alkoxycarbonyl group substituted with at least one fluorine atom

X ^- is the general formula (2), at X in (3) ^- is the same as the.

  Specific examples of the compounds represented by the general formulas (I) to (III) are shown below, but are not limited thereto.

The compounds of general formula (I) and general formula (II) are prepared by reacting an aryl Grignard reagent such as arylmagnesium bromide with a substituted or unsubstituted phenyl sulfoxide, and converting the resulting triarylsulfonium halide into the corresponding sulfonic acid and salt. A method of exchanging, or a method in which a substituted or unsubstituted phenyl sulfoxide and a corresponding aromatic compound are condensed and salt exchanged using an acid catalyst such as methanesulfonic acid / phosphorus pentoxide or aluminum chloride, a diaryl iodonium salt and a diaryl sulfide Can be synthesized by a method such as condensation and salt exchange using a catalyst such as copper acetate.
The compound of the general formula (III) can be synthesized by salt exchange in which an aromatic compound is reacted with periodate.

  In the present invention, the compound (A1) and the compound (A2) can be used in combination in the following ratio. The compound of (A1) / (A2) has a molar ratio of 100/0 to 10/90, preferably 90/10 to 30/70, and more preferably 80/20 to 40/60.

(A3) Compound capable of generating fluorine-containing carboxylic acid upon irradiation with actinic rays or radiation (hereinafter also referred to as (A3) compound)
The resist composition according to the present invention may further contain the compound (A3) as an acid generator.

Examples of the fluorine-containing carboxylic acid include a fluorine-substituted aliphatic carboxylic acid and a fluorine-substituted aromatic carboxylic acid.
Examples of the fluorine-substituted aliphatic carboxylic acid include acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, trimethylacetic acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, Examples thereof include fluorine-substituted products of aliphatic carboxylic acids such as palmitic acid, stearic acid, undecanoic acid, and tridecanoic acid. These may have a hydroxyl group, an alkoxy group, or a halogen atom other than a fluorine atom as a substituent. Further, the aliphatic chain may contain a linking group such as an oxygen atom, a sulfur atom, a carbonyl group, an ester group, or a sulfonyl group.
Preferred fluorine-substituted aliphatic carboxylic acids include those represented by the following general formula.
_{L- (CH 2) p (CF} 2) q (CH 2) r-COOH
In the general formula, L represents a hydrogen atom or a fluorine atom. p and r each independently represents an integer of 0 to 15, and q represents an integer of 1 to 15. The hydrogen atom or fluorine atom of the alkyl chain in this general formula is an alkyl group (preferably having 1 to 5 carbon atoms) which may be substituted with a fluorine atom, or an alkoxy group (preferably carbon atom) which may be substituted with a fluorine atom. Formula 1-5) or may be substituted with a hydroxyl group.
The fluorine-substituted aliphatic carboxylic acid is preferably a fluorine-substituted product of a saturated aliphatic carboxylic acid having 2 to 20 carbon atoms, more preferably 4 to 20 carbon atoms. By setting the number of carbon atoms to 4 or more, the diffusibility of the generated carboxylic acid decreases, and the change in line width over time from exposure to post-heating can be further suppressed. Among these, a fluorine-substituted product of a linear or branched saturated aliphatic carboxylic acid having 4 to 18 carbon atoms is preferable.

  The fluorine-substituted aromatic carboxylic acid is a fluorine-substituted aromatic carboxylic acid having 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms, and further preferably 7 to 11 carbon atoms. Is preferred. Specifically, benzoic acid, substituted benzoic acid, naphthoic acid, substituted naphthoic acid, anthracene carboxylic acid, substituted anthracene carboxylic acid (wherein the substituents are alkyl groups, alkoxy groups, hydroxyl groups, halogen atoms, aryl groups, acyls) A fluorine-substituted product of an aromatic carboxylic acid such as a group, an acyloxy group, a nitro group, an alkylthio group, and an arylthio group. Of these, fluorine-substituted products of benzoic acid and substituted benzoic acid are preferable.

The aliphatic or aromatic carboxylic acid substituted with a fluorine atom is one in which one or more hydrogen atoms existing in the skeleton other than the carboxyl group are substituted with a fluorine atom, and particularly preferably a skeleton other than the carboxyl group. Is an aliphatic or aromatic carboxylic acid (perfluoro-saturated aliphatic carboxylic acid or perfluoroaromatic carboxylic acid) in which all hydrogen atoms present in are substituted with fluorine atoms. As a result, the sensitivity is further improved.
As for the aliphatic carboxylate anion, in particular, an anion having a fluorine atom on the α-carbon atom of the carboxylic acid has a high acid strength and easily undergoes salt exchange with respect to the carboxylate anion having no fluorine atom. There is a tendency. In addition, perfluoroaliphatic carboxylic acid has higher acid strength.

As the compound of (A3), preferably, an onium salt compound (sulfonium salt, iodonium salt, etc.) or carboxylic acid ester having an anion of an aliphatic or aromatic carboxylic acid substituted with a fluorine atom as described above as a counter anion Examples thereof include an imidocarboxylate compound having a group or a nitrobenzyl ester compound.
More preferred examples of the compound (A3) include compounds represented by the following general formulas (IF) to (IIIF).
As a result, sensitivity, resolution, and exposure margin are further improved. By irradiating this compound with actinic rays or radiation, a saturated aliphatic or aromatic carboxylic acid substituted with at least one fluorine atom corresponding to X ⁻ in the general formulas (IF) to (IIIF) is generated, Functions as an acid generator.

(In the above formula, R ₁ To R ₃₇ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, hydroxy group, a halogen atom or -S-R ₃₈ group,. Here, R ₃₈ represents a linear, branched, cyclic alkyl group or aryl group. X ⁻ is an anion of an aliphatic or aromatic carboxylic acid substituted with at least one fluorine atom. )
X ⁻ is preferably an anion of a perfluoroaliphatic carboxylic acid or a perfluoroaromatic carboxylic acid, and more preferably an anion of a fluorine-substituted alkylcarboxylic acid having 4 or more carbon atoms.

In the general formulas (IF) to (IIIF), the linear or branched alkyl group of R _{1 to} R ₃₈ may have a substituent, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec -A C1-C4 thing like a butyl group and t-butyl group is mentioned. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
As the alkoxy group for R _{1 to} R ₃₇ , which may have a substituent, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy Examples thereof include those having 1 to 4 carbon atoms such as groups.
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 for R ₃₈ include those having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group. The aryl group may have a substituent.
These substituents are preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, iodine atom), an aryl group having 6 to 10 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms. , Cyano group, hydroxy group, carboxy group, alkoxycarbonyl group, nitro group and the like.

The iodonium compound or sulfonium compound represented by the general formulas (IF) to (IIIF) used in the present invention has, as its counter anion X ⁻ , a saturated aliphatic or aromatic carboxylic acid substituted with at least one fluorine atom. Has an acid anion. These anions are anions (—COO ⁻ ) from which a hydrogen atom of the carboxylic acid (—COOH) has been removed.

Specific examples are shown below, but the present invention is not limited thereto.
Specific examples (I-1f) to (I to 36f) of the acid generator represented by the general formula (IF):

  Specific examples (II-1f) to (II to 67f) of the acid generator represented by the general formula (IIF):

  Specific examples (III-1f) to (III to 4f) of the acid generator represented by the general formula (IIIF):

  Specific examples of other acid generators (IV-1f) to (V to 4f):

The compound represented by the above general formula (IF) can be synthesized by reacting an aromatic compound using periodate and exchanging the obtained iodonium salt with the corresponding carboxylic acid.
The compounds represented by the general formula (IIF) and the general formula (IIIF) correspond to the triarylsulfonium halide obtained by reacting, for example, an aryl Grignard reagent such as arylmagnesium bromide with a substituted or unsubstituted phenyl sulfoxide. It can be synthesized by a method of salt exchange with carboxylic acid. Also, a method in which a substituted or unsubstituted phenyl sulfoxide and a corresponding aromatic compound are condensed and salt exchanged using an acid catalyst such as methanesulfonic acid / phosphorus pentoxide or aluminum chloride, and a diaryl iodonium salt and a diaryl sulfide are mixed with copper acetate. It can be synthesized by a method such as condensation or salt exchange using a catalyst such as
The salt exchange can also be performed by once converting to a halide salt and then converting to a carboxylate using a silver reagent such as silver oxide, or by using an ion exchange resin. The carboxylic acid or carboxylate used for salt exchange can be obtained by using a commercially available product or by hydrolysis of a commercially available carboxylic acid halide.

Fluoro-substituted carboxylic acids as anionic moieties may be those derived from fluoroaliphatic compounds produced by the telomerization method (also called telomer method) or the oligomerization method (also called oligomer method). preferable. Regarding the production method of these fluoroaliphatic compounds, for example, “Synthesis and function of fluorine compounds” (supervision: Nobuo Ishikawa, published by CMC Co., 1987), “Chemistry of Organic Fluorine Compounds” II "(Monograph 187, Ed by Milos Hudlicky and Attila E. Pavlath, American Chemical Society 1995), pages 747-752. The telomerization method is a method of synthesizing a telomer by radical polymerization of a fluorine-containing vinyl compound such as tetrafluoroethylene using an alkyl halide having a large chain transfer constant such as iodide as a telogen. In the synthesis by the telomer method, a mixture of a plurality of compounds having different carbon chain lengths is obtained, but this may be used as a mixture or may be used after purification.

  In the present invention, the compound (A1) and the compound (A3) can be used in combination in the following ratio. The compound of (A1) / (A3) is in a molar ratio of 100/0 to 10/90, preferably 90/10 to 30/70, more preferably 80/20 to 40/60.

(A4) A compound that generates a fluorine-free carboxylic acid upon irradiation with actinic rays or radiation (hereinafter also referred to as (A4) compound)
The resist composition according to the present invention may further contain the compound (A4) as an acid generator.

  Examples of the compound of (A4) include compounds represented by the following general formulas (AI) to (AV).

In the above formula, R _{301 to} R ₃₃₇ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxy group, a halogen atom, or a —S—R ₀ group. . R ₀ represents a linear, branched, cyclic alkyl group or an aryl group.
Ra and Rb each independently represent a hydrogen atom, a nitro group, a halogen atom, or an alkyl group or an alkoxy group which may have a substituent. Rc and Rd each independently represent a halogen atom or an optionally substituted alkyl group or aryl group. Rc and Rd may combine to form an aromatic ring, monocyclic or polycyclic aliphatic cyclic hydrocarbon (which may contain an oxygen atom or a nitrogen atom). Y ₁ and Y _{2 each} represent a carbon atom, and the Y ₁ -Y ₂ bond may be a single bond or a double bond. X ⁻ represents an anion of a carboxylic acid compound represented by the following formula. X ₁ and X ₂ each independently represent a carboxylic acid compound represented by the following formula, which has become an ester group at the carboxyl group portion.

In the above formula, R ₃₃₈ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms (wherein the chain of the alkyl group may contain an oxygen atom or a nitrogen atom), carbon number A linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkynyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms A group wherein at least part of the hydrogen atoms of the alkyl group are substituted with halogen atoms and / or hydroxyl groups, a group wherein at least part of the hydrogen atoms of the alkenyl group are substituted with halogen atoms and / or hydroxyl groups, or carbon The substituted or unsubstituted aryl group of Formula 6-20 is shown. Here, examples of the substituent of the aryl group include an alkyl group, a nitro group, a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, and a halogen atom.

R ₃₃₉ is a single bond or a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms (wherein the chain of the alkylene group may contain an oxygen atom or a nitrogen atom), carbon number 2-20 linear, branched or cyclic alkenylene groups, groups in which at least some of the hydrogen atoms of the alkylene group are substituted with halogen atoms and / or hydroxyl groups, and at least some of the hydrogen atoms of the alkenylene group A group substituted with a halogen atom or an alkoxyalkylene group having 2 to 20 carbon atoms, and a plurality of R ₃₃₈ and R ₃₃₉ may be the same or different from each other.

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

As the linear or branched alkyl group in R _{301 to} R ₃₃₇ , Ra, Rb, Rc, Rd, R ₀ in the general formulas (AI) to (AV), a methyl group which may have a substituent, Examples thereof include those having 1 to 4 carbon atoms such as ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
As the alkoxy group of R _{301 to} R ₃₃₇ , Ra and Rb, a methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group which may have a substituent. And those having 1 to 4 carbon atoms such as t-butoxy group.
Examples of the halogen atom for R _{301 to} R ₃₃₇ , Ra, Rb, Rc, and Rd include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the aryl group for R ₀ , Rc, and Rd include those having 6 to 14 carbon atoms that may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group.
These substituents are preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, iodine atom), an aryl group having 6 to 10 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms. , Cyano group, hydroxy group, carboxy group, alkoxycarbonyl group, nitro group and the like.

  An aromatic ring, monocyclic or polycyclic aliphatic cyclic hydrocarbon formed by combining Rc and Rd (which may contain an oxygen atom or a nitrogen atom) includes a benzene structure, A naphthalene structure, a cyclohexane structure, a norbornene structure, an oxabicyclo structure, etc. are mentioned.

The sulfonium and iodonium compounds represented by the general formulas (AI) to (AIII) used in the present invention are at least the carboxylic acid compounds represented by the above formulas (C1) to (C10) as the counter anion X ^−. It includes those in which the carboxyl group (—COOH) of one compound is an anion (—COO ⁻ ).
The compounds represented by the general formulas (AIV) to (AV) used in the present invention are at least one of the carboxylic acid compounds represented by the above formulas (C1) to (C10) as substituents X ₁ and X _2. It includes a substituent in which the carboxyl group (—COOH) of the seed compound is an ester group (—COO—).

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

As R ₃₃₉ , a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms (wherein the chain of the alkylene group may contain an oxygen atom or a nitrogen atom), methylene, ethylene , Propylene, butylene, isobutylene, ethoxyethylene, cyclohexylene and the like.
Examples of the linear, branched or cyclic alkenylene group having 2 to 20 carbon atoms include vinylene and arylene.

 Although a specific example is shown, this invention is not limited to these.

  In the present invention, the compound (A1) and the compound (A4) can be used in combination in the following ratio. The compound of (A1) / (A4) has a molar ratio of 100/0 to 10/90, preferably 90/10 to 30/70, more preferably 80/20 to 40/60.

(Other compounds that generate acid by actinic rays or radiation)
Furthermore, in addition to the compound (A1), the compound (A2), the compound (A3), and the compound (A4), other compounds that generate an acid upon irradiation with radiation can be used in combination.
The ratio of the compound (A1), (A2), (A3), and (A4) of the present invention to the compound that generates an acid upon irradiation with radiation that can be used in combination is 100/0 to 10 in terms of molar ratio. / 90, preferably 98/2 to 40/60, more preferably 95/5 to 50/50.

  Examples of such other compounds that generate acid by actinic rays or radiation include cationic polymerization photoinitiators, photoradical polymerization photoinitiators, dye photodecolorants, photochromic agents, and microresists. The compound which generate | occur | produces an acid by the well-known light used, and those mixtures can be selected suitably, and can be used.

For example, diazonium salts described in SI Schlesinger, Photogr. Sci. Eng., 18,387 (1974), TSBal etal, Polymer, 21,423 (1980), U.S. Pat.Nos. 4,069,055, 4,069,056, Ammonium salts described in No. 140140, DCNecker etal, Macromolecules, 17, 2468 (1984), CSWen etal, Teh, Proc. Conf Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056 Phosphonium salts, JVCrivello etal, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent Nos. 104,143, 339,049, etc. 410, 201, JP-A-2-150,848, JP-A-2-296,514, etc., iodonium salts, JVCrivello etal, Polymer J. 17, 73 (1985), JVCrivello etal. J. Org. Chem., 43, 3055 (1978), WRWatt etal, J. Polymer Sci., Polymer
Chem. Ed., 22, 1789 (1984), JVCrivello etal, Polymer Bull., 14, 279 (1985), JVCrivello etal, Macromorecules, 14 (5), 1141 (1981), JVCrivello etal, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patent Nos. 370,693, 161,811, 410,201, 339,049, 233,567, 297,443, 297,442, U.S. Patents 3,902,114 and 4,933,377 4,760,013, 4,734,444, 2,833,827, Yasukuni Patent Nos. 2,904,626, 3,604,580, 3,604,581, etc. etal, J. PolymerSci., Polymer Chem. Ed., 17, 1047 (1979) etc., selenonium salt, CSWen etal, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) etc. Onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, JP-B 46-4605, JP-A 48-36281, JP-A 55-32070, JP-A 60-239736, JP-A 61- 169835, JP 61-169837, JP 62-58241 , Organic halogen compounds described in JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, etc., K. Meier etal, J. Rad. Curing, 13 (4), 26 ( 1986), TPGill
etal, Inorg. Chem., 19,3007 (1980), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896)
Organometallic / organic halides described in JP-A-2-16145, S. Hayase etal, J. Polymer
Sci., 25, 753 (1987), E. Reichmanis etal, J. Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhu etal, J. Photochem., 36, 85, 39, 317 (1987), B Amit etal, Tetrahedron Lett., (24) 2205 (1973), DHR Barton etal, J. Chem Soc., 3571 (1965), PMCollins etal, J. Chem. SoC., Perkin I, 1695 (1975), M. Rudinstein etal, Tetrahedron Lett., (17), 1445 (1975), JWWalker etal J. Am. Chem. Soc., 110, 7170 (1988), SCBusman etal, J. Imaging Technol., 11 (4), 191 (1985) ), HMHoulihan etal, Macormolecules, 21, 2001 (1988), PMCollins etal, J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayase etal, Macromolecules, 18, 1799 (1985), E. Reichmanis etal, J. Electrochem. Soc., Solid State Sci. Technol., 130 (6), FM Houlihan etal, Macromolcules, 21, 2001 (1988), European Patent Nos. 0290,750, 046,083, 156,535, Photoacid generators having o-nitrobenzyl type protecting groups described in US Pat. Nos. 271,851, 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-198538, JP-A-53-133022, etc. , M.TUNOOKA etal, Polymer Preprints Japan, 35 (8), G. Berner
etal, J. Rad. Curing, 13 (4), WJMijs etal, Coating Technol., 55 (697), 45 (1983), Akzo, H. Adachi etal, Polymer Preprints, Japan, 37 (3), European Patent No. 0199,672, 84515, 044,115, 618,564, 0101,122, U.S. Pat.Nos. 4,371,605, 4,431,774, JP 64-18143, JP 2-245756, JP Examples thereof include compounds that generate photosulfonic acid by photolysis, such as iminosulfonates described in JP-A-3-140109, and disulfone compounds described in JP-A-61-166544.

Further, these light-generating groups, or compounds in which a compound is introduced into the main chain or side chain of the polymer, for example, MEWoodhouse etal, J. Am. Chem. Soc., 104, 5586 (1982), S
P. Pappas etal, J. Imaging Sci., 30 (5), 218 (1986), S. Kondoetal, Makromol. Chem., Rapid Commun., 9,625 (1988), Y. Yamada etal, Makromol. Chem., 152,153,163 (1972), JVCrivello etal, J. PolymerSci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.No. 3,849,137, Korean Patent No. 3914407, JP-A-6
JP 3-26653, JP 55-164824, JP 62-69263, JP 63-146038, JP 63-163452, JP 62-153853, JP 63- The compounds described in No. 146029 and the like can be used.

  Furthermore, VNRPillai, Synthesis, (1), 1 (1980), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971), DHR Barton etal, J. Chem. Soc., (C), 329 (1970) ), Compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

(BN) Alkali-soluble resin (hereinafter also referred to as (BN) component, (BN) resin)
The alkali-soluble resin used in the negative resist composition of the present invention comprises the phenol novolak resin, polyvinyl phenol resin, copolymer having a structural unit derived from vinyl phenol, and polyvinyl phenol resin disclosed so far in the negative resist. A polymer having a phenol skeleton such as a resin obtained by partial protection or modification can be widely used.

  It is preferable that the resin of (BN) component is resin containing the repeating unit of general formula (a).

In the formula, R ₁ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or 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 have a hydrogen atom, a halogen atom, a cyano group, or a substituent, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group Represents.

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—. O—R ₆ — and —CO—N (R ₇ ) —R ₈ — are represented.
R ₅ , R ₆ and R ₈ may be the same or different, and may have a single bond or a substituent, an alkylene group, an alkenylene group, a cycloalkylene group, or an arylene group alone, or these groups It represents a divalent group formed by combining at least one selected from the group of ether structure, ester structure, amide structure, urethane structure or ureido structure.
R ₇ 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. A plurality of R _{2 s} , or R ₂ and R ₃ or R ₄ may be bonded to form a ring.
More preferably, the phenol resin containing the repeating structural unit represented by the general formula (a) can be mentioned.

The alkyl group for R _{1 to} R ₄ and R ₇ is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- Preferred examples include a butyl group, a hexyl group, a 2-ethylhexyl group, and an octyl group. The cycloalkyl group of R _{2 to} 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 exemplified. Preferred examples of the polycyclic type include an adamantyl group, a norbornyl group, an isobornyl group, a dicyclopentyl group, an α-pinel group, and a tricyclodecanyl group.
Examples of the alkenyl group represented by R ₃ and R ₄ include alkenyl groups having 2 to 8 carbon atoms, and specific examples include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

Examples of the aryl group represented by R _{2 to} R ₄ and R ₇ include an aryl group having 6 to 15 carbon atoms, and specifically include a phenyl group, a tolyl group, a dimethylphenyl group, and 2,4,6-trimethyl. A phenyl group, a naphthyl group, an anthryl group, etc. can be mentioned preferably.
As an aralkyl group of R _{2 to} R ₄ and R ₇ , for example, an aralkyl group having 7 to 12 carbon atoms, specifically, a benzyl group, a phenethyl group, a naphthylmethyl group, and the like can be preferably exemplified.

As the haloalkyl group for R ₁ , for example, a haloalkyl group having 1 to 4 carbon atoms, specifically, a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, a bromomethyl group, a bromoethyl group, and the like are preferable. Can do.

The acyl group for R ₂ is, for example, an acyl group having 1 to 8 carbon atoms, and specifically, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, a benzoyl group, and the like are preferable. it can.

The alkylene group for A, R ₅ , R ₆ , and R ₈ is preferably an optionally substituted group having 1 carbon atom such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. There are ~ 8.
Examples of the alkenylene group of A, R ₅ , R ₆ , and R ₈ include those having 2 to 6 carbon atoms, such as an ethenylene group, a propenylene group, and a butenylene group, which may preferably have a substituent.

Examples of the cycloalkylene group of A, R ₅ , R ₆ , and R ₈ preferably include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group, which may have a substituent. .
The arylene group for A, R ₅ , R ₆ and R ₈ is preferably an arylene group having 6 to 12 carbon atoms such as a phenylene group, a tolylene group or a naphthylene group which may have a substituent.

Substituents substituted with these groups include those having active hydrogen such as amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, 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, benzoyl) Oxy group etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group etc.), cyano group, nitro group and the like. In particular, those having active hydrogen such as amino group, hydroxyl group and carboxyl group are preferred.

In addition, as a ring formed by combining a plurality of R ₂ or R ₂ and R ₃ or R ₄ , a 4- to 7-membered ring containing an oxygen atom such as a benzofuran ring, a benzodioxonol ring, or a benzopyran ring is included. Can be mentioned.

  The resin (BN) of the present invention may be a resin composed 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 polymerizations are possible. A copolymerizable monomer may be copolymerized.

  Examples of copolymerizable monomers that can be used include those shown below. For example, it has one addition polymerizable unsaturated bond selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, etc. A compound.

Among these, monomers having a carboxyl group such as carboxystyrene, N- (carboxyphenyl) acrylamide, N- (carboxyphenyl) methacrylamide and the like, and monomers that improve alkali solubility, such as maleimide, are preferable as the copolymer component.
As content of the other polymerizable monomer in resin in this invention, 50 mol% or less is preferable with respect to all the repeating units, More preferably, it is 30 mol% or less.

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

  N in the above specific examples represents a positive integer. x, y, z represents the molar ratio of the resin composition, and in the case of a resin composed of two components, x = 10 to 95, y = 5 to 90, preferably x = 40 to 90, y = 10 to 60 Is done. In the resin composed of three components, x = 10 to 90, y = 5 to 85, z = 5 to 85, preferably x = 40 to 80, y = 10 to 50, z = 10 to 50 are used. .

A preferred molecular weight of the resin having a repeating structural unit represented by the above (BN), preferably the general formula (a) is 1,000 to 200,000 on a weight average, and more preferably 3,000 to 50,000. Used in range. The molecular weight distribution is 1 to 10, preferably 1 to 3, more preferably 1 to 1.5. The smaller the molecular weight distribution, the higher the resolution, the better the resist shape, the smoother the side wall of the resist pattern, and the better the roughness.
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 resin having the repeating unit of the general formula (a).

The alkali-soluble resin containing the structural unit represented by the general formula (a) used in the present invention is Macromolecules (1995), 28 (11), 3787-3789, Polym. Bull. (Berlin) (1990), 24 ( 4), 385 to 389, and the method described in JP-A-8-286375. 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.

Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.
The alkali dissolution rate of the alkali-soluble resin is preferably 20 測定 / sec or more as measured with a 0.261N tetramethylammonium hydroxide (TMAH) aqueous solution (23 ° C.). More preferably, it is 200 Å / second or more.
In the present invention, the alkali-soluble resin having the repeating unit represented by the general formula (a) may be used alone, but other alkali-soluble resins may be used in combination. As for the use ratio, other alkali-soluble resins other than 100 parts by weight of the alkali-soluble resin having a repeating unit represented by the general formula (a) can be used in combination up to 100 parts by weight. Examples of the alkali-soluble resin that can be used together are shown below.
For example, novolak resin, hydrogenated novolac resin, acetone-pyrogallol resin, styrene-maleic anhydride copolymer, carboxyl group-containing methacrylic resin and derivatives thereof can be mentioned, but are not limited thereto.

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

(C) Compound cross-linked by acid (also referred to as (C) component or (C) cross-linking agent)
The compound used for the negative resist composition of the present invention that crosslinks with an acid (hereinafter, appropriately referred to as an acid crosslinker or simply a crosslinker) is an alkali in the presence of an acid, for example, an acid generated by irradiation with radiation. It is a compound that can crosslink soluble resins. Examples of such a crosslinking agent include compounds having one or more substituents (hereinafter referred to as “crosslinkable substituents”) having crosslinking reactivity with an alkali-soluble resin.

Specific examples of such crosslinkable substituents include (i) hydroxyalkyl groups such as hydroxyalkyl groups, alkoxyalkyl groups, and acetoxyalkyl groups or derivatives thereof; (ii) carbonyl groups such as formyl groups and carboxyalkyl groups. Or a derivative thereof;
(Iii) nitrogen-containing group-containing substituents such as dimethylaminomethyl group, diethylaminomethyl group, dimethylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group;
(Iv) Glycidyl group-containing substituents such as glycidyl ether group, glycidyl ester group, glycidylamino group;
(V) aromatic derivatives such as allylcarbonyloxyalkyl groups such as benzyloxymethyl group and benzoyloxymethyl group, and aralkyloxyalkyl groups;
(Vi) Substituents containing polymerizable multiple bonds such as vinyl groups and isopropenyl groups. As the crosslinkable substituent of the crosslinking agent of the present invention, a hydroxyalkyl group, an alkoxyalkyl group or the like is preferable, and an alkoxymethyl group is more preferable.

Examples of the crosslinking agent having a crosslinkable substituent include (i) methylol groups such as (i) methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing glycoluril compounds, and methylol group-containing phenol compounds. Containing compounds;
(Ii) alkoxyalkyl group-containing compounds such as alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing glycoluril compounds, alkoxyalkyl group-containing phenol compounds;
(Iii) Carboxymethyl group-containing compounds such as carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, carboxymethyl group-containing glycoluril compounds, carboxymethyl group-containing phenol compounds;
(Iv) Examples include bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac resin-based epoxy compounds, resol resin-based epoxy compounds, and epoxy compounds such as poly (hydroxystyrene) -based epoxy compounds. it can.

  As the cross-linking agent, it is possible to use a resin in which the cross-linkable substituent is introduced into the acidic functional group in the alkali-soluble resin and the property as the cross-linking agent is imparted. In this case, the introduction rate of the crosslinkable substituent is usually 5 to 60 mol%, preferably 10 to 50 mol%, more preferably 15 to 40 mol%, based on all acidic functional groups in the alkali-soluble resin. Adjusted. If the introduction ratio of the crosslinkable substituent is less than 5 mol%, it is difficult to cause a sufficient crosslinking reaction, the remaining film ratio is decreased, the pattern swelling phenomenon and the meandering are likely to occur, and it exceeds 60 mol%. Then, the alkali solubility of the alkali-soluble resin is lowered, and the developability tends to deteriorate.

In the resist composition of the present invention, the cross-linking agent is preferably an alkoxymethylated urea compound or a resin thereof, or an alkoxymethylated glycoluril compound or a resin thereof.
Particularly preferred examples of the crosslinking agent (C1) include compounds represented by the above formulas (4) to (6) and alkoxymethylated melamine compounds.

R _5b in the formulas (4) to (6) each independently represents a hydrogen atom, an alkyl group (1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group) or an acyl. Represents a group (preferably having 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, for example, an acetyl group or a propionyl group).
R _{6b to} R _9b in formula (4) are each independently a hydrogen atom, a hydroxyl group, or an alkyl group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. ) Or an alkoxyl group (preferably having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, for example, a methoxy group, an ethoxy group, or a propoxy group). X represents a single bond, a methylene group or an oxygen atom. X is preferably a single bond or a methylene group.
These groups may further have an alkyl group such as a methyl group or an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, a substituent such as a hydroxyl group or a halogen atom.

  Specific examples of the compounds represented by the formulas (4) to (6) and the alkoxymethylated melamine compound are shown below, but are not limited thereto.

  The cross-linking agent is, for example, a condensation reaction between a urea compound or glycoluril compound and formalin to introduce a methylol group, and then etherification with lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, etc. It is obtained by recovering the compound or its resin which cools and precipitates. The crosslinking agent can also be obtained as a commercial product such as CYMEL (trade name, manufactured by Mitsui Cyanamid) or Nicarad (manufactured by Sanwa Chemical).

Further, as a particularly preferred crosslinking agent (C2), a phenol derivative having 1 to 6 benzene rings in the molecule, and having two or more hydroxymethyl groups and / or alkoxymethyl groups in the molecule, And a compound in which is bonded to at least one of the benzene rings.
Preferably, it has a molecular weight of 1500 or less, 1 to 6 benzene rings in the molecule, and 2 or more hydroxymethyl groups and / or alkoxymethyl groups, and the hydroxymethyl group and alkoxymethyl group Phenol derivatives formed by concentrating or allocating to at least one of the benzene rings can be exemplified.

  As the alkoxymethyl group bonded to the benzene ring, those having 6 or less carbon atoms are preferable. Specifically, a methoxymethyl group, an ethoxymethyl group, an n-propoxymethyl group, an i-propoxymethyl group, an n-butoxymethyl group, an i-butoxymethyl group, a sec-butoxymethyl group, and a t-butoxymethyl group are preferable. Furthermore, alkoxy-substituted alkoxy groups such as 2-methoxyethoxy group and 2-methoxy-1-propyloxy group are also preferable. Among these phenol derivatives, particularly preferable ones are listed below.

(In formula, L < ¹ > -L < ⁸ > may be same or different and shows a hydroxymethyl group, a methoxymethyl group, or an ethoxymethyl group.)
A phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound not having a corresponding hydroxymethyl group (a compound in which L ^{1 to} L ⁸ are hydrogen atoms in the above formula) with formaldehyde in the presence of a base catalyst. it can. At this time, in order to prevent resinification or gelation, the reaction temperature is preferably 60 ° C. or lower. Specifically, they can be synthesized by the methods described in JP-A-6-282067, JP-A-7-64285 and the like.

A phenol derivative having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst. At this time, in order to prevent resinification and gelation, the reaction temperature is preferably 100 ° C. or lower. Specifically, it can be synthesized by the method described in European Patent EP632003A1 and the like.

  A phenol derivative having a hydroxymethyl group or an alkoxymethyl group is preferable from the viewpoint 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 on any benzene ring or distributed and bonded may be used alone or in combination of two kinds. A combination of the above may also be used.

  In the present invention, the crosslinking agent is used in an amount of 3 to 70% by weight, preferably 5 to 50% by weight, based on the total solid content of the resist composition. If the addition amount of the crosslinking agent is less than 3% by weight, the residual film ratio decreases, and if it exceeds 70% by weight, the resolving power decreases, and further, it is not preferable from the viewpoint of stability during storage of the resist solution.

  A compound having the above N-hydroxymethyl group, N-alkoxymethyl group or N-acyloxymethyl group and a phenol derivative having a hydroxymethyl group or an alkoxymethyl group may be used in combination of two or more.

Other components used in the resist composition of the present invention If necessary, the resist composition of the present invention may further include an organic basic compound, a dye, a solvent, a fluorine-based and / or silicon-based surfactant, and other components. A surfactant or the like can be contained.

Organic Basic Compound The organic basic compound used in the present invention is preferably an organic basic compound that is more basic than phenol. Of these, nitrogen-containing basic compounds are preferred.
As a preferable chemical environment of the nitrogen-containing basic compound, structures of the following formulas (A) to (E) can be exemplified.

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms. 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 each represents an alkyl group having 1 to 6 carbon atoms.
Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms of different chemical environments in one molecule, and particularly preferably both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom. Or a compound having an alkylamino group.

  Preferred 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 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. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

  Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4 , 5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (Aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4- Aminoethylpyridine,

3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl)- Examples include 5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine. It is not limited to this.
These organic basic compounds are used alone or in combination of two or more.

  The use ratio of the acid generator and the organic basic compound in the positive resist composition is preferably (acid generator) / organic basic compound) (molar ratio) = 2.5 to 300. (Acid generator) / (organic basic compound) (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

  The usage-amount of an organic basic compound is 0.001-10 mass% normally with respect to solid content of the whole composition of a negative resist composition, Preferably it is 0.01-5 mass%.

Dyes Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (oriental chemical industry) Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI522015) and the like.

Solvent The resist composition of the present invention is dissolved in a solvent that dissolves each of the above components and coated on a support. Solvents used here include 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, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran, and the like are preferable. Or mixed to use.
Particularly preferred solvents are propylene glycol monomethyl ether acetate and a mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether.

Fluorine-based and / or silicon-based surfactant The resist composition of the present invention further comprises a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant and silicon-based surfactant, both fluorine atom and silicon atom). It is preferable to contain any one or two or more surfactants.
When the resist composition of the present invention contains a fluorine-based and / or silicon-based surfactant, when using an exposure light source of 250 nm or less, particularly 220 nm or less, good sensitivity and resolution, and less adhesion and development defects. A resist pattern can be provided.
Examples of the fluorine-based and / or silicon-based surfactant include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, Japanese Unexamined Patent Publication No. 63-34540, Japanese Unexamined Patent Publication No. 7-230165, Japanese Unexamined Patent Publication No. 8-62834, Japanese Unexamined Patent Publication No. 9-54432, Japanese Unexamined Patent Publication No. 9-5988, Japanese Unexamined Patent Publication No. 2002-277862, US Patent 5,405,720, 5,360,692, 5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511, 5,824,451 Activators can be mentioned, and the following commercially available surfactants can be used as they are.
Examples of commercially available fluorine-based and / or silicon-based surfactants that can be used include F-top EF301, EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, R08 (Dainippon Ink Chemical Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical) Fluorine-based surfactants or silicon-based surfactants such as those manufactured by K.K. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants shown above, fluorine-based and / or silicon-based surfactants can be produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). A surfactant using a polymer having a fluoroaliphatic group derived from a fluoroaliphatic compound can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.
As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like, and a poly (oxyethylene, oxypropylene, and oxyethylene group). A unit having different chain lengths in the same chain length, such as a block linked body) or a poly (block linked body of oxyethylene and oxypropylene) group, may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).
For example, as a commercially available fluorine-based and / or silicon-based surfactant, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by Dainippon Ink & Chemicals, Inc.) Can be mentioned. Further, a copolymer of an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), an acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxy) (Ethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate) copolymer, acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate having C ₈ F ₁₇ groups (or Copolymer of acrylate (or methacrylate), (poly (oxyethylene)) acrylate (or methacrylate), and (poly (oxypropylene)) acrylate (or methacrylate) having a C ₈ F ₁₇ group Coalesce, etc. Can.

  The amount of the fluorine-based and / or silicon-based surfactant used is preferably 0.0001-2% by mass, more preferably 0.001-1% by mass, based on the total amount of the resist composition (excluding the solvent). .

Other surfactants As surfactants that can be used in addition to the above, specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, etc. Polyoxyethylene alkyl ethers, polyoxyethylene octylphenol ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan Sorbitan fatty acid esters such as monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxye Nonions such as polyoxyethylene sorbitan fatty acid esters such as tylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate And surface active agents.
The amount of these other surfactants is usually 2 parts by mass or less, preferably 1 part by mass or less per 100 parts by mass of the solid content in the composition of the present invention.

  In the manufacture of precision integrated circuit elements, etc., the pattern formation process on the resist film is carried out by applying the resist composition of the present invention on a substrate (eg, a transparent substrate such as a silicon / silicon dioxide cover, a glass substrate, an ITO substrate). A good resist pattern can be formed by coating by an appropriate coating method such as a spinner or coater, then exposing through a predetermined mask, heating, developing, rinsing and drying.

  Here, examples of the exposure light include electron beams, EUV (extreme ultraviolet), and X-rays.

  In the present invention, a known inorganic or organic antireflection film can be used if necessary. Further, an antireflection film can be applied on the resist layer.

  As the antireflection film used as the lower layer of the resist, either an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, or an organic film type made of a light absorber and a polymer material may be used. it can. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. Examples of the organic antireflection film include a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin described in JP-B-7-69611, an alkali-soluble resin, a light absorber, and maleic anhydride copolymer described in US Pat. No. 5,294,680. A reaction product of a coalescence and a diamine type light absorbing agent, a resin binder described in JP-A-6-186863 and a methylolmelamine thermal crosslinking agent, a carboxylic acid group, an epoxy group and a light-absorbing group described in JP-A-6-118656. An acrylic resin-type antireflection film in the same molecule, a composition comprising methylol melamine and a benzophenone-based light absorber described in JP-A-8-87115, and a low-molecular light absorber added to a polyvinyl alcohol resin described in JP-A-8-179509 And the like.

  In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

As a developing solution of the resist composition of the present invention, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, and primary amines such as ethylamine and n-propylamine are used. Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxy Aqueous solutions of alkalis such as quaternary ammonium salts such as copper and choline, cyclic amines such as pyrrole and piperidine, and the like can be used. In addition, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution.
Among these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are more preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, the content of this invention is not limited by this.

Experimental example (measurement of reduction potential)
The reduction potential of the acid generator was measured by cyclic voltammetry.
That is, the acid generators shown in Tables 1 and 2 were dissolved in acetonitrile distilled under argon and used as a 1 mM solution for measurement. A 0.1 M solution of tetrabutylammonium perchlorate was used as the supporting electrolyte. As the electrode, MP-2 of Yanaco Equipment Development Co., Ltd. was used for the working electrode, C-2U of Yanaco Equipment Development Co., Ltd. was used for the counter electrode, and Ag / AgCl was used for the reference electrode. Measured. The scanning speed was 50 mV / cm ² . The acid generator is irreversible because it is decomposed by reduction, and only a reduction peak was observed.

(1) Synthesis of Compound (A1) Dibenzothiophene (10 g) was dissolved in 200 ml of benzene, cooled to 5 ° C., and concentrated sulfuric acid (40 ml) was slowly added dropwise while stirring the solution. Next, it returned to room temperature and stirred for 48 hours. The reaction mixture was poured onto ice and the aqueous layer was extracted 3 times with 1 liter of ether. The aqueous layer after extraction with ether was cooled to 0 ° C., and then an aqueous solution of trimethylammonium-3,5-ditrifluoromethylbenzenesulfonate (16.95 g / 1 l) was added dropwise, followed by stirring at 0 ° C. for 2 hours. Thereafter, chloroform extraction (3 × 1 l) was performed. The organic layer was washed with water and concentrated to obtain 2.5 g of A1-1 oil.
A1-2 to A1-15 can also be synthesized using the same method.

(2) Synthesis of Compound (A2) (2-1) Synthesis of pentafluorobenzenesulfonic acid tetramethylammonium salt 25 g of pentafluorobenzenesulfonyl chloride was dissolved in 100 ml of methanol under ice-cooling, and 25% tetramethylammonium hydroxide was added thereto. 100 g of aqueous solution was slowly added. When stirred for 3 hours at room temperature, a solution of pentamethylbenzenesulfonic acid tetramethylammonium salt was obtained. This solution was used for salt exchange with sulfonium salt and iodonium salt.

(2-2) Synthesis of triphenylsulfonium pentafluorobenzenesulfonate 50 g of diphenylsulfoxide was dissolved in 800 ml of benzene, 200 g of aluminum chloride was added thereto, and the mixture was refluxed for 24 hours. The reaction solution was slowly poured into 2 L of ice water, 400 ml of concentrated hydrochloric acid was added thereto, and the mixture was heated at 70 ° C. for 10 minutes. This aqueous solution was washed with 500 ml of ethyl acetate and filtered, and then 200 g of ammonium iodide dissolved 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.
30.5 g of triphenylsulfonium iodide was dissolved in 1000 ml of methanol, and 19.1 g of silver oxide was added to this solution, followed by stirring at room temperature for 4 hours. The solution was filtered, and an excess amount of a solution of tetrafluoroammonium sulfonic acid tetramethylammonium salt was added thereto. The reaction solution was concentrated, dissolved in 500 ml of dichloromethane, and this solution was washed with 5% aqueous tetramethylammonium hydroxide solution and water. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain triphenylsulfonium pentafluorobenzene sulfonate (I-1).

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

(3) Synthesis of alkali-soluble resin (BN) (3-1) Synthesis of resin a- (29) 4-acetoxystyrene 3.9 g (0.024 mol), 4-methoxystyrene 0.8 g (0.006 mol) ) Was dissolved in 30 ml of 1-methoxy-2-propanol, and the polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd.) at 70 ° C. under a nitrogen stream and stirring. Product name: V-65) 50 mg, 4-acetoxystyrene 9.1 g (0.056 mol), 4-methoxystyrene 1.9 g (0.014 mol) in 1-methoxy-2-propanol 70 ml solution for 2 hours It was dripped over. Two hours later, 50 mg of 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. The reaction solution was allowed to cool and then poured into 1 L of ion exchange water with vigorous stirring to precipitate a white resin. The obtained resin was dried and then dissolved in 100 mL of methanol. A 25% tetramethylammonium hydroxide aqueous solution was added to hydrolyze the acetoxy group in the resin, and then neutralized with an aqueous hydrochloric acid solution to precipitate a white resin. . After washing with ion-exchanged water and drying under reduced pressure, 11.6 g of resin a- (29) of the present invention was obtained.
When the molecular weight was measured by GPC, it was 9,200 in terms of weight average (Mw: polystyrene conversion) and 2.2 in terms of dispersity (Mw / Mn). The composition ratio was calculated by NMR measurement, and the molar ratio was x / y = 80/20.

(3-2) Synthesis of Resin a- (39) 12.0 g of poly (4-hydroxystyrene) (Mw = 10,500, Mw / Mn = 1.2) was dissolved in 100 ml of acetone, and 2.0 g of pyridine was dissolved. In addition, 1.3 g of acetic anhydride was added, and the mixture was reacted at 50 ° C. with stirring for 3 hours. The reaction solution was poured into 1 L of ion exchange water with vigorous stirring to precipitate a white resin. After the obtained resin was dried under reduced pressure, 12.2 g of the resin a- (39) of the present invention was obtained.
When the molecular weight was measured by GPC, it was 11,400 in terms of weight average (Mw: polystyrene conversion) and 1.2 in terms of dispersity (Mw / Mn). Further, the composition ratio was calculated by NMR measurement, and the molar ratio was x / y (4-hydroxystyrene / 4-acetoxystyrene) = 88/12.

(3-3) Synthesis of Resin a- (91)
2-[(4′-hydroxyphenyl) carbonyloxy] ethyl methacrylate 3.8 g (0.015 mol), 2-hydroxyethyl acrylate 1.0 g (0.009 mol), acrylonitrile 0.3 g (0.006 mol) Was dissolved in 30 ml of 1-methoxy-2-propanol, and polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) at 70 ° C. under a nitrogen stream and stirring. Trade name V-65) 50 mg, 2-[(4′-hydroxyphenyl) carbonyloxy] ethyl methacrylate 8.8 g (0.035 mol), 2-hydroxyethyl acrylate 2.4 g (0.021 mol), acrylonitrile A solution of 0.7 g (0.014 mol) of 1-methoxy-2-propanol in 70 ml was added dropwise over 2 hours. Two hours later, 50 mg of 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. The reaction solution was allowed to cool and then poured into 1 L of ion exchange 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, it was 11,000 in terms of weight average (Mw: polystyrene conversion) and 1.5 in terms of dispersity (Mw / Mn). The composition ratio was calculated by NMR measurement, and the molar ratio was x / y / z = 60/30/10.
Hereinafter, the resin of the present invention (BN) was synthesized in the same manner.

(4) Synthesis of Crosslinker (4-1) Synthesis of Crosslinker [HM-0] p-Aminophenol (1 mol) and sodium acetate (1 mol) are placed in a flask together with acetone (1 liter), and isobutyric acid chloride (1 mol) ) Is added dropwise under ice cooling. After 5 hours, the mixture was poured into ice water to precipitate crystals, and the crystals were collected by filtration to obtain HM-0-X at a yield of 80%.
HM-0-X (0.8 mol), KOH (0.8 mol), water 500 ml, 37% formalin aqueous solution (4.8 mol) were placed in a flask, heated at 50 ° C. for 5 hours, neutralized with acetic acid, Was concentrated in vacuo and the resulting oil was dissolved in ethyl acetate / methanol = 1/1 and separated by SiO ₂ column chromatography to obtain the desired product HM-0 (L ₁ = L ₂ = CH ₂ OH) as colorless crystals. As an overall yield of 50%.

(4-2) Synthesis of cross-linking agent [HM-1] 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene 20 g (Trisp-PA manufactured by Honshu Chemical Industry Co., Ltd.) was added to a 10% aqueous potassium hydroxide solution and stirred and dissolved. Next, 60 ml of 37% formalin aqueous solution was gradually added over 1 hour at room temperature while stirring this solution. The mixture was further stirred at room temperature for 6 hours, and then poured into a dilute sulfuric acid aqueous solution. The precipitate was filtered, sufficiently washed 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).

(4-3) Synthesis of cross-linking agent [MM-1] 20 g of the phenol derivative [HM-1] having a hydroxymethyl group obtained in the above synthesis example was added to 1 liter of methanol and dissolved by heating under stirring. Next, 1 ml of concentrated sulfuric acid was added to this solution and 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 then concentrated to dryness to obtain 22 g of a phenol derivative [MM-1] having a methoxymethyl group having the following structure as a white solid. The purity was 90% (liquid chromatography method).

Examples 1 to 17 and Comparative Examples 1 to 5
(1) Coating of resist composition
Alkali-soluble resin (BN) 2.0g
Total amount of acid generator 0.20g
Total amount of crosslinking agent (C) 0.35 g
0.0080 g of organic basic compound as required
0.0040g surfactant as needed
Was dissolved in a total amount of solvent of 18.0 g to prepare a negative resist composition of the present invention.

  Each sample solution was filtered through a 0.1 μm polytetrafluoroethylene filter, and then applied onto a silicon wafer subjected to hexamethyldisilazane treatment by a spin coater Mark8 manufactured by Tokyo Electron. Heat drying on the plate gave a resist film with a film thickness of 0.3 μm.

  In Table 3, resins a- (1), a- (2), a- (3), a- (25), a- (27), a- (29), a- (30), a- The composition (molar ratio) and molecular weight of (31), a- (32), a- (35), a- (39), a- (57), a- (91), a- (93) are as follows. Street.

a- (1) Mw = 15,000, Mw / Mn = 1.1
a- (2) Mw = 9,000, Mw / Mn = 1.2
a- (3) Mw = 8,000, Mw / Mn = 1.3
a- (25) x / y = 70: 30, Mw = 16,000, Mw / Mn = 1.5
a- (27) x / y = 80: 20, Mw = 9,500, Mw / Mn = 1.5
a- (29) x / y = 80: 20, Mw = 9,200, Mw / Mn = 2.2
a- (30) x / y = 80: 20, Mw = 12,000, Mw / Mn = 1.2
a- (31) x / y = 90: 10, Mw = 8,500, Mw / Mn = 1.3
a- (32) x / y = 75: 25, Mw = 9,000, Mw / Mn = 1.2
a- (35) x / y = 75: 25, Mw = 20,000, Mw / Mn = 2.1
a- (39) x / y = 88: 12, Mw = 11,400, Mw / Mn = 1.2
a- (57) x / y = 95: 5, Mw = 5,000, Mw / Mn = 1.2
a- (91) x / y / z = 60: 30: 10, Mw = 11,000, Mw / Mn = 1.5
a- (93) x / y = 85: 15, Mw = 9,300, Mw / Mn = 1.1

  The acid generators used in Table 3 are as follows.

The organic basic compound is as follows.
(1) 1,8-diazabicyclo [4.3.0] non-5-ene,
(2) 2,6-diisopropylaniline,
(3) 4-dimethylaminopyridine,
(4) 2,4,5-triphenylimidazole,
(5) piperazine,
(6) 1,5-diazabicyclo [4.3.0] non-5-ene,
(7) phenylguanidine,
(8) hexamethylenetetramine,
(9) CHMETU,

Surfactants are as follows.
W1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (fluorine-based),
W2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicone),
W3: polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.),
W4: polyoxyethylene triphenyl ether,
W5: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)

Solvents are as follows.
S1: propylene glycol monomethyl ether acetate,
S2: propylene glycol monomethyl ether propionate,
S3: ethyl lactate,
S4: Butyl acetate,
S5: 2-heptanone,
S6: propylene glycol monomethyl ether,
S7: Ethoxytylpropionate
S8: γ-butyrolactone,
S9: ethylene carbonate,
S10: propylene carbonate,
S11: cyclohexanone

(2) Creation of resist pattern This resist film was irradiated using an electron beam drawing apparatus (HL750 manufactured by Hitachi, acceleration voltage 50 KeV). After irradiation, each was heated on a vacuum adsorption hot plate at 110 ° C. for 60 seconds, immersed in an aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds and dried. The cross-sectional shape of a 0.15 μm (line: space) pattern was observed with a scanning electron microscope.

In addition, the sensitivity is defined as the minimum irradiation energy when resolving a 0.20 μm line (line: space = 1: 1), and the resolving power is the limiting resolution (line and space are separated and resolved) at that irradiation amount. . For a 0.20 μm line (line: space = 1: 1) not resolving, the resolving power was defined as the limiting resolving power.
The performance evaluation results are shown in Table 4.

The results in Table 4 indicate that the composition of the present invention has a high sensitivity, high resolution and rectangular profile, and has excellent performance.
Moreover, the same effect was obtained in the implementation using the X-ray drawing apparatus.

Claims (7)

(A1) A compound having a structure represented by the following general formula (1), (2) or (3) having a reduction potential higher than −0.78 V and generating an acid upon irradiation with actinic rays or radiation,
A negative resist composition for electron beam, EUV, or X-ray, comprising (BN) an alkali-soluble resin and (C) a crosslinking agent that is crosslinked with an acid.

In general formula (1),
Y represents an aryl group which may have a substituent or an alkyl group which may have a substituent.
R _{1a to} R _8a each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a carboxyl group, an optionally substituted alkyl group or an optionally substituted cycloalkyl group. Represents.

In general formulas (2) and (3),
R _{1 to} R ₁₅ each independently represents a hydrogen atom, a nitro group, a cyano group, or a trifluoromethyl group. However, at least two of R _{1 to} R ₁₅ are selected from a nitro group, a cyano group, and a trifluoromethyl group.
R _{16 to} R ₁₉ and R _{22 to} R ₂₇ each independently represent a hydrogen atom, a nitro group, a cyano group, a trifluoromethyl group, or a halogen atom.
X ^- it is,
At least one fluorine atom,
An alkyl group substituted with at least one fluorine atom,
An alkoxy group substituted with at least one fluorine atom,
An acyl group substituted with at least one fluorine atom,
An acyloxy group substituted with at least one fluorine atom,
A sulfonyl group substituted with at least one fluorine atom,
A sulfonyloxy group substituted with at least one fluorine atom,
A sulfonylamino group substituted with at least one fluorine atom,
An aryl group substituted with at least one fluorine atom,
An aralkyl group substituted with at least one fluorine atom, and an alkoxycarbonyl group substituted with at least one fluorine atom;
An anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from Furthermore, (A2) the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation which has a structure represented by the following general formula (I)-general formula (III) is contained. Negative resist composition for electron beam, EUV or X-ray.

In the general formulas (I) to (III),
R _{1 to} R ₃₇ are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, or a —S—R ₃₈ group. _R38 represents an alkyl group or an aryl group.
X ^- it is,
At least one fluorine atom,
An alkyl group substituted with at least one fluorine atom,
An alkoxy group substituted with at least one fluorine atom,
An acyl group substituted with at least one fluorine atom,
An acyloxy group substituted with at least one fluorine atom,
C ₄ F ₉ -SO ₂ - group,
C ₄ F ₉ -SO ₂ -NH- group,
An aryl group substituted with at least one fluorine atom,
An aralkyl group substituted with at least one fluorine atom, and an alkoxycarbonyl group substituted with at least one fluorine atom;
An anion of alkylsulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least one selected from   And (A3) containing at least one of a compound that generates a fluorine-containing carboxylic acid upon irradiation with actinic rays or radiation and (A4) a compound that generates a fluorine-free carboxylic acid upon irradiation with actinic rays or radiation. 3. A negative resist composition for electron beam, EUV or X-ray according to claim 1 or 2. The negative resist composition for electron beam, EUV or X-ray according to any one of claims 1 to 3, wherein the (BN) component resin has a repeating unit represented by the following general formula (a): object.

Where
R ₁ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or 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 have a hydrogen atom, a halogen atom, a cyano group, or a substituent, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl Represents a group.
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 —O—R ₆ — and —CO—N (R ₇ ) —R ₈ — are represented.
R ₅ , R ₆ and R ₈ may be the same or different and each may have a single bond or a substituent, an alkylene group, an alkenylene group, a cycloalkylene group, or an arylene group alone, or these groups And a divalent group formed by combining 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 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.
A plurality of R _{2 s} or R ₂ and R ₃ or R ₄ may combine to form a ring. (C) The crosslinking agent that crosslinks with an acid is at least one selected from compounds represented by the following general formulas (4) to (6) and alkoxymethylated melamine compounds: 5. A negative resist composition for electron beam, EUV or X-ray according to any one of 4 above.

In the general formulas (4) to (6), R _5b each independently represents a hydrogen atom, an alkyl group or an acyl group.
R _{6b to} R _9b in the general formula (4) each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, or an alkoxyl group.
X represents a single bond, a methylene group or an oxygen atom.   (C) The crosslinking agent that crosslinks with an acid is a phenol derivative having 1 to 6 benzene rings in the molecule, and has at least two hydroxymethyl groups and / or alkoxymethyl groups in the molecule, and these groups The negative resist composition for electron beam, EUV or X-ray according to any one of claims 1 to 5, which is a compound in which is bonded to any benzene ring atomic group.   A pattern formation comprising a step of forming a resist film from the negative resist composition according to claim 1, and exposing and developing the resist film with an electron beam, EUV, or X-ray. Method.