JP2003327560A - New anthracene derivative and radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new anthracene derivative as an additive for a radiation- sensitive resin composition useful for a chemical amplification resist optimally controlling the radiation transimmisivity and effectively suppressing a change in line breadth of a resist pattern due to fluctuation of film thickness of a resist film without especially deteriorating resolution performances and having excellent compatibility with other components in the composition with low sublimability. <P>SOLUTION: The anthracene derivative is represented by general formula (1) [wherein, R<SP>1</SP>s denote each a hydroxy group or a 1-20C monovalent organic group; n denotes an integer of 0-9; X denotes a single bond or a 1-12C bivalent organic group; and R<SP>2</SP>denotes a monovalent acid-dissociable group]. The radiation-sensitive resin composition comprises (A) the anthracene derivative, (B) an alkali-insoluble or a sparingly alkali-soluble resin which becomes readily soluble in alkalis in the presence of an acid and (C) a radiation-sensitive acid generator. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel anthracene derivative and a radiation-sensitive resin composition, and more specifically to far ultraviolet rays such as KrF excimer laser, ArF excimer laser or F ₂ excimer laser, synchrotron radiation and the like. Anthracene derivative which can be particularly preferably used as an additive of a radiation sensitive resin composition useful for a chemically amplified resist useful for microfabrication using various kinds of radiation such as charged particle beams such as X-rays and electron beams And a radiation-sensitive resin composition containing the anthracene derivative.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit devices, recently, in order to obtain a higher degree of integration, a lithography technique capable of microfabrication at a level of 0.20 μm or less is recently required. Has been done. However, in conventional lithographic processes, i
Near-ultraviolet rays such as lines are used, but it is said that with this near-ultraviolet rays, microfabrication at a subquarter micron level or less is extremely difficult. Therefore, 0.20μ
In order to enable fine processing at a level of m or less,
The use of shorter wavelength radiation is being considered. Examples of such short-wavelength radiation include bright line spectra of mercury lamps, deep ultraviolet rays represented by excimer lasers, and X-rays.
Ray, electron beam, etc.
Especially KrF excimer laser (wavelength 248 nm), Ar
The F excimer laser (wavelength 193 nm) or the F ₂ excimer laser (wavelength 157 nm) is drawing attention.
As the radiation-sensitive resin composition suitable for the radiation of the short wavelength, a component having an acid dissociative functional group and a radiation-sensitive acid generator that generates an acid by irradiation with radiation (hereinafter, referred to as “exposure”) A number of compositions utilizing the chemical amplification effect between the two (hereinafter referred to as "chemical amplification type radiation-sensitive composition") have been proposed. As the chemically amplified radiation-sensitive composition, for example, Japanese Patent Publication No. 27660/1990 discloses a polymer having a t-butyl ester group of a carboxylic acid or a t-butyl carbonate group of a phenol and a radiation-sensitive acid generator. A composition containing an agent has been proposed. In this composition, the t-butyl ester group or t-butyl carbonate group present in the polymer is dissociated by the action of the acid generated by exposure to light, and the polymer is acidified with a carboxyl group or a phenolic hydroxyl group. This utilizes a phenomenon in which a group is formed, and as a result, an exposed region of the resist film becomes easily soluble in an alkali developing solution.

By the way, in recent years, the photolithography process has been rapidly miniaturized, and particularly in the case of the lithography process by the KrF excimer laser, the limit resolution is about to be less than half of the light source wavelength. Therefore, the demands on the chemically amplified radiation-sensitive resin composition are becoming more and more strict, and not only higher resolution is required, but also substrates having various reflectances must be applicable. In particular, in order to deal with a substrate having a high reflectance, it is necessary to reduce the effect of standing waves and the effect of swing curves, and therefore control of the radiation transmittance is essential. In order to reduce the radiation transmittance, it is possible to increase the addition amount of the radiation-sensitive acid generator having a low radiation transmittance, but this method is not necessarily suitable for the performance as a resist, and the third component (for example, It is more preferable to add a dye or the like).

Therefore, in order to control the radiation transmittance of the chemically amplified radiation sensitive resin composition, it is preferable to add an anthracene compound as a dye.
It is proposed in Japanese Patent No. 155 and Japanese Patent Laid-Open No. 11-265061. However, simply adding a compound having a low radiation transmittance may cause a reduction in resolution and residual development, and there is a problem that the performance as a resist is impaired. Further, since the anthracene compound generally has a sublimation property, there is a problem that it adversely affects the exposure apparatus. Further, the anthracene-based compounds have a drawback that many compounds have insufficient compatibility with the resin components and additives contained in the chemically amplified radiation-sensitive resin composition. Further, in JP-A-10-120628, a tricyclic aromatic skeleton such as anthracene skeleton has a divalent hydrocarbon group or a carboxyl group bonded through an oxygen atom, and the carboxyl group is acid-labile. It is disclosed that a carboxylic acid derivative protected by a group has excellent light absorption and is suitable as an additive for a chemically amplified radiation-sensitive resin composition.

However, from the viewpoint of further technological development related to the photolithography process in which miniaturization is rapidly progressing and required performance is becoming more and more severe, a chemical amplification type radiation sensitive resin composition sensitive to far ultraviolet rays and the like is prepared. As an additive, it is still important to develop a new compound that can appropriately control the radiation transmittance, has a low sublimation property, and has excellent compatibility with other components in the radiation-sensitive resin composition. Has become a technical issue.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to provide a radiation-sensitive compound useful for a chemically amplified resist sensitive to actinic radiation, for example, deep ultraviolet rays represented by KrF excimer laser, ArF excimer laser or F ₂ excimer laser. As an additive to the resin composition, the radiation transmittance can be optimally controlled, and the line width change of the resist pattern due to the fluctuation of the resist film thickness can be effectively suppressed without particularly impairing the resolution performance. In addition, it is to provide a novel anthracene derivative having low sublimation property and excellent compatibility with other components in the composition.

[0007]

The present invention firstly comprises an anthracene derivative represented by the following general formula (1).

[Chemical 2] [In the general formula (1), R ^1's each independently represent a hydroxyl group or a monovalent organic group having 1 to 20 carbon atoms, a plurality of R ^1's may be the same or different, and n is 0. To an integer of 9 and X is a single bond or a carbon number of 1 to 12.
And a divalent organic group, and R ² represents a monovalent acid-dissociable group. ]

Secondly, the present invention is (A) an anthracene derivative represented by the general formula (1), and (B) an alkali-insoluble or sparingly alkali-soluble resin, which is easily soluble in an alkali in the presence of an acid. And a radiation-sensitive acid generator (C), which is a radiation-sensitive resin composition.

The present invention will be described in detail below. Anthracene derivative (1) The anthracene derivative in the present invention comprises the compound represented by the general formula (1) (hereinafter referred to as "anthracene derivative (1)").

In the general formula (1), R ¹ has 1 to ¹⁰ carbon atoms.
Examples of the monovalent organic group of 20 include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t
-C1-12 linear or branched alkyl group such as butyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1- A straight-chain or branched alkoxyl group having 1 to 12 carbon atoms such as methylpropoxy group and t-butoxy group; phenyl group, o-tolyl group, m-tolyl group,
p-tolyl group, 1-naphthyl group, 2-naphthyl group, 1-
6 carbon atoms such as anthracenyl group and 2-anthracenyl group
To 20 aryl groups; phenoxy groups, o-tolyloxy groups, m-tolyloxy groups, p-tolyloxy groups and other aryloxy groups having 6 to 20 carbon atoms.

R ¹ in the general formula (1) is preferably a hydroxyl group, a methyl group, an ethyl group, a methoxy group, a t-butoxy group, a phenyl group or the like. Further, n in the general formula (1) is preferably 0 to 2.

In the general formula (1), the carbon number of X is 1 to 1
Examples of the divalent organic group of 2 include a methylene group, 1,
1-ethylene group, 1,1-propylene group, 1,1-butylene group, 1,2-ethylene group, 1,2-propylene group,
1,2-butylene group, methylene group such as trimethylene group or linear or branched alkylene group having 2 to 12 carbon atoms; 1,4-phenylene group, 1,3-phenylene group,
1,2-phenylene group, 1,2-naphthylene group, 1,3
-Naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 1,8-naphthylene group, 2,6-naphthylene group, phenylmethylene group, Carbon number 6 such as 1-phenyl-1,2-ethylene group, 1-phenyl-1,2-propylene group
~ 12 arylene groups;

Methyleneoxy group such as methyleneoxy group, 1,1-ethyleneoxy group, 1,2-ethyleneoxy group, 1,2-propyleneoxy group, 1,2-butyleneoxy group, trimethyleneoxy group or carbon A linear or branched alkyleneoxy group having a number of 2 to 12; 1,4-phenyleneoxy group, 1,3-phenyleneoxy group, 1,
An aryleneoxy group having 6 to 12 carbon atoms such as a 2-phenyleneoxy group and a phenylmethyleneoxy group;

Methyleneoxymethyl group, 1,1-ethyleneoxymethyl group, 1,2-ethyleneoxymethyl group,
Trimethyleneoxymethyl group, 2- (methyleneoxy)
Methyleneoxymethyl group such as ethyl group or having 3 to 3 carbon atoms
12 linear or branched alkyleneoxyalkyl groups; carbon number of 1,4-phenyleneoxymethyl group, 1,3-phenyleneoxymethyl group, 1,2-phenyleneoxymethyl group, phenylmethyleneoxymethyl group, etc. 7
To 12 aryleneoxyalkyl groups and the like.

As X in the general formula (1), a methylene group, a 1,1-ethylene group, a 1,4-phenylene group, a methyleneoxy group and the like are preferable.

In the general formula (1), the monovalent acid-dissociable group for R ² is, for example, a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group or a straight chain group. A branched or cyclic alkoxycarbonyl group,
Examples thereof include linear, branched or cyclic acyl groups and cyclic acid dissociable groups.

Examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxymethoxymethyl group,
(2-Methoxyethoxy) methyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4-methoxyphenacyl group, 4-methylthiophenacyl group, α-methylphenacyl group, cyclopropyl Methyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, 4-bromobenzyl group, 4
-Nitrobenzyl group, 4-methoxybenzyl group, 4-methylthiobenzyl group, 4-ethoxybenzyl group, 4-ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, Examples thereof include i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group and t-butoxycarbonylmethyl group.

As the 1-substituted ethyl group, for example, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1 , 1-diethoxyethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1-cyclohexylthioethyl group,
1-phenoxyethyl group, 1-phenylthioethyl group,
1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group , 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-i-propoxycarbonylethyl group, 1-n-butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group and the like.

Further, as the 1-branched alkyl group,
For example, i-propyl group, 1-methylpropyl group, t-
Examples thereof include a butyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group and a 1,1-dimethylbutyl group. Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i.
-Propylsilyl group, t-butyldimethylsilyl group, methyldi-t-butylsilyl group, tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilyl group, triphenylsilyl group and the like can be mentioned.

The germyl group is, for example,
Trimethylgermyl group, ethyldimethylgermyl group, methyldiethylgermyl group, triethylgermyl group, i-
Propyldimethylgermyl group, methyldi-i-propylgermyl group, tri-i-propylgermyl group, t-butyldimethylgermyl group, methyldi-t-butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group Group, methyldiphenylgermyl group, triphenylgermyl group and the like. Examples of the linear, branched or cyclic alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group. Group, cyclopentyloxycarbonyl group,
Examples thereof include a cyclohexyloxycarbonyl group.

Examples of the linear, branched or cyclic acyl group include acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauroyl group and myristoyl group. Group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group,
Azela oil group, sebacoyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group,
Isophthaloyl group, terephthaloyl group, naphthoyl group,
Examples thereof include a toluoyl group, a hydroatropoyl group, an atropoyl group, a cinnamoyl group, a furoyl group, a thenoyl group, a nicotinoyl group, an isonicotinoyl group, a p-toluenesulfonyl group and a mesyl group.

Examples of the cyclic acid-dissociable group include cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, 4-methoxycyclohexyl group, 2-tetrahydropyranyl group, 2-tetrahydrofuranyl group, 2-tetrahydrothiopyranyl group, 2
-Tetrahydrothiofuranyl group, 3-bromo-2-tetrahydropyranyl group, 4-methoxy-2-tetrahydropyranyl group, 4-methoxy-2-tetrahydrothiopyranyl group, 3-tetrahydrothiophene-1,1- Dioxide group, 3-methylcyclopentyl group, 3-ethylcyclopentyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, norbornyl group, isobornyl group, dicyclopentenyl group, tricyclodecanyl group, tricyclododecenyl group Group, adamantyl group, adamantylmethyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group and the like.

Among these acid dissociable groups, t-butyl group, benzyl group, t-butoxycarbonylmethyl group, 1
-Methoxyethyl group, 1-ethoxyethyl group, trimethylsilyl group, t-butoxycarbonyl group, 2-tetrahydropyranyl group, 2-tetrahydrofuranyl group, 2-tetrahydrothiopyranyl group, 2-tetrahydrothiofuranyl group, 4 -Methylcyclohexyl group, 4-ethylcyclopentyl group, 2-methyl-2-adamantyl group and the like are preferable.

Examples of preferable anthracene derivative (1) include compounds represented by the following formula (1-a) or formula (1-b).

[0025]

[Chemical 3] In [Formula (1-a) and (1-b), R ² has the same meaning as R ² in the general formula (1). ]

Examples of the method for synthesizing the anthracene derivative (1) include a method in which a carboxylic acid having a corresponding anthracene skeleton is esterified in a suitable solvent with an acid catalyst or a base catalyst. Hereinafter, this method will be further described.

Synthetic Method (Esterification by Acid Catalyst) The anthracene derivative (1) is obtained by dissolving the corresponding carboxylic acid and the acid catalyst in a solvent and adding the corresponding olefin such as isobutene to effect esterification. You can Examples of the acid catalyst include p-toluenesulfonic acid and sulfuric acid. Examples of the solvent include dimethylformamide, dimethylacetamide, dimethylsulfoxide, t-butanol,
Acetone, acetonitrile, tetrahydrofuran, chloroform, methylene chloride and the like can be mentioned. The reaction conditions are such that the reaction temperature is usually -20 ° C to + 150 ° C, preferably 0 to 70 ° C, and the reaction time is usually 1 minute to
It is 96 hours, preferably 30 minutes to 48 hours.

Synthetic Method (Esterification with Base Catalyst) The anthracene derivative is prepared by dissolving the corresponding carboxylic acid and the base catalyst in a solvent and adding the corresponding bromoacetic acid ester such as t-butyl bromoacetate to effect esterification. (1) can be obtained. Examples of the base catalyst include super strong basic catalysts such as sodium amide, sodium hydride, n-butyllithium, and 1,8-diazabicyclo [5.4.0] -7-undecene;
Strongly basic catalysts such as methoxypotassium, ethoxypotassium and potassium t-butoxide; triethylamine, tri-n
-A weakly basic catalyst such as butylamine may be mentioned. Examples of the solvent include dimethylformamide,
Examples thereof include dimethylacetamide, dimethylsulfoxide, t-butanol, acetone, acetonitrile, tetrahydrofuran, chloroform and methylene chloride. The reaction conditions are such that the reaction temperature is usually -20 ° C to +1.
The temperature is 50 ° C., preferably 0 to 70 ° C., and the reaction time is generally 1 minute to 96 hours, preferably 30 minutes to 48 hours.

Since the anthracene derivative (1) has an anthracene skeleton, for example, the KrF excimer laser (248 nm) is shielded in the E1 absorption band, and the ArF excimer laser (193 nm) is shielded in the B absorption band. The radiation can be effectively absorbed at the wavelength of. Further, in the radiation-sensitive resin composition described later, the resolution performance does not decrease and the undeveloped residue does not occur, and the sublimation point of the compound (B-1) synthesized in Example 1 described below at atmospheric pressure is 200, for example. Since it has a high sublimation point and has a large number of polar sites as it is at or above 0 ° C, it is also excellent in compatibility with other components constituting the radiation-sensitive resin composition.
Therefore, the anthracene derivative (1) can be very suitably used as an additive for optimally controlling the radiation transmittance of the radiation-sensitive resin composition, and is also useful as an intermediate for synthesizing various anthracene derivatives. Is.

Radiation-Sensitive Resin Composition The radiation-sensitive resin composition in the present invention is (A) anthracene derivative (1), (B) an alkali-insoluble or sparingly alkali-soluble resin, which is easily dissolved in the presence of an acid. It is characterized by containing a soluble resin (hereinafter referred to as "resin (B)") and (C) a radioactive acid generator (hereinafter referred to as "acid generator (C)"). is there. The term "alkali-insoluble or alkali-insoluble" as used herein means
Only the resin (B) is used in place of the resist coating under the alkaline developing conditions adopted when forming a resist pattern from the resist coating formed from the radiation-sensitive resin composition described below containing the resin (B). When the used coating is developed, it means that 50% or more of the initial thickness of the coating remains after the development.

-(A) Anthracene derivative (1) -In the radiation-sensitive resin composition of the present invention, the anthracene derivative (1) may be used alone or in combination of two or more kinds. In the radiation-sensitive resin composition of the present invention, the amount of the anthracene derivative (1) used is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, per 100 parts by weight of the resin (B). And particularly preferably 0.2 to 10 parts by weight. In this case, if the amount of the anthracene derivative (1) used is less than 0.1 parts by weight, it tends to be difficult to appropriately suppress the radiation transmittance of the resulting composition, while if it exceeds 20 parts by weight, The radiation transmittance of the obtained composition tends to be too small, and the sensitivity tends to be lowered.

-Resin (B) -The resin (B) is not particularly limited as long as it is an alkali-insoluble or sparingly alkali-soluble resin and becomes a readily alkali-soluble resin in the presence of an acid. For example, a resin in which the acidic functional group in an alkali-soluble resin having an acidic functional group such as a phenolic hydroxyl group or a carboxyl group is protected by an acid dissociable group can be exemplified. Examples of the preferred resin (B) in the present invention include a repeating unit represented by the following general formula (2) (hereinafter referred to as “repeating unit (2)”) and a repeating unit having an acid dissociable group (hereinafter referred to as “repeating unit”). It is called "acid dissociable repeating unit".)
And a resin (hereinafter, referred to as “resin (B1)”). The resin (B1) is particularly suitable for a radiation sensitive resin composition using a KrF excimer laser.

[0033]

[Chemical 4] [In the general formula (2), R ³ represents a hydrogen atom or a monovalent organic group (provided that an acid dissociable group is excluded), and i is 1 to 1).
An integer of 3 and j is an integer of 0 to 3 and satisfies (i + j) ≦ 5. ]

In the general formula (2), the monovalent organic group for R ³ is, for example, the same as the group exemplified for the monovalent organic group having 1 to 20 carbon atoms for R ¹ in the general formula (1). You can list the following. Of these organic groups, the methyl group is particularly preferable. In the general formula (2), i is preferably 1 to 3, and j is preferably 0 or 1.

The repeating unit (2) is, for example, 4
-Hydroxystyrene, 3-hydroxystyrene, 2-
Hydroxystyrene, α-methyl-4-hydroxystyrene, α-methyl-3-hydroxystyrene, α-methyl-2-hydroxystyrene, 3-methyl-4-hydroxystyrene, 2-methyl-4-hydroxystyrene,
2-methyl-3-hydroxystyrene, 4-methyl-3
-Hydroxystyrene, 5-methyl-3-hydroxystyrene, 3,4-dihydroxystyrene, 2,4,6-
A unit derived from trihydroxystyrene or the like is preferable.
Among these repeating units (2), 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, α-methyl-4-hydroxystyrene, α-methyl-3-hydroxystyrene, α-methyl-2-hydroxy. Units derived from styrene and the like are more preferable. In the resin (B), the repeating unit (2) is used alone or 2
There can be more than one species.

Examples of the acid dissociable repeating unit include 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, α-methyl-4-hydroxystyrene, α-methyl-3-hydroxystyrene,
Substituted methyl group, 1-substituted, in which the phenolic hydroxyl group or carboxyl group such as α-methyl-2-hydroxystyrene or (meth) acrylic acid is exemplified as the monovalent acid dissociable group represented by R ² in the general formula (1). Ethyl group, 1
A unit derived from a compound protected by a branched alkyl group, a triorganosilyl group, a triorganogermyl group, an alkoxycarbonyl group, an acyl group, a cyclic acid dissociable group and the like can be mentioned.

Of these acid dissociable groups, t-butyl group, benzyl group, t-butoxycarbonylmethyl group, 1
-Methoxyethyl group, 1-ethoxyethyl group, trimethylsilyl group, t-butoxycarbonyl group, 2-tetrahydropyranyl group, 2-tetrahydrofuranyl group, 2-tetrahydrothiopyranyl group, 2-tetrahydrothiofuranyl group, etc. preferable. In the resin (B), the acid dissociable repeating unit may be present alone or in combination of two or more.

The resin (B) may have a repeating unit other than the repeating unit (2) and the acid dissociable repeating unit (hereinafter referred to as "other repeating unit"). Examples of other repeating units include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene,
4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4- (2-t-)
Butoxycarbonylethyloxy) styrene and other vinyl aromatic compounds;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate, (meth) acrylic acid n-pentyl, n-hexyl (meth) acrylate, (meth) acrylic acid 2-
Ethylhexyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
3-hydroxypropyl (meth) acrylate, (meth)
Phenyl acrylate, phenethyl (meth) acrylate,

Monomer represented by the following formula (3)

[Chemical 5] [In Formula (3), k is an integer of 1-6. ],

Monomer represented by the following formula (4)

[Chemical 6] [In Formula (4), k is an integer of 1-6. ],

Monomer represented by the following formula (5)

[Chemical 7] [In Formula (5), each k is an integer of 1 to 6 independently of each other. ] (Meth) acrylic acid esters such as;

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and cinnamic acid;
Carboxyalkyl esters of unsaturated carboxylic acids such as 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate; (meth) acrylonitrile,
unsaturated nitrile compounds such as α-chloroacrylonitrile, crotonnitrile, malein nitrile and fumaronitrile; unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramide; maleimide, Unsaturated imide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide; N-vinyl-ε-caprolactam, N-vinylpyrrolidone, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, 4 Examples thereof include units derived from other nitrogen-containing vinyl compounds such as vinylimidazole.

Among these other repeating units, styrene, α-methylstyrene, 4- (2-t-butoxycarbonylethyloxy) styrene, the monomer represented by the above formula (3) and the above formula (4) A unit derived from a monomer or the like represented by (4) is preferable. In the resin (B), other repeating units may be used alone or in combination of two or more.

As the resin (B), a resin having a main chain derived from norbornenes and / or (meth) acrylic acid esters and having an acid dissociable group can also be preferably used. This resin is suitably used for a radiation sensitive resin composition using an ArF excimer laser.

The rate of introduction of the acid-dissociable group in the resin (B) (the ratio of the number of acid-dissociable groups to the total number of unprotected acidic functional groups and acid-dissociable groups in the resin (B)) is Although it cannot be unconditionally specified depending on the kind of the acid-dissociable group and the alkali-soluble resin into which the group is introduced, it is preferably 10 to 10
It is 0%, more preferably 15 to 100%.

The polystyrene-equivalent weight molecular weight (hereinafter referred to as "Mw") of the resin (B) measured by gel permeation chromatography (GPC) is preferably 1,000 to 150,000, more preferably 3,0.
00 to 100,000. Also, the Mw of the resin (B)
And gel permeation chromatography (GPC)
Polystyrene equivalent number molecular weight measured by
Say. ) And the ratio (Mw / Mn) is usually 1 to 10,
It is preferably 1 to 5.

-Acid Generator (C) -As the acid generator (C), for example, a sulfonimide compound, an onium salt compound, a sulfone compound, a sulfonate compound, a disulfonyldiazomethane compound, a disulfonylmethane compound, an oximesulfonate. Examples thereof include compounds and hydrazine sulfonate compounds.
Hereinafter, examples of these acid generators (C) will be shown. Sulfonimide Compounds Examples of sulfonimide compounds include compounds represented by the following general formula (6).

[0049]

[Chemical 8] [In the general formula (6), R ⁴ represents a monovalent organic group,
R ⁵ represents a divalent organic group. ]

Specific examples of the sulfonimide compound include:
N- (trifluoromethanesulfonyloxy) succinimide, N- (trifluoromethanesulfonyloxy)
Phthalimide, N- (trifluoromethanesulfonyloxy) diphenylmaleimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoro Rmethanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) naphthylimide, N- (10-
Camphorsulfonyloxy) succinimide, N-
(10-camphorsulfonyloxy) phthalimide,
N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1
0-camphorsulfonyloxy) bicyclo [2.2.
1] heptane-5,6-oxy-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide,

N- (n-octanesulfonyloxy) succinimide, N- (n-octanesulfonyloxy)
Phthalimide, N- (n-octanesulfonyloxy)
Diphenylmaleimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (n-octanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(N-Octanesulfonyloxy) bicyclo [2.2.
1] Heptane-5,6-oxy-2,3-dicarboximide, N- (n-octanesulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) succinimide, N- (p-toluenesulfonyloxy) Phthalimide, N- (p-toluenesulfonyloxy) diphenylmaleimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N- (p-toluenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-
Toluenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide,

N- (2-trifluoromethylbenzenesulfonyloxy) succinimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide,
N- (2-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- (2-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2 -Trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4-trifluoromethylbenzenesulfonyloxy) succinimide, N- (4-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) ) Diphenylmaleimide, N- (4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-Dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-
5,6-oxy-2,3-dicarboximide, N-
(4-trifluoromethylbenzenesulfonyloxy)
Naphthyl imide,

N- (perfluorobenzenesulfonyloxy) succinimide, N- (perfluorobenzenesulfonyloxy) phthalimide, N- (perfluorobenzenesulfonyloxy) diphenylmaleimide, N-
(Perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluorobenzenesulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5
Ene-2,3-dicarboximide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1]
Heptane-5,6-oxy-2,3-dicarboximide, N- (perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) succinimide, N- (1-naphthalenesulfonyloxy) phthalimide, N- (1-naphthalenesulfonyloxy) diphenylmaleimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 1-naphthalenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,
3-dicarboximide, N- (1-naphthalenesulfonyloxy) naphthylimide,

N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (nonafluoro-n-
Butanesulfonyloxy) phthalimide, N- (nonafluoro-n-butanesulfonyloxy) diphenylmaleimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) -7-oxabicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-di Carboximide, N- (nonafluoro-
n-butanesulfonyloxy) naphthylimide, N-
(Perfluoro-n-octanesulfonyloxy) succinimide, N- (perfluorooctanesulfonyloxy) phthalimide, N- (perfluoro-n-octanesulfonyloxy) diphenylmaleimide, N- (perfluoro-n-octanesulfonyloxy) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5- Ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (per Fluoro-n-octanesulfonyloxy) naphthylimide, N- (benzenesulfonyloxy) su Cinimide, N- (benzenesulfonyloxy) phthalimide, N- (benzenesulfonyloxy) diphenylmaleimide, N- (benzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(Benzenesulfonyloxy) bicyclo [2.2.1]
Heptane-5,6-oxy-2,3-dicarboximide, N- (benzenesulfonyloxy) naphthylimide and the like can be mentioned.

Onium salt compound: Examples of the onium salt compound include iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt and pyridinium salt. Specific examples of the onium salt compound include bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate and bis (4
-T-butylphenyl) iodonium nonafluoro-n
-Butane sulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octane sulfonate, bis (4-t-butylphenyl) iodonium pyrene sulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzene sulfonate , Bis (4-t-butylphenyl) iodonium p-toluene sulfonate, bis (4-t-butylphenyl) iodonium benzene sulfonate, bis (4-t-butylphenyl) iodonium 10-camphor sulfonate,
Bis (4-t-butylphenyl) iodonium n-octane sulfonate, bis (4-t-butylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium 4-
Trifluoromethylbenzene sulfonate, bis (4-
t-butylphenyl) iodonium perfluorobenzenesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, Diphenyliodonium p-toluene sulfonate, diphenyliodonium benzene sulfonate, diphenyl iodonium 10-camphor sulfonate, diphenyl iodonium n-octane sulfonate, diphenyl iodonium 2-trifluoromethylbenzene sulfonate, diphenyl iodonium 4-trifluoromethylbenzene sulfonate, diphenyl iodonium E sulfonyl iodonium perfluoro sulfonate,

Di (p-toluyl) iodonium trifluoromethanesulfonate, di (p-toluyl) iodonium nonafluoro-n-butanesulfonate, di (p-
Toluyl) iodonium perfluoro-n-octane sulfonate, di (p-toluyl) iodonium pyrene sulfonate, di (p-toluyl) iodonium n-dodecylbenzene sulfonate, di (p-toluyl) iodonium p-toluene sulfonate, di (p- Toluil)
Iodonium benzene sulfonate, di (p-toluyl) iodonium 10-camphor sulfonate, di (p-toluyl) iodonium n-octane sulfonate, di (p-toluyl) iodonium 2-trifluoromethylbenzene sulfonate, di (p-toluyl) iodonium 4-trifluoromethylbenzenesulfonate, di (p-toluyl) iodonium perfluorobenzenesulfonate, di (3,4-dimethylphenyl) iodonium trifluoromethanesulfonate, di (3,3
4-dimethylphenyl) iodonium nonafluoro-n
-Butane sulfonate, di (3,4-dimethylphenyl) iodonium perfluoro-n-octane sulfonate, di (3,4-dimethylphenyl) iodonium pyrene sulfonate, di (3,4-dimethylphenyl) iodonium n-dodecylbenzene sulfonate , Di (3,4-dimethylphenyl) iodonium p-toluenesulfonate, di (3,4-dimethylphenyl) iodonium benzenesulfonate, di (3,4-dimethylphenyl) iodonium 10-camphorsulfonate, di (3,4- Dimethylphenyl) iodonium n-
Octane sulfonate, di (3,4-dimethylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (3,4-dimethylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, di (3,4-dimethylphenyl) iodonium per Fluorobenzene sulfonate,

4-nitrophenyl phenyliodonium trifluoromethane sulfonate, 4-nitrophenyl phenyliodonium nonafluoro-n-butane sulfonate, 4-nitrophenyl phenyliodonium perfluoro-n-octane sulfonate, 4-nitrophenyl phenyl Iodonium pyrene sulfonate, 4-nitrophenyl phenyliodonium n-dodecylbenzene sulfonate, 4-nitrophenyl phenyliodonium p-toluene sulfonate, 4-nitrophenyl phenyliodonium benzene sulfonate, 4-nitrophenyl phenyliodonium 10
-Camphor sulfonate, 4-nitrophenyl phenyliodonium n-octane sulfonate, 4-nitrophenyl phenyliodonium 2-trifluoromethylbenzene sulfonate, 4-nitrophenyl phenyliodonium 4-trifluoromethylbenzene sulfonate, 4-nitrophenyl -Phenyliodonium perfluorobenzenesulfonate, di (3-nitrophenyl) iodonium trifluoromethanesulfonate, di (3-nitrophenyl) iodonium nonafluoro-n-butanesulfonate, di (3-nitrophenyl) iodonium perfluoro-n-octane Sulfonate, di (3-nitrophenyl) iodonium pyrene sulfonate, di (3-nitrophenyl) iodonium n
-Dodecylbenzenesulfonate, di (3-nitrophenyl) iodonium p-toluenesulfonate, di (3
-Nitrophenyl) iodonium benzene sulfonate, di (3-nitrophenyl) iodonium 10-camphor sulfonate, di (3-nitrophenyl) iodonium n-octane sulfonate, di (3-nitrophenyl) iodonium 2-trifluoromethylbenzene sulfonate, Di (3-nitrophenyl) iodonium 4
-Trifluoromethylbenzene sulfonate, di (3-
(Nitrophenyl) iodonium perfluorobenzenesulfonate,

4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium nonafluoro-n-butanesulfonate, 4-methoxyphenylphenyliodonium perfluoro-n-octanesulfonate, 4
-Methoxyphenyl phenyliodonium pyrene sulfonate, 4-methoxyphenyl phenyliodonium n-dodecylbenzene sulfonate, 4-methoxyphenyl phenyliodonium p-toluene sulfonate, 4-methoxyphenyl phenyliodonium benzene sulfonate, 4-methoxyphenyl phenyl Iodonium 10-camphor sulfonate, 4-methoxyphenyl phenyliodonium n-octane sulfonate, 4-methoxyphenyl phenyliodonium 2-trifluoromethylbenzene sulfonate, 4-methoxyphenyl phenyliodonium 4-trifluoromethylbenzene sulfonate, 4- Methoxyphenyl / phenyliodonium perfluorobenzenesulfonate, di (4-qua Rofeniru) iodonium trifluoromethanesulfonate, di (4-chlorophenyl) iodonium nonafluoro -n- butane sulfonate, di (4-chlorophenyl) iodonium perfluoro -n
-Octane sulfonate, di (4-chlorophenyl) iodonium pyrene sulfonate, di (4-chlorophenyl) iodonium n-dodecylbenzene sulfonate,
Di (4-chlorophenyl) iodonium p-toluene sulfonate, di (4-chlorophenyl) iodonium benzene sulfonate, di (4-chlorophenyl) iodonium 10-camphor sulfonate, di (4-chlorophenyl) iodonium n-octane sulfonate, di (4- Chlorophenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (4-chlorophenyl) iodonium 4-trifluoromethylbenzenesulfonate, di (4-chlorophenyl) iodonium perfluorobenzenesulfonate,

Di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-
Trifluoromethylphenyl) iodonium nonafluoro-n-butane sulfonate, di (4-trifluoromethylphenyl) iodonium perfluoro-n-octane sulfonate, di (4-trifluoromethylphenyl) iodonium pyrene sulfonate, di (4-tri Fluoromethylphenyl) iodonium n-dodecylbenzenesulfonate, di (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, di (4-
Trifluoromethylphenyl) iodonium benzene sulfonate, di (4-trifluoromethylphenyl) iodonium 10-camphor sulfonate, di (4-trifluoromethylphenyl) iodonium n-octane sulfonate, di (4-trifluoromethylphenyl)
Iodonium 2-trifluoromethylbenzenesulfonate, di (4-trifluoromethylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, di (4-trifluoromethylphenyl) iodonium perfluorobenzenesulfonate, di (1-naphthyl) iodonium trifluoro Rmethanesulfonate, di (1-
Naphthyl) iodonium nonafluoro-n-butane sulfonate, di (1-naphthyl) iodonium perfluoro-n-octane sulfonate, di (1-naphthyl) iodonium pyrene sulfonate, di (1-naphthyl) iodonium n-dodecylbenzene sulfonate, di (1
-Naphthyl) iodonium p-toluenesulfonate,
Di (1-naphthyl) iodonium benzene sulfonate, dinaphthyl iodonium 10-camphor sulfonate, di (1-naphthyl) iodonium n-octane sulfonate, di (1-naphthyl) iodonium 2-trifluoromethylbenzene sulfonate, di (1-naphthyl) ) Iodonium 4-trifluoromethylbenzenesulfonate, di (1-naphthyl) iodonium perfluorobenzenesulfonate,

Biphenylene iodonium trifluoromethane sulfonate, biphenylene iodonium nonafluoro-n-butane sulfonate, biphenylene iodonium perfluoro-n-octane sulfonate, biphenylene iodonium pyrene sulfonate, biphenylene iodonium n-dodecyl benzene sulfonate, biphenylene iodonium p-toluene sulfonate, biphenylene Iodonium benzene sulfonate, biphenylene iodonium 10-camphor sulfonate, biphenylene iodonium n-octane sulfonate, biphenylene iodonium 2-trifluoromethylbenzene sulfonate, biphenylene iodonium 4-trifluoromethylbenzene sulfonate, biphenylene iodonium perfluor Benzene sulfonate, 2-chlorobiphenylene iodonium trifluoromethane sulfonate, 2-chlorobiphenylene iodonium nonafluoro-n-butane sulfonate, 2-chlorobiphenylene iodonium perfluoro-n-octane sulfonate, 2-chlorobiphenylene iodonium pyrene sulfonate, 2-chlorobiphenylene Iodonium n-dodecylbenzene sulfonate, 2-chlorobiphenylene iodonium p-toluene sulfonate, 2-chlorobiphenylene iodonium benzene sulfonate, 2-chlorobiphenylene iodonium 10-camphor sulfonate, 2-chlorobiphenylene iodonium n-octane sulfonate, 2-chlorobiphenylene iodonium 2-trifluoromethylbenzenesul Sulfonate, 2-chloro-biphenylene iodonium 4-trifluoromethyl benzenesulfonate, 2-chloro-biphenylene iodonium perfluoro sulfonate,

Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium pyrenesulfonate, triphenylsulfonium n-dodecylbenzenesulfonate, triphenylsulfonium p-toluene sulfonate, triphenyl sulfonium benzene sulfonate, triphenyl sulfonium 10-camphor sulfonate, triphenyl sulfonium n-octane sulfonate, triphenyl sulfonium 2-trifluoromethylbenzene sulfonate, triphenyl sulfonium 4-trifluoromethyl benzene sulfonate, tri Phenylsulfonium hexaflu Roanchimoneto, triphenylsulfonium 1-naphthalenesulfonate, triphenylsulfonium perfluoro benzene sulfonate, 4-
t-Butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyl diphenylsulfonium perfluoro-n-octanesulfonate, 4-t
-Butylphenyl diphenylsulfonium pyrene sulfonate, 4-t-butylphenyl diphenylsulfonium n-dodecylbenzene sulfonate, 4-t-butylphenyl diphenylsulfonium p-toluene sulfonate, 4-t-butylphenyl diphenylsulfonium benzene sulfonate, 4-t-butylphenyl diphenylsulfonium 10-camphorsulfonate, 4-t-butylphenyl diphenylsulfonium n-octanesulfonate, 4-t-butylphenyl diphenylsulfonium 2-trifluoromethylbenzenesulfonate, 4-t-butyl Phenyl / diphenylsulfonium 4-trifluoromethanebenzenesulfonate, 4-t-butylphenyl / diphenylsulfonium perfluoro Down Zen sulfonate,

4-t-butoxyphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-
Butoxyphenyl diphenylsulfonium nonafluoro-n-butane sulfonate, 4-t-butoxyphenyl diphenylsulfonium perfluoro-n-octane sulfonate, 4-t-butoxyphenyl diphenylsulfonium pyrene sulfonate, 4-t-butoxyphenyl diphenyl Sulfonium n-dodecylbenzene sulfonate, 4-t-butoxyphenyl diphenylsulfonium p-toluene sulfonate, 4-t-butoxyphenyl diphenylsulfonium benzene sulfonate, 4-t-butoxyphenyl diphenylsulfonium 10-camphor sulfonate, 4-t -Butoxyphenyl diphenylsulfonium n-octane sulfonate, 4-t-butoxyphenyl diphenylsulfonium 2-to Fluoro-methylbenzenesulfonate, 4-t-butoxyphenyl · diphenylsulfonium 4-trifluoromethylbenzenesulfonate, 4-
t-Butoxyphenyl diphenylsulfonium perfluorobenzene sulfonate, 4-hydroxyphenyl diphenylsulfonium trifluoromethane sulfonate, 4-hydroxyphenyl diphenylsulfonium nonafluoro-n-butane sulfonate, 4-hydroxyphenyl diphenylsulfonium perfluoro-
n-octane sulfonate, 4-hydroxyphenyl
Diphenylsulfonium pyrene sulfonate, 4-hydroxyphenyl diphenylsulfonium n-dodecylbenzene sulfonate, 4-hydroxyphenyl diphenylsulfonium p-toluene sulfonate, 4-hydroxyphenyl diphenylsulfonium benzene sulfonate, 4-hydroxyphenyl diphenylsulfonium 10-camphor Sulfonate, 4-hydroxyphenyl diphenylsulfonium n-octane sulfonate, 4-hydroxyphenyl diphenylsulfonium 2-trifluoromethylbenzene sulfonate,
4-hydroxyphenyl diphenylsulfonium 4-
Trifluoromethylbenzene sulfonate, 4-hydroxyphenyl diphenylsulfonium perfluorobenzene sulfonate,

Tri (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-methoxyphenyl) sulfonium nonafluoro-n-butanesulfonate, tri (4-methoxyphenyl) sulfonium perfluoro-n-octanesulfonate, tri (4
-Methoxyphenyl) sulfonium pyrene sulfonate, tri (4-methoxyphenyl) sulfonium n-dodecylbenzene sulfonate, tri (4-methoxyphenyl) sulfonium p-toluene sulfonate, tri (4-methoxyphenyl) sulfonium benzene sulfonate, tri (4- Methoxyphenyl) sulfonium 1
0-camphorsulfonate, tri (4-methoxyphenyl) sulfonium n-octanesulfonate, tri (4-methoxyphenyl) sulfonium 2-trifluoromethylbenzenesulfonate, tri (4-methoxyphenyl) sulfonium 4-trifluoromethylbenzenesulfonate, Tri (4-methoxyphenyl) sulfonium perfluorobenzene sulfonate, di (methoxyphenyl) .p-toluylsulfonium trifluoromethanesulfonate, di (methoxyphenyl) .p-toluylsulfonium nonafluoro-n-butanesulfonate, di (methoxyphenyl) -P-toluylsulfonium perfluoro-n-octane sulfonate, di (methoxyphenyl) -p-toluylsulfonium pyrene sulfonate, di (meth) Cyphenyl) / p-toluylsulfonium n-dodecylbenzene sulfonate, di (methoxyphenyl) / p-toluylsulfonium p-toluenesulfonate, di (methoxyphenyl) / p-toluylsulfonium benzenesulfonate, di (methoxyphenyl) / p-toluyl Sulfonium 10-camphorsulfonate, di (methoxyphenyl) .p-toluylsulfonium n-octanesulfonate, di (methoxyphenyl) .p-toluylsulfonium 2-trifluoromethylbenzenesulfonate, di (methoxyphenyl) .p-toluylsulfonium 4 -Trifluoromethylbenzenesulfonate, di (methoxyphenyl) p
-Toluylsulfonium perfluorobenzene sulfonate,

Phenyl tetramethylene sulfonium trifluoromethane sulfonate, phenyl tetramethylene sulfonium nonafluoro-n-butane sulfonate, phenyl tetramethylene sulfonium perfluoro-n-octane sulfonate, phenyl tetramethylene sulfonium pyrene sulfonate, phenyl tetramethylene Sulfonium n-dodecylbenzene sulfonate, phenyl tetramethylene sulfonium p-toluene sulfonate, phenyl tetramethylene sulfonium benzene sulfonate, phenyl tetramethylene sulfonium 10-camphor sulfonate, phenyl tetramethylene sulfonium n-octane sulfonate, phenyl tetramethylene sulfonium 2-trifluoromethylben Sulfonate, phenyl tetramethylene sulfonium 4-trifluoromethylbenzene sulfonate, phenyl tetramethylene sulfonium perfluorobenzene sulfonate, 4-hydroxyphenyl tetramethylene sulfonium trifluoromethane sulfonate, 4-hydroxyphenyl tetramethylene sulfonium nonafluoro-n -Butane sulfonate, 4-hydroxyphenyl tetramethylene sulfonium perfluoro-n-octane sulfonate, 4-hydroxyphenyl tetramethylene sulfonium pyrene sulfonate, 4-hydroxyphenyl tetramethylene sulfonium n-dodecylbenzene sulfonate
-Hydroxyphenyl tetramethylene sulfonium p
-Toluene sulfonate, 4-hydroxyphenyl tetramethylene sulfonium benzene sulfonate, 4-
Hydroxyphenyl tetramethylene sulfonium 10
-Camphor sulfonate, 4-hydroxyphenyl
Tetramethylene sulfonium n-octane sulfonate, 4-hydroxyphenyl tetramethylene sulfonium 2-trifluoromethylbenzene sulfonate, 4
-Hydroxyphenyl tetramethylene sulfonium 4
-Trifluoromethylbenzene sulfonate, 4-hydroxyphenyl tetramethylene sulfonium perfluorobenzene sulfonate,

Phenyl biphenylene sulfonium trifluoromethane sulfonate, phenyl biphenylene sulfonium nonafluoro-n-butane sulfonate,
Phenyl biphenylene sulfonium perfluoro-n
Octane sulfonate, phenyl biphenylene sulfonium pyrene sulfonate, phenyl biphenylene sulfonium n-dodecylbenzene sulfonate, phenyl biphenylene sulfonium p-toluene sulfonate, phenyl biphenylene sulfonium benzene sulfonate, phenyl biphenylene sulfonium 10
-Camphor sulfonate, phenyl biphenylene sulfonium n-octane sulfonate, phenyl biphenylene sulfonium 2-trifluoromethylbenzene sulfonate, phenyl biphenylene sulfonium 4
-Trifluoromethylbenzene sulfonate, phenyl biphenylene sulfonium perfluorobenzene sulfonate, (4-phenylthiophenyl) diphenylsulfonium trifluoromethane sulfonate, (4-
(Phenylthiophenyl) / diphenylsulfonium nonafluoro-n-butanesulfonate, (4-phenylthiophenyl) / diphenylsulfonium perfluoro-
n-octane sulfonate, (4-phenylthiophenyl) / diphenylsulfonium pyrene sulfonate,
(4-phenylthiophenyl) -diphenylsulfonium n-dodecylbenzene sulfonate, (4-phenylthiophenyl) -diphenylsulfonium p-toluenesulfonate, (4-phenylthiophenyl) -diphenylsulfonium benzenesulfonate, (4-phenylthiophenyl) ). Diphenylsulfonium 10-camphorsulfonate, (4-phenylthiophenyl).
Diphenylsulfonium n-octane sulfonate,
(4-phenylthiophenyl) -diphenylsulfonium 2-trifluoromethylbenzenesulfonate, (4
-Phenylthiophenyl) / diphenylsulfonium 4
-Trifluoromethylbenzenesulfonate, (4-phenylthiophenyl) / diphenylsulfonium perfluorobenzenesulfonate,

4,4'-bis (diphenylsulfoniophenyl) sulfide di (trifluoromethanesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide di (nonafluoro-n-butanesulfonate), 4,4'-bis (Diphenylsulfoniophenyl) sulfide di (perfluoro-n-octane sulfonate), 4,4′-bis (diphenylsulfoniophenyl) sulfide di (pyrene sulfonate), 4,4 ′
-Bis (diphenylsulfoniophenyl) sulfide di (n-dodecylbenzene sulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide di (p
-Toluenesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide di (benzenesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide di (10-camphorsulfonate), 4,4'-bis ( Diphenylsulfoniophenyl) sulfide di (n-octane sulfonate), 4,
4'-bis (diphenylsulfoniophenyl) sulfide di (2-trifluoromethylbenzenesulfonate), 4,4'-bis (diphenylsulfoniophenyl) sulfide di (4-trifluoromethylbenzenesulfonate), 4,4'-bis (Diphenylsulfoniophenyl) sulfide di (perfluorobenzene sulfonate) and the like can be mentioned.

Sulfone compound: Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and these α-diazo compounds. Specific examples of the sulfone compound include phenacylphenyl sulfone, mesitylphenacyl sulfone, bis (phenylsulfonyl) methane, and 4-trisphenacyl sulfone. Sulfonic acid ester compound: Examples of the sulfonic acid ester compound include alkyl sulfonic acid ester, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, imino sulfonate and the like.
Specific examples of the sulfonate compound include benzoin tosylate, pyrogallol tris (trifluoromethane sulfonate), pyrogallol tris (nonafluoro-n-butane sulfonate), pyrogallol tris (methane sulfonate), nitrobenzyl-9,10-diethoxyanthracene. -2-sulfonate, α-methylolbenzoin tosylate, α-methylolbenzoin n
-Octane sulfonate, α-methylol benzoin trifluoromethane sulfonate, α-methylol benzoin n-dodecane sulfonate and the like can be mentioned.

Disulfonyldiazomethane compound: Examples of the disulfonyldiazomethane compound include compounds represented by the following general formula (7).

[0069]

[Chemical 9] [In the general formula (7), R ⁶ and R ⁷ are each independently an alkyl group, an aryl group, a halogen-substituted alkyl group,
A monovalent group such as a halogen-substituted aryl group is shown. ]

Specific examples of the disulfonyldiazomethane compound include bis (trifluoromethanesulfonyl) diazomethane, bis (cyclohexanesulfonyl) diazomethane, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (2,2).
4-dimethylbenzenesulfonyl) diazomethane, methanesulfonyl / p-toluenesulfonyldiazomethane,
Bis (4-t-butylbenzenesulfonyl) diazomethane, bis (4-chlorobenzenesulfonyl) diazomethane, cyclohexanesulfonyl.p-toluenesulfonyldiazomethane, cyclohexylsulfonyl. (1,1
-Dimethylethanesulfonyl) diazomethane, bis (1,1-dimethylethanesulfonyl) diazomethane,
Bis (1-methylethanesulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.
5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] decane-7-sulfonyl) diazomethane and the like can be mentioned.

Disulfonylmethane compound: Examples of the disulfonylmethane compound include compounds represented by the following general formula (8).

[0072]

[Chemical 10] [In the general formula (8), R ⁸ and R ⁹ are each independently a linear or branched monovalent aliphatic hydrocarbon group, a cycloalkyl group, an aryl group, an aralkyl group or a monovalent group having a hetero atom. And V and W each independently represent an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group, or another monovalent organic group having a hetero atom. And at least one of V and W is an aryl group, or V and W are connected to each other to form a monocyclic or polycyclic ring having at least one unsaturated bond, or V and W Are linked to each other to form a group represented by the following formula (9).

[0073]

[Chemical 11] (However, V'and W'may be the same or different from each other, and a plurality of V'and W'may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a linear or branched alkyl group. A group, a cycloalkyl group, an aryl group or an aralkyl group, or V'and W'bonded to the same or different carbon atoms are linked to each other to form a carbon monocyclic structure, and m is 2 to It is an integer of 10.)]]

Oxime Sulfonate Compound Examples of the oxime sulfonate compound include compounds represented by the following general formula (10) or general formula (11).

[0075]

[Chemical 12] [In the general formula (10), R ¹⁰ and R ¹¹ each independently represent a monovalent organic group. ]

In the general formula (10), specific examples of R ¹⁰ include methyl group, ethyl group, n-propyl group, phenyl group, tosyl group, trifluoromethyl group and nonafluoro-n-butyl group. Further, specific examples of R ¹¹ include phenyl group, tosyl group, 1-naphthyl group and the like.

[0077]

[Chemical 13] [In General Formula (11), R ¹² , R ¹³ , R ¹⁴ and R
^15's each independently represent a monovalent organic group. ]

In the general formula (11), R ¹² and R ¹³
Specific examples of R include methyl group, ethyl group, n-propyl group, phenyl group, tosyl group, trifluoromethyl group, nonafluoro-n-butyl group and the like, and specific examples of R ¹⁴ and R ¹⁵ Examples thereof include a phenyl group, a tosyl group and a 1-naphthyl group.

Hydrazine Sulfonate Compound Specific examples of the hydrazine sulfonate compound include bis (benzenesulfonyl) hydrazine, bis (p-toluenesulfonyl) hydrazine, bis (trifluoromethanesulfonyl) hydrazine, bis (nonafluoro-n-butanesulfonyl) hydrazine, Bis (n-propanesulfonyl) hydrazine, benzenesulfonylhydrazine,
Examples thereof include p-toluenesulfonylhydrazine, trifluoromethanesulfonylhydrazine, nonafluoro-n-butanesulfonylhydrazine, n-propanesulfonylhydrazine, and trifluoromethanesulfonyl.p-toluenesulfonylhydrazine.

In the radiation-sensitive resin composition of the present invention,
The acid generator (C) can be used alone or in combination of two or more. In the radiation-sensitive resin composition of the present invention, the amount of the acid generator (C) used is 100 parts of the resin (B).
It is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 15 parts by weight, per part by weight.

-Other Components-The radiation-sensitive resin composition of the present invention further controls the diffusion phenomenon of the acid generated from the acid generator (C) upon exposure in the resist film to prevent exposure to unexposed areas. It is preferable to add an acid diffusion controller having an action of suppressing an undesired chemical reaction. By using such an acid diffusion control agent, the storage stability of the composition is improved, the resolution as a resist is improved, and the retention time (PED) from exposure to heat treatment after exposure varies. The change in the line width of the resist pattern can be suppressed, and the process stability becomes extremely excellent.

The acid diffusion controller is preferably a nitrogen-containing organic compound whose basicity does not change due to exposure or heat treatment during the resist pattern forming step. As such a nitrogen-containing organic compound, for example, a compound represented by the following general formula (12) (hereinafter referred to as "nitrogen-containing compound (I)").

[0083]

[Chemical 14] [In the general formula (12), R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. The cycloalkyl group, aryl group and aralkyl group may be substituted with a substituent such as a hydroxy group. ],

A diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as "nitrogen-containing compound (II)"),
A diamino polymer having three or more nitrogen atoms (hereinafter referred to as "nitrogen-containing compound (III)"), an amide group-containing compound,
Examples thereof include urea compounds and nitrogen-containing heterocyclic compounds.

As the nitrogen-containing compound (I), for example, n
-Hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and other monoalkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di- Dialkylamines such as n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine , Tri-n-hexylamine, tri-n-heptylamine,
Tri-n-octylamine, tri-n-nonylamine,
Trialkylamines such as tri-n-decylamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenyl Examples thereof include aromatic amines such as amine and 1-naphthylamine.

Examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetrakis (2
-Hydroxypropyl) ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,
4'-diaminodiphenylamine, 2,2'-bis (4
-Aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4
-Aminophenyl) -2- (3-hydroxyphenyl)
Propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4
-Aminophenyl) -1-methylethyl] benzene,
1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene and the like can be mentioned. Examples of the nitrogen-containing compound (III) include polyethyleneimine, polyallylamine, and a polymer of N- (2-dimethylaminoethyl) acrylamide.

Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-
Examples thereof include dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone and N-methylpyrrolidone. Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, tetramethylurea,
1,3-diphenyl urea, tri-n-butyl thiourea, etc. can be mentioned. Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole and 2-phenylbenzimidazole; pyridine, 2-methylpyridine and 4-methyl. Pyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2
-Methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinoline, acridine and other pyridines, as well as pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4- Methylmorpholine,
Examples thereof include piperazine, 1,4-dimethylpiperazine and 1,4-diazabicyclo [2.2.2] octane.

A base precursor having an acid dissociable group can also be used as the acid diffusion control agent. Specific examples of the base precursor include N- (t-butoxycarbonyl)
Piperidine, N- (t-butoxycarbonyl) imidazole, N- (t-butoxycarbonyl) benzimidazole, N- (t-butoxycarbonyl) 2-phenylbenzimidazole, N- (t-butoxycarbonyl) di-n-octyl Examples thereof include amine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine and N- (t-butoxycarbonyl) diphenylamine.

Among these nitrogen-containing organic compounds, the nitrogen-containing compound (I), the nitrogen-containing compound (II), the nitrogen-containing heterocyclic compound and the like are preferable. The acid diffusion control agent may be used alone or 2
More than one species can be used together. The amount of the acid diffusion controller to be added is usually 15 parts by weight or less, preferably 0.001 to 10 parts by weight, and more preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the resin (B). In this case, if the amount of the acid diffusion controller is more than 15 parts by weight, the sensitivity of the resist and the developability of the exposed area tend to be lowered.
If the amount of the acid diffusion controller is less than 0.001 part by weight, the pattern shape and dimensional fidelity of the resist may be reduced depending on the process conditions.

If desired, an alkali-soluble resin can be added to the radiation-sensitive resin composition of the present invention. Examples of the alkali-soluble resin include poly (4-hydroxystyrene) and partially hydrogenated poly (4
-Hydroxystyrene), poly (3-hydroxystyrene), poly (3-hydroxystyrene), 4-hydroxystyrene / 3-hydroxystyrene copolymer, 4-hydroxystyrene / styrene copolymer, novolac resin, polyvinyl alcohol, Polyacrylic acid etc. can be mentioned. The Mw of these alkali-soluble resins is
Usually, it is 1,000-1,000,000, preferably 2,000-100,000. The alkali-soluble resins may be used alone or in combination of two or more. The content of the alkali-soluble resin is preferably 20 parts by weight or less per 100 parts by weight of the resin (B).

Further, the radiation-sensitive resin composition of the present invention may contain a surfactant having an effect of improving the coating property, striation, developability as a resist and the like of the composition. Examples of such a surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenol ether, polyoxyethylene n-nonylphenol ether, polyethylene glycol dilaurate, polyethylene glycol diether. Examples of the commercially available products include F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), Megafax F171 and F173 (above,
Dainippon Ink and Chemicals, Inc., Florard FC43
0, the same FC431 (above, Sumitomo 3M Co., Ltd.),
Asahi Guard AG710, Surflon S-382, S
C101, SC102, SC103, SC10
4, the same SC105, the same SC106 (above, Asahi Glass Co., Ltd.
Manufactured by Shin-Etsu Chemical Co., Ltd., Polyflow No. 75, the same No. 95 (above, Kyoeisha Chemical Co., Ltd. product) etc. can be mentioned. The surfactants may be used alone or in admixture of two or more. The blending amount of the surfactant is preferably 2 parts by weight or less per 100 parts by weight of the resin (B).

Further, preferably, sensitizers such as benzophenones, rose bengals, anthracenes and the like can be added. The compounding amount of the sensitizer is preferably 50 parts by weight or less per 100 parts by weight of the resin (B). Further, by blending a dye and / or a pigment, the latent image in the exposed area can be visualized and the effect of halation during exposure can be mitigated. By blending an adhesion aid, the adhesiveness with the substrate is improved. be able to. Further, as an additive other than the above, an antihalation agent such as 4-hydroxy-4′-methylchalcone, a shape improving agent, a storage stabilizer, an antifoaming agent and the like can be blended.

-Solvent- The radiation-sensitive resin composition of the present invention is usually used such that the concentration of the total solid content is, for example, 0.1 to 50% by weight, preferably 1 to 40% by weight. After being uniformly dissolved in a solvent, for example, a composition solution is prepared by filtering with a filter having a pore size of about 0.2 μm. Examples of the solvent used for preparing the composition solution include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, and the like. Glycol monoalkyl ether acetates; Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, and other propylene glycol monoalkyl ethers; Propylene glycol dimethyl ether, propylene glycol diethyl Ether, propylene glycol di-n-propyl ether, propylene Propylene glycol dialkyl ethers such as recall di-n-butyl ether; propylene glycol monoalkyl such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Ether acetates;

Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate; n-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate, i-propyl acetate, acetic acid. n-butyl, i-butyl acetate, n-amyl acetate, i-amyl acetate, i-propionate
-Propyl, n-butyl propionate, propionate i
-Aliphatic carboxylic acid esters such as butyl; ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate,
Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3
-Methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate and other esters; aromatic hydrocarbons such as toluene and xylene Ketones such as methyl ethyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N- Examples thereof include amides such as dimethylacetamide and N-methylpyrrolidone; and lactones such as γ-butyrolactone. These solvents may be used alone or in admixture of two or more.

Formation of resist pattern When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution prepared as described above is subjected to spin coating, cast coating, roll coating, etc. By a suitable coating means, for example, by coating on a substrate such as a silicon wafer, a wafer covered with aluminum, etc., a resist film is formed, and depending on the case, 70 ° C.
After heat treatment (hereinafter referred to as “PB”) at a temperature of about 160 ° C., exposure is performed through a predetermined mask pattern. The radiation used at that time may be, for example, F ₂ excimer laser (wavelength 157 nm) or ArF excimer laser (wavelength 1) depending on the type of the acid generator (C).
93nm) or KrF excimer laser (wavelength 248n
Far ultraviolet rays such as m), X-rays such as synchrotron radiation, and charged particle beams such as electron beams are appropriately selected and used. In addition, the exposure conditions such as the exposure amount are appropriately selected according to the composition of the radiation-sensitive resin composition, the type of each additive, and the like.

In the present invention, in order to stably form a highly precise fine pattern, after exposure, the temperature is 70 to 160 ° C.
It is preferable to perform heat treatment (hereinafter referred to as “PEB”) at the temperature of 30 seconds or more. In this case, if the temperature of the PEB is lower than 70 ° C., there is a possibility that variations in sensitivity will spread depending on the type of substrate. Then, using an alkaline developer, it is usually at 10 to 50 ° C. for 10 to 200 seconds, preferably at 15 to 30 ° C. for 15 to 100 seconds, and particularly preferably 2
A predetermined resist pattern is formed by developing at 0 to 25 ° C. for 15 to 90 seconds.

Examples of the alkali developer include alkali metal hydroxides, aqueous ammonia, mono-, di- or tri-alkylamines, mono-, di- or tri-alkanolamines, and heterocyclic amines. , Tetraalkylammonium hydroxides, choline, 1,8
-Diazabicyclo- [5.4.0] -7-undecene,
Alkaline compounds such as 1,5-diazabicyclo- [4.3.0] -5-nonene are usually used in a concentration of 1 to 10% by weight, preferably 1 to 5% by weight, particularly preferably 1 to 3% by weight. An alkaline aqueous solution dissolved so that is used is used.
In addition, a water-soluble organic solvent such as methanol or ethanol, or a surfactant can be appropriately added to the developer containing the alkaline aqueous solution. In forming the resist pattern, a protective film may be provided on the resist film in order to prevent the influence of basic impurities contained in the ambient atmosphere.

[0098]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described more specifically below with reference to examples. However, the present invention is not limited to these examples.

EXAMPLES [Synthesis of Anthracene Derivative (1)] Example 1 100 g of 9-anthracenecarboxylic acid and 55 g of potassium t-butoxide were mixed with 500 g of dehydrated dimethylformamide.
100 g of t-butyl bromoacetate was added, and the mixture was reacted at 23 ° C. for 2 hours. Then ethyl acetate 20
After adding 0 g and discarding the aqueous layer, the organic layer was washed with water and the solvent was distilled off to obtain 112 g of a compound represented by the following formula (1-1) as a yellow solid. This compound is referred to as Compound (A-1).

The ¹ H-NMR spectrum and the ultraviolet absorption spectrum of the compound (A-1) are shown in FIGS. 1 and 2, respectively. The ¹ H-NMR spectrum is F manufactured by JEOL Ltd.
It was measured by TNMR (solvent: deuterated acetone), and the ultraviolet absorption spectrum was measured by UV / VIS spectrophotometer (solvent: acetonitrile, in air atmosphere) manufactured by JASCO Corporation.

[0100]

[Chemical 15]

Example 2 100 g of 9-anthracene aldehyde was dissolved in 500 g of dehydrated tetrahydrofuran, and then the concentration was adjusted to 1 at -78 ° C.
500 g of mol / l n-hexane solution of n-butyllithium was gradually added dropwise. Thereafter, 100 g of t-butyl bromoacetate was added at room temperature, and the mixture was reacted at 60 ° C. for 5 hours. Thereafter, 200 g of ethyl acetate was added, the aqueous layer was discarded, the organic layer was washed with water, and n-hexane was added to recrystallize the reaction product, followed by vacuum drying to obtain the compound represented by the following formula (1-2 56 g of a compound represented by the formula (4) was obtained as a yellow solid. This compound is referred to as a compound (A-2).

[0102]

[Chemical 16]

[Synthesis of Resin (B)] Synthesis Example 1 4-acetoxystyrene 101 g, styrene 5 g, 4-
After dissolving 42 g of t-butoxystyrene, 6 g of azobisisobutyronitrile and 1 g of t-dodecyl mercaptan in 160 g of propylene glycol monomethyl ether, the reaction temperature was kept at 70 ° C. under a nitrogen atmosphere,
It was polymerized for 16 hours. Then, the reaction solution was dropped into a large amount of n-hexane to solidify and purify the produced resin. Next, 150 g of propylene glycol monomethyl ether was added again to this purified resin, and then 300 g of methanol, 80 g of triethylamine and 15 g of water were added, and the hydrolysis reaction was carried out for 8 hours while refluxing at the boiling point. Then, the solvent and triethylamine were distilled off under reduced pressure, the obtained resin was dissolved in acetone, and then dropped into a large amount of water to be solidified, and the produced white powder was filtered and dried under reduced pressure at 50 ° C. overnight. . The resin obtained is M
w is 16,000, Mw / Mn is 1.7, and ¹³ C-
As a result of NMR analysis, the copolymerization molar ratio of 4-hydroxystyrene, styrene and 4-t-butoxystyrene was 7
It was 2: 5: 23. This resin is referred to as resin (B-1).

The Mw and Mn of the resin (B-1) and the resins obtained in the following Synthesis Examples 2 and 3 were measured by Tosoh Corp. G
PC column (G2000H _XL 2 this, G3000H _XL
One, using G4000H _XL one), Flow rate: 1.0 ml / minute, eluting solvent tetrahydrofuran, in the analysis conditions of column temperature 40 ° C., gel permeation chromatography using monodisperse polystyrene as a standard (GPC)
It was measured by.

Synthesis Example 2 4-acetoxystyrene 100 g, t-butyl acrylate 25 g, styrene 18 g, azobisisobutyronitrile 6 g and t-dodecyl mercaptan 1 g were dissolved in propylene glycol monomethyl ether 230 g,
Polymerization was carried out for 16 hours while maintaining the reaction temperature at 70 ° C under a nitrogen atmosphere. After the polymerization, the reaction solution was dropped into a large amount of n-hexane to solidify and purify the produced resin. Next, 150 g of propylene glycol monomethyl ether was added again to the purified resin, 300 g of methanol, 80 g of triethylamine and 15 g of water were further added, and the hydrolysis reaction was carried out for 8 hours while refluxing at the boiling point. After that, the solvent and triethylamine were distilled off under reduced pressure, the obtained resin was dissolved in acetone, and then dropped into a large amount of water to coagulate, and the produced white powder was filtered, and the mixture was dried under reduced pressure.
Dry overnight at ° C. The resin obtained has an Mw of 11,50.
0, Mw / Mn was 1.6, and as a result of ¹³ C-NMR analysis, the copolymerization molar ratio of 4-hydroxystyrene, t-butyl acrylate and styrene was 61:19:20. This resin is referred to as resin (B-2).

Synthesis Example 3 4-Hydroxystyrene / 4 with a molar ratio of copolymerization of 90:10
After dissolving 25 g of -t-butoxystyrene copolymer in 100 g of n-butyl acetate and bubbling with nitrogen gas for 30 minutes, 3.3 g of ethyl vinyl ether was added, and 1 g of p-toluenesulfonic acid pyridinium salt was added as a catalyst. Was added and reacted at room temperature for 12 hours. Then, the reaction solution was dropped into a 1 wt% aqueous ammonia solution to precipitate a resin, which was then filtered and dried overnight in a vacuum dryer at 50 ° C. The obtained resin has Mw of 13,000 and M
w / Mn is 1.01, and as a result of ¹³ C-NMR analysis,
It had a structure in which 23 mol% of the hydrogen atoms of the phenolic hydroxyl group in poly (4-hydroxystyrene) were substituted with 1-ethoxyoxyethyl groups and 10 mol% were substituted with t-butyl groups. This resin is referred to as resin (B-3).

[Radiation-Sensitive Resin Compositions] Examples 3 to 9 and Comparative Example 1 The components shown in Table 1 (however, parts are based on weight) were mixed to form a uniform solution, and then the solution having a pore size of 0.2 μm was prepared. A composition solution was prepared by filtering with a membrane filter. afterwards,
After spin coating each composition solution on a silicon wafer, PB was performed under the conditions shown in Table 2 to obtain a film thickness of 0.5 μm.
To form a resist film. Then, after using the stepper NSR2205 EX12B (numerical aperture 0.55) manufactured by Nikon Co., Ltd., each composition was exposed with the optimum exposure amount described later, PEB was performed under the conditions shown in Table 2. Then, using a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C.
After 1 minute of development by the paddle method, the resist pattern was formed by washing with pure water and drying. The evaluation results of each resist are shown in Table 3.

Here, the evaluation of each resist was carried out in the following manner. Sensitivity: The resist film formed on the silicon wafer is exposed to light, PEB is immediately performed, and alkali development is performed.
When washed with water and dried to form a resist pattern,
The exposure amount for forming a line-and-space pattern (1L1S) having a line width of 0.22 μm with a line width of 1: 1 was taken as the optimum exposure amount, and the sensitivity was evaluated by this optimum exposure amount. Resolution: The minimum dimension of the line-and-space pattern (1L1S) that is resolved when exposed with the optimum exposure amount is defined as the resolution. Line width fluctuation value: from film thickness 0.5 μm to −40 nm, −30
nm, -20 nm, -10 nm, +10 nm, + 20n
Lines formed with the optimum exposure dose for each resist coating with a film thickness deviated by m, +30 nm or +40 nm
The line width of the and space pattern (1L1S) was measured, and the difference between the maximum value and the minimum value of the line width was taken as the line width variation value.

The acid generator (C), acid diffusion control agent and solvent in Table 1 are as follows. Acid generator (C): C-1: bis (4-t-butylphenyl) iodonium 1
0-camphorsulfonate C-2: bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate C-3: N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-Dicarboximide C-4: Bis (cyclohexylsulfonyl) diazomethane C-5: N- (10-camphorsulfonyloxy) succinimide

Acid diffusion control agent: D-1: tri-n-octylamine D-2: N, N, N, N-tetrakis (2-hydroxypropyl) ethylenediamine D-3: N- (t-butoxycarbonyl) 2-Phenylbenzimidazole solvent: E-1: ethyl lactate E-2: 3-ethyl ethoxypropionate E-3: propylene glycol monomethyl ether acetate

[0111]

[Table 1]

[0112]

[Table 2]

[0113]

[Table 3]

[0114]

According to the present invention, actinic radiation such as K
It is possible to optimally control the radiation transmittance as an additive of a radiation-sensitive resin composition useful for a chemically amplified resist sensitive to deep ultraviolet rays represented by rF excimer laser, ArF excimer laser or F ₂ excimer laser. In particular, it is possible to effectively suppress the change in the line width of the resist pattern due to the variation in the film thickness of the resist film without impairing the resolution performance, and the sublimability is low, and the other components in the composition Provided is a novel anthracene derivative having excellent compatibility.

[Brief description of drawings]

1 of the anthracene derivative (1) obtained in Example ¹
It is a figure which shows a H-NMR spectrum.

FIG. 2 is a diagram showing an ultraviolet absorption spectrum of the anthracene derivative (1) obtained in Example 1.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H025 AB16 AC04 AC05 AC06 AC08                       AD03 BE00 BG00 CC02 FA03                       FA12 FA17                 4H006 AA01 AB48 BJ50 BR30 KA05

Claims (2)

[Claims] 1. An anthracene derivative represented by the following general formula (1): [Chemical 1] [In the general formula (1), R ^1's each independently represent a hydroxyl group or a monovalent organic group having 1 to 20 carbon atoms, a plurality of R ^1's may be the same or different, and n is 0. To an integer of 9 and X is a single bond or a carbon number of 1 to 12.
And a divalent organic group, and R ² represents a monovalent acid-dissociable group. ] 2. (A) The anthracene derivative according to claim 1, (B) an alkali-insoluble or sparingly alkali-soluble resin, which easily dissolves in the presence of an acid, and (C) a radioactive acid. A radiation-sensitive resin composition comprising a generator.