JPH11223950A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition superior in transparency to radiation and resolution, and also the balance of characteristics including sensitivity and developability, and pattern forms, and dry etching resistance, and the like. SOLUTION: The radiation sensitive resin composition comprises (A) an alkali-insoluble or hardly soluble resin having, as acid dissociable groups, repeating units each represented by the formula and solubilizable in alkali, when these acid-dissociable groups and/or lactone rings in these groups are dissociated, and (B) a radiation-sensitive acid-generator. In the formula, each of R<1> -R<4> is, independently, an H atom or a 1-6C straight or branched alkyl or 5- to 8-membered cycloalkyl group and R<1> and R<2> , or R<3> and R<4> may combine with each other to form a 5- to 8-membered cycloalkyl group; and (n) is an integer of 1-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive resin composition. The present invention relates to a radiation-sensitive resin composition which can be suitably used as a chemically amplified resist useful for fine processing using various radiations such as

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit elements, recently, it is said that a fine processing technique at a level of 0.20 μm or less is required in order to obtain a higher degree of integration. . In the conventional lithography process, near-ultraviolet rays such as i-rays are generally used as radiation, but it is said that it is extremely difficult to perform sub-quarter micron level fine processing with near-ultraviolet rays.
Therefore, in order to enable fine processing at a level of 0.20 μm or less, utilization of radiation having a shorter wavelength is being studied. Examples of such short-wavelength radiation include the emission line spectrum of a mercury lamp, deep ultraviolet rays represented by an excimer laser, X-rays, and electron beams. Of these, KrF excimer laser or Ar
F excimer lasers are receiving attention. As such a radiation-sensitive resin composition suitable for irradiation with an excimer laser, an acid-dissociable functional group (hereinafter, referred to as "protecting group").
(Hereinafter, referred to as "chemically amplified type") using a chemical amplification effect of a component having the formula Many "radiation-sensitive compositions" have been proposed. As such a chemically amplified radiation-sensitive composition, for example, Japanese Patent Publication No. 2-27660 discloses a polymer having a t-butyl ester group of carboxylic acid or a t-butyl carbonate group of phenol and acid generation. And compositions containing the agent. 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 the exposure, and the polymer is formed of a carboxyl group or a phenolic hydroxyl group. This makes use of the phenomenon that the exposed region of the resist film becomes easily soluble in an alkali developing solution. Many of the conventional chemically amplified radiation-sensitive compositions are based on phenolic resins, but in the case of such resins, the far-ultraviolet rays are absorbed by the aromatic ring, so that the exposed far-ultraviolet rays are exposed. However, the exposure amount is large in the upper layer of the resist film and smaller in the lower layer, and the resist pattern after development is thinner in the upper part and thicker in the lower part. There was a problem that the shape was not obtained and sufficient resolution could not be obtained. In addition, when the resist pattern after development has a trapezoidal shape, desired dimensional accuracy cannot be achieved in the next step, ie, etching or ion implantation, which has been a problem. In addition, if the shape of the upper part of the resist pattern is not rectangular, the rate of disappearance of the resist by dry etching is increased, and there is a problem that it is difficult to control the etching conditions. On the other hand, the shape of the resist pattern can be improved by increasing the radiation transmittance of the radiation-sensitive resin composition. For example, a (meth) acrylate resin represented by polymethyl methacrylate is highly transparent to far ultraviolet rays and is a very preferable resin from the viewpoint of radiation transmittance. Discloses a chemically amplified radiation-sensitive resin composition using a methacrylate resin. However, although this composition is excellent in terms of fine processing performance, it has no aromatic ring and thus has a drawback that dry etching resistance is low, and in this case also, it is difficult to perform high-precision etching processing. It is. On the other hand, in order to improve dry etching resistance without impairing the transparency to ultraviolet light, a method of introducing an alicyclic group instead of an aromatic ring is known,
For example, JP-A-7-234511 proposes a chemically amplified radiation-sensitive resin composition using a (meth) acrylate resin having an alicyclic group. However, in the above-mentioned conventional chemically amplified radiation-sensitive composition,
As a functional group component, a group that is relatively easily dissociated by an acid (for example, an acetal-based functional group such as a tetrahydropyranyl group)
Resins having groups that are relatively difficult to dissociate with acid or acid (for example, t-butyl-based functional groups such as t-butyl ester group and t-butyl carbonate group) are generally used. The amplified radiation-sensitive composition has good basic physical properties, particularly sensitivity and shape of the resist, but has poor storage stability. Although the stability is good, there is a drawback that the basic physical properties of the resist, particularly the sensitivity and the pattern shape are insufficient, and improvement thereof is required.
In recent years, as a chemically amplified radiation-sensitive composition using a resin having a functional group other than the above, which is effectively sensitive to far ultraviolet rays such as an ArF excimer laser, JP-A-9-90637 is disclosed.
In the publication, a composition containing a resin having a lactone-based functional group such as a mevalonic lactone ester group has also been proposed.This composition has transparency to far ultraviolet rays, dry etching resistance, sensitivity, resolution, and the like. It is said to be good.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made by further diligent studies on a resin component having a lactone-based protecting group used in a chemically amplified radiation-sensitive composition. As a chemically amplified resist that responds to radiation, for example, far ultraviolet rays represented by KrF excimer laser or ArF excimer laser, it has excellent transparency and resolution to radiation, and includes sensitivity, developability, pattern shape, dry etching resistance, etc. Another object of the present invention is to provide a radiation-sensitive resin composition having an excellent property balance.

[0004]

According to the present invention, an object of the present invention is to provide (A) an alkali-insoluble or alkali-insoluble resin having a group represented by the following general formula (1) as an acid-dissociable group. A resin which becomes alkali-soluble when the lactone ring in the acid-dissociable group itself and / or the acid-dissociable group is dissociated,

[0005]

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[In the general formula (1), R ^{1 to} R ⁴ are
Each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having a 5- to 8-membered ring, or R ¹ and R ² are bonded to each other to form 5 ~ 8
A 3-membered cyclic alkyl group is formed or R ³ and R ⁴ are mutually bonded to form a 5- to 8-membered cyclic alkyl group, and n is an integer of 1 to 4. And (B) a radiation-sensitive resin composition containing a radiation-sensitive acid generator. As used herein, the term “alkali-insoluble or alkali-insoluble resin” refers to an alkali developing agent used when a resist pattern is formed from a resist film formed using a radiation-sensitive resin composition containing the component (A). Under the conditions, when a film using only the component (A) instead of the resist film is developed, 50% or more of the initial film thickness of the film remains after development.

Hereinafter, the present invention will be described in detail. Resin (A) The component (A) in the present invention is an alkali-insoluble or alkali having a group represented by the following general formula (1) as an acid-dissociable group (hereinafter, referred to as “acid-dissociable group (1)”). A resin which is hardly soluble and which becomes alkali-soluble when the lactone ring in the acid-dissociable group (1) itself and / or the acid-dissociable group (1) is dissociated (hereinafter referred to as “resin (A)”) )). Here, the acid dissociable group (1) in the resin (A)
More specifically, the mode of dissociation of the lactone ring in itself and / or in the acid dissociable group (1) is described in the following (i) to (iii).
There is a case. (I) The case where the lactone ring in the acid dissociable group (1) is dissociated by the action of an acid to produce a functional group represented by the following general formula (2).

[0008]

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(Ii) The bond between the acid-dissociable group (1) itself and an atom adjacent to the acid-dissociable group (1) is dissociated by the action of an acid, and a phenolic hydroxyl group (including a naphtholic hydroxyl group).
The same applies hereinafter. ) Or when a carboxyl group is generated. (Iii) When the above (i) and (ii) occur simultaneously.

The resin (A) of the present invention includes, for example, the following resin (AI) and resin (A-II). The resin (A-I) is an alkali-soluble resin containing at least one kind of acidic functional group such as a phenolic hydroxyl group and a carboxyl group. Consisting of a resin having a structure substituted with
As such, it is an alkali-insoluble or alkali-insoluble resin. When the resin (AI) has an alicyclic skeleton in the side chain, a radiation-sensitive resin composition excellent in radiation transparency and dry etching resistance can be obtained as a resist. Resin (A-II) has an alicyclic skeleton in the main chain and a group -COOZ in the side chain, where Z
Represents an acid dissociable group (1). Is an alkali-insoluble or alkali-insoluble resin per se.

Specific examples of the acid dissociable group (1) include:
(2′-γ-butyrolactonyl) methyl group, 1- (2 ′
-Γ-butyrolactonyl) ethyl group, 1-methyl-1-
(2′-γ-butyrolactonyl) ethyl group, 1-methyl-1- (2′-γ-butyrolactonyl) propyl group, 2
-Methyl-1- (2′-γ-butyrolactonyl) propyl group, 1-cyclohexyl-1- (2′-γ-butyrolactonyl) ethyl group, 1- (2′-γ-butyrolactonyl) cyclohexyl group, (3′- Methyl-2′-γ-butyrolactonyl) methyl group, 1- (3′-methyl-2 ′)
-Γ-butyrolactonyl) ethyl group, 1-methyl-1-
(3′-methyl-2′-γ-butyrolactonyl) ethyl group, 1-methyl-1- (3′-methyl-2′-γ-butyrolactonyl) propyl group, 2-methyl-1- (3′-
Methyl-2′-γ-butyrolactonyl) propyl group, 1
-Cyclohexyl-1- (3'-methyl-2'-γ-butyrolactonyl) ethyl group, 1- (3'-methyl-2 '
-Γ-butyrolactonyl) cyclohexyl group, (3 ′,
3′-dimethyl-2′-γ-butyrolactonyl) methyl group, 1- (3 ′, 3′-dimethyl-2′-γ-butyrolactonyl) ethyl group, 1-methyl-1- (3 ′, 3′-
Dimethyl-2′-γ-butyrolactonyl) ethyl group, 1
-Methyl-1- (3 ′, 3′-dimethyl-2′-γ-butyrolactonyl) propyl group, 2-methyl-1-
(3 ′, 3′-dimethyl-2′-γ-butyrolactonyl) propyl group, 1-cyclohexyl-1- (3 ′,
3′-dimethyl-2′-γ-butyrolactonyl) ethyl group, 1- (3 ′, 3′-dimethyl-2′-γ-butyrolactonyl) cyclohexyl group, (3′-ethyl-2′-
γ-butyrolactonyl) methyl group, 1- (3′-ethyl-2′-γ-butyrolactonyl) ethyl group, 1-methyl-1- (3′-ethyl-2′-γ-butyrolactonyl)
Ethyl group, 1-methyl-1- (3′-ethyl-2′-γ
-Butyrolactonyl) propyl group, 2-methyl-1-
(3′-ethyl-2′-γbutyrolactonyl) propyl group, 1-cyclohexyl-1- (3′-ethyl-2 ′
-Γ-butyrolactonyl) ethyl group, 1- (3′-ethyl-2′-γ-butyrolactonyl) cyclohexyl group,
(3 ′, 3′-diethyl-2′-γ-butyrolactonyl) methyl group, 1- (3 ′, 3′-diethyl-2′-γ)
-Butyrolactonyl) ethyl group, 1-methyl-1-
(3 ′, 3′-diethyl-2′-γ-butyrolactonyl) ethyl group, 1-methyl-1- (3 ′, 3′-diethyl-2′-γ-butyrolactonyl) propyl group, 2-methyl-1- (3 ′, 3′-diethyl-2′-γ-butyrolactonyl) propyl group, 1-cyclohexyl-1-
(3 ′, 3′-diethyl-2′-γ-butyrolactonyl) ethyl group, 1- (3 ′, 3′-diethyl-2′-γ)
-Butyrolactonyl) cyclohexyl group,

(2′-δ-valerolactonyl) methyl group, 1- (2′-δ-valerolactonyl) ethyl group, 1
-Methyl-1- (2′-δ-valerolactonyl) ethyl group, 1-methyl-1- (3′-δ-valerolactonyl)
Propyl group, 2-methyl-1- (2′-δ-valerolactonyl) propyl group, 1-cyclohexyl-1- (2 ′
-Δ-valerolactonyl) ethyl group, 1- (2′-δ-
Valerolactonyl) cyclohexyl group, (3′-methyl-2′-δ-valerolactonyl) methyl group, 1- (3 ′
-Methyl-2'-δ-valerolactonyl) ethyl group, 1
-Methyl-1- (3′-methyl-2′-δ-valerolactonyl) ethyl group, 1-methyl-1- (3′-methyl-
2′-δ-valerolactonyl) propyl group, 2-methyl-1- (3′-methyl-2′-δ-valerolactonyl)
Propyl group, 1-cyclohexyl-1- (3′-methyl-2′-δ-valerolactonyl) ethyl group, 1- (3 ′
-Methyl-2′-δ-valerolactonyl) cyclohexyl group, (3 ′, 3′-dimethyl-2′-δ-valerolactonyl) methyl group, 1- (3 ′, 3′-dimethyl-2 ′)
-Δ-valerolactonyl) ethyl group, 1-methyl-1-
(3 ′, 3′-dimethyl-2′-δ-valerolactonyl) ethyl group, 1-methyl-1- (3 ′, 3′-dimethyl-2′-δ-valerolactonyl) propyl group, 2-methyl-1- (3 ′, 3′-dimethyl-2′-δ-valerolactonyl) propyl group, 1-cyclohexyl-1-
(3 ′, 3′-dimethyl-2′-δ-valerolactonyl) ethyl group, 1- (3 ′, 3′-dimethyl-2′-δ)
-Valerolactonyl) cyclohexyl group, (3′-ethyl-2′-δ-valerolactonyl) methyl group, 1-
(3′-ethyl-2′-δ-valerolactonyl) ethyl group, 1-methyl-1- (3′-ethyl-2′-δ-valerolactonyl) ethyl group, 1-methyl-1- (3′-ethyl- 2′-δ-valerolactonyl) propyl group, 2-
Methyl-1- (3′-ethyl-2′-δ-valerolactonyl) propyl group, 1-cyclohexyl-1- (3′-
Ethyl-2′-δ-valerolactonyl) ethyl group, 1-
(3′-ethyl-2′-δ-valerolactonyl) cyclohexyl group, (3 ′, 3′-diethyl-2′-δ-valerolactonyl) methyl group, 1- (3 ′, 3′-diethyl-2′-δ) -Valerolactonyl) ethyl group, 1-methyl-1- (3 ′, 3′-diethyl-2′-δ-valerolactonyl) ethyl group, 1-methyl-1- (3 ′, 3′-diethyl-2′-δ) -Valerolactonyl) propyl group, 2
-Methyl-1- (3 ′, 3′-diethyl-2′-δ-valerolactonyl) propyl group, 1-cyclohexyl-1
-(3 ′, 3′-diethyl-2′-δ-valerolactonyl) ethyl group, 1- (3 ′, 3′-diethyl-2′-δ
-Valerolactonyl) cyclohexyl group and the like.

Among these acid dissociable groups (1), 1-
(2′-γ-butyrolactonyl) ethyl group, 1-methyl-1- (2′-γ-butyrolactonyl) ethyl group, 1-
Methyl-1- (2′-γ-butyrolactonyl) propyl group, 1- (2′-δ-valerolactonyl) ethyl group, 1
-Methyl-1- (2′-δ-valerolactonyl) ethyl group, 1-methyl-1- (2′-δ-valerolactonyl)
A propyl group is preferred.

Hereinafter, resin (AI) and resin (AI)
I) will be described sequentially. The resin (AI) may optionally contain an acid-dissociable group other than the acid-dissociable group (1) (hereinafter, referred to as “acid-dissociable group”).
It is called "another acid dissociable group (i)". ). Examples of the other acid dissociable group (i) include, for example, a t-butyl group, a t-butoxycarbonyl group, an acetyl group,
A methoxyethyl group, a 1-ethoxyethyl group, a tetrahydropyranyl group, a methyltetrahydropyranyl group, a tetrahydrofuranyl group, a methyltetrahydrofuranyl group, a carbobutoxymethyl group, a 2-carbobutoxyethyl group,
3-carbobutoxypropyl group, 3-oxo-1,1-
Dimethylbutyl group, 3-oxo-1-i-propylbutyl group, 3-oxo-1-methylbutyl group, lactone group represented by the following general formula (3) (hereinafter, referred to as “lactone group (3)”). And a trialkylsilyl group.

[0015]

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[In the general formula (3), R ⁵ represents a hydrogen atom, a methyl group or an ethyl group, and m is 1 or 2. Among these other acid dissociable groups (i), a t-butyl group,
t-butoxycarbonyl group, 1-ethoxyethyl group, 1
-Butoxyethyl group, tetrahydropyranyl group, methyltetrahydropyranyl group, tetrahydrofuranyl group, methyltetrahydrofuranyl group, 3-oxo-1,1-dimethylbutyl group, 3-oxo-1-i-propylbutyl group, 3 -Oxo-1-methylbutyl group, lactone group (3) and the like are preferable.

The resin (AI) may be prepared by, for example, (a) a method of introducing one or more acid-dissociable groups (1) into a previously produced alkali-soluble resin, and (b) one or more acid-dissociable groups. (Co) polymerization of a polymerizable unsaturated monomer having (1), (c) (co) polycondensation of a polycondensable component having one or more acid dissociable groups (1), and the like. Can be manufactured.

Examples of the alkali-soluble resin used in the method (a) include an addition polymerization type resin or a polycondensation type resin having at least one kind of a repeating unit having an acidic functional group. Examples of the polymerizable unsaturated monomer that provides a repeating unit having an acidic functional group in the alkali-soluble resin of the addition polymerization system include, for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α -Methylstyrene, m-
Hydroxy-α-methylstyrene, p-hydroxy-α
-Methylstyrene, p-carboxystyrene, p-carboxymethylstyrene, p- (2-carboxyethyl)
Styrene, p-carboxymethoxystyrene, p- (2
(Α-methyl) styrene derivatives such as -carboxyethoxy) styrene, p-carboxymethylcarbonyloxystyrene and p- (2-carboxyethyl) carbonyloxystyrene; 2-hydroxy-1-vinylnaphthalene, 3-hydroxy-1- Vinylnaphthalene, 4-hydroxy-1-vinylnaphthalene, 5-hydroxy-1-
Vinyl naphthalene, 6-hydroxy-1-vinyl naphthalene, 7-hydroxy-1-vinyl naphthalene, 8-hydroxy-1-vinyl naphthalene, 2-hydroxy-1
-Isopropenylnaphthalene, 3-hydroxy-1-isopropenylnaphthalene, 4-hydroxy-1-isopropenylnaphthalene, 5-hydroxy-1-isopropenylnaphthalene, 6-hydroxy-1-isopropenylnaphthalene, 7-hydroxy-1 -Isopropenylnaphthalene, 8-hydroxy-1-isopropenylnaphthalene, 2-carboxy-1-vinylnaphthalene, 3-carboxy-1-vinylnaphthalene, 4-carboxy-1-
Vinylnaphthalene, 5-carboxy-1-vinylnaphthalene, 6-carboxy-1-vinylnaphthalene, 7-carboxy-1-vinylnaphthalene, 8-carboxy-1
-Vinyl naphthalene derivatives such as vinyl naphthalene or isopropenyl naphthalene derivatives;

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and cinnamic acid; 2-carboxyethyl (meth) acrylate, (meth) acrylate 2-carboxypropyl acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, and 5-carboxybicyclo (meth) acrylate as a compound having an alicyclic skeleton [2.2. 1] Heptyl, 8-carboxytetracyclo (meth) acrylate [4.4.
0.1 ^2,5 . [ ^17,10 ] carboxyl group-containing unsaturated carboxylic acid esters such as dodecyl.

Of these polymerizable unsaturated monomers, p-
Hydroxystyrene, p-hydroxy-α-methylstyrene, p-carboxystyrene, (meth) acrylic acid,
5-carboxybicyclo (meth) acrylate [2.2.
1] Heptyl, 8-carboxytetracyclo (meth) acrylate [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecyl and the like.

The alkali-soluble resin of the addition polymerization system may be composed of only a repeating unit having an acidic functional group. , "Other polymerizable unsaturated monomer (i)") may contain one or more repeating units in which the polymerizable unsaturated bond is cleaved. Examples of the other polymerizable unsaturated monomers (i) include styrene, α-methylstyrene, 4-t-butylstyrene, 4-t-butyl-α-methylstyrene, 1-vinylnaphthalene,
Methyl-1-vinylnaphthalene, 5-methyl-1-vinylnaphthalene, 1-isopropenylnaphthalene, 4-chloro-1-vinylnaphthalene, 5-chloro-1-vinylnaphthalene, 4-methoxy-1-vinylnaphthalene, 5
Vinyl aromatic compounds such as -methoxy-1-vinylnaphthalene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic N-butyl acid,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and norbornyl (meth) acrylate and (meth) acryl as compounds having an alicyclic skeleton Isobornyl acid, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, 1- (meth) acrylate
(Meth) acrylic esters such as methyl adamantyl and adamantyl methyl (meth) acrylate; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; (meth) acrylonitrile, α-chloroacrylonitrile, crotonitrile, maleinnitrile, Fumaronitrile, Mesaconitrile, Citraconitrile,
Unsaturated nitrile compounds such as itaconitrile; (meth)
Unsaturated amide compounds such as acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide and itaconamide; N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine, Other nitrogen-containing vinyl compounds such as vinylimidazole can be exemplified.

Among these other polymerizable unsaturated monomers (i), styrene, α-methylstyrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid 2 -Hydroxypropyl, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, 1-methyladamantyl (meth) acrylate, (meth) Adamantyl methyl acrylate and the like are preferred.

[0023] The polycondensation-based alkali-soluble resin may comprise one or more phenols and one or more aldehydes, together with a polycondensation component which may optionally form another repeating unit, in the presence of an acidic catalyst. It can be produced by polycondensation in an aqueous medium or a mixed medium of water and a hydrophilic solvent. Examples of the phenols include phenol, o-cresol, m-cresol, p
-Cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol , Resorcinol, catechol, pyrogallol, 1-naphthol, 2-naphthol and the like. Examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde,
Acetaldehyde, propylaldehyde, phenylacetaldehyde and the like can be mentioned.

The content of the repeating unit having an acidic functional group in the addition-polymerization type and polycondensation type alkali-soluble resin used in the method (a) is stipulated by the type of the repeating unit and other repeating units. No, but usually
It is 10 to 100 mol%, preferably 15 to 100 mol%. The introduction of the acid dissociable group (1) in the method (a) is performed by synthesizing an acidic functional group in an alkali-soluble resin via, for example, a reaction represented by the following general formula (4) and a reaction intermediate. It can be carried out by esterification or etherification by a conventional method using a tertiary alcohol (hereinafter, referred to as “tertiary alcohol (4)”).

[0025]

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[0026] In [Formula (4), R ¹ to R ⁴ and n have the same meanings as R ¹ to R ⁴ and n, respectively, in the general formula (1). ]

Examples of the polymerizable unsaturated monomer having an acid-dissociable group (1) used in the method (B) include, for example, a polymer having an acidic functional group exemplified in the method (A). Compounds in which the hydrogen atom of the acidic functional group in the unsaturated monomer is substituted with an acid dissociable group (1), and the acid dissociable group (1) used in the method (c) can be mentioned. Examples of the polycondensable component having) include compounds in which the hydrogen atom of the phenolic hydroxyl group of the phenol exemplified in the above method (a) is substituted with an acid dissociable group (1) and aldehydes. . In the method (b) or (c), in addition to the polymerizable unsaturated monomer having the acid dissociable group (1) or the polycondensable component having the acid dissociable group (1),
Other polymerizable unsaturated monomers or other polycondensable components,
Usually, it can be used in an amount of 90 mol% or less, preferably 85 mol% or less. The polymerization in producing the addition-polymerization-based alkali-soluble resin in the method (A) and the polymerization in the method (B) include, for example, a radical polymerization initiator, an anion polymerization catalyst, a coordination anion polymerization catalyst, and a cationic polymerization catalyst. Is appropriately selected, bulk polymerization, solution polymerization,
The polymerization can be carried out by an appropriate polymerization method such as precipitation polymerization, emulsion polymerization, suspension polymerization, or bulk-suspension polymerization. Resin (A-
Introduction rate of acid dissociable group (1) in I) ｛Acid dissociable group (1) based on the total number of acid dissociable group (1), other acid dissociable groups (i) and acidic functional groups in the resin. ) Cannot be unconditionally defined by the type of the acid-dissociable group (1) or the constituent monomer of the resin, but is usually 15 to 100 mol%, more preferably 20 to 100 mol%. is there.

Specific examples of the preferred resin (AI) in the present invention are as follows. Poly [4- @ 1'-
(2 ″ -γ-butyrolactonyl) ethoxy} styrene], poly [4- {1′-methyl-1 ′-(2 ″ -γ-
Butyrolactonyl) ethoxy {styrene], poly [4-
{1′-methyl-1 ′-(2 ″ -γ-butyrolactonyl) propoxy} styrene], poly [4- {1′-
(2 ″ -δ-valerolactonyl) ethoxy} styrene], poly [4- {1′-methyl-1 ′-(2 ″ -δ-
Valerolactonyl) ethoxy {styrene], poly [4-
{1′-methyl-1 ′-(2 ″ -δ-valerolactonyl) propoxy} styrene], 4- {1 ′-(2 ″ -γ
-Butyrolactonyl) ethoxy} styrene / 4-hydroxystyrene copolymer, 4- {1′-methyl-1′-
(2 ″ -γ-butyrolactonyl) ethoxy styrene /
4-hydroxystyrene copolymer, 4- {1′-methyl-1 ′-(2 ″ -γ-butyrolactonyl) propoxy}
Styrene / 4-hydroxystyrene copolymer, 4-
{1 ′-(2 ″ -δ-valerolactonyl) ethoxy} styrene / 4-hydroxystyrene copolymer, 4- {1 ′
-Methyl-1 ′-(2 ″ -δ-valerolactonyl) ethoxy} styrene / 4-hydroxystyrene copolymer, 4
Styrene resins such as-{1′-methyl-1′-methyl- (2 ″ -δ-valerolactonyl) propoxy} styrene / 4-hydroxystyrene copolymer;

Poly [4- {1 ′-(2 ″ -γ-butyrolactonyl) ethoxy} -1-vinylnaphthalene], poly [4- {1′-methyl-1 ′-(2 ″ -γ-butyrolactonyl) ) Ethoxy} -1-vinylnaphthalene], poly [4- {1′-methyl-1 ′-(2 ″ -γbutyrolactonyl) propoxy} -1-vinylnaphthalene], poly [4- {1 '-(2''-δ-valerolactonyl) ethoxy} -1-vinylnaphthalene), poly [4- {1'-methyl-1'-(2 "-δ-valerolactonyl) ethoxy} -1-vinylnaphthalene] , Poly [4- {1′-methyl-1 ′-(2 ″ -δ-valerolactonyl) propoxy} -1-vinylnaphthalene], 4- {1 ′-(2 ″-)
γ-butyrolactonyl) ethoxy {-1-vinylnaphthalene / 4-hydroxy-1-vinylnaphthalene copolymer, 4- {1′-methyl-1 ′-(2′-γ-butyrolactonyl) ethoxy} -1-vinylnaphthalene / 4-hydroxy-1-vinylnaphthalene copolymer, 4- {1 ′
-Methyl-1 ′-(2 ″ -γ-butyrolactonyl) propoxy} -1-vinylnaphthalene / 4-hydroxy-1
-Vinyl naphthalene copolymer, 4- {1 ′-(2 ″ -δ)
-Valerolactonyl) ethoxy} -1-vinylnaphthalene / 4-hydroxy-1-vinylnaphthalene copolymer,
4- {1′-methyl-1 ′-(2 ″ -δ-valerolactonyl) ethoxy} -1-vinylnaphthalene / 4-hydroxy-1-vinylnaphthalene copolymer, 4- {1′-methyl-1 ′ Vinyl naphthalene-based resins such as-(2 ″ -δ-valerolactonyl) propoxy} -1-vinylnaphthalene / 4-hydroxy-1-vinylnaphthalene copolymer;

Poly [(meth) acrylic acid {1- (2'-
γ-butyrolactonyl) ethyl}], poly [1-methyl-1- (2′-γ-butyrolactonyl) ethyl}], poly [(meth) acrylic acid} 1-methyl-1- (2 '-Γ-butyrolactonyl) propyl}], poly [(meth) acrylic acid} 1- (2'-δ-
Valerolactonyl) ethyl}], poly [1-methyl-1- (2′-δ-valerolactonyl) ethyl} (meth) acrylate}, poly [(meth) acrylate} 1-methyl-1- (2′- δ-valerolactonyl) propyl}], (meth) acrylic acid {1- (2′-γ-butyrolactonyl) ethyl} / (meth) acrylic acid copolymer,
{1-methyl-1- (2′-γ-butyrolactonyl) ethyl} (meth) acrylate / (meth) acrylic acid copolymer, {1-methyl-1- (2′-γ) (meth) acrylate
-Butyrolactonyl) propyl} / (meth) acrylic acid copolymer, (meth) acrylic acid {1- (2′-δ-valerolactonyl) ethyl} / (meth) acrylic acid copolymer, (meth) acrylic acid} 1 -Methyl-1- (2'-δ
-Valerolactonyl) ethyl} / (meth) acrylic acid copolymer, (meth) acrylic acid {1-methyl-1- (2 ′)
-Δ-valerolactonyl) propyl} / (meth) acrylic acid copolymer,

(Meth) acrylic acid {1- (2′-γ-butyrolactonyl) ethyl} / tricyclodecanyl (meth) acrylate / (meth) acrylic acid copolymer, (meth)
{1-methyl-1- (2′-γ-butyrolactonyl) ethyl acrylate} / tricyclodecanyl (meth) acrylate / (meth) acrylic acid copolymer; {1-methyl-1 (meth) acrylate] -(2'-γ-butyrolactonyl)
Propyl｝ / tricyclodecanyl (meth) acrylate /
(Meth) acrylic acid copolymer, (meth) acrylic acid ｛1
-(2'-δ-valerolactonyl) ethyl} / (meth)
Tricyclodecanyl acrylate / (meth) acrylic acid copolymer, {1-methyl-1- (2 ′) (meth) acrylate
-Δ-valerolactonyl) ethyl} / (tricyclodecanyl (meth) acrylate / (meth) acrylic acid copolymer,
(1-methyl-1- (2′-δ-valerolactonyl) propyl) (meth) acrylate / tricyclodecanyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid {1- (2′-γ-butyrolactonyl)
Ethyl｝ / adamantyl acrylate (meth) / (meth)
Acrylic acid copolymer, (1-methyl-1- (2′-γ-butyrolactonyl) ethyl) (meth) acrylate / adamantyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid {1-methyl-1- (2′-
γ-butyrolactonyl) propyl} / adamantyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid {1- (2′-δ-valerolactonyl)
Ethyl / adamantyl (meth) acrylate / (meth) acrylic acid copolymer, {1-methyl- (meth) acrylate-
1- (2′-δ-valerolactonyl) ethyl} / adamantyl (meth) acrylate / (meth) acrylic acid copolymer, {1-methyl-1- (2′-meth) acrylate)
δ-valerolactonyl) propyl} / adamantyl (meth) acrylate / (meth) acrylic acid copolymer,

(Meth) acrylic acid {1- (2'-γ-butyrolactonyl) ethyl} / (meth) acrylic acid 1-methyladamantyl / (meth) acrylic acid copolymer, (meth) acrylic acid {1-methyl) -1- (2′-γ-butyrolactonyl) ethyl} / 1-methyladamantyl (meth) acrylate / (meth) acrylic acid copolymer, (meth)
{1-methyl-1- (2′-γ-butyrolactonyl) propyl acrylate} / 1-methyladamantyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid {1- (2 ′) -Δ-valerolactonyl) ethyl} / 1-methyladamantyl (meth) acrylate /
(Meth) acrylic acid copolymer, (meth) acrylic acid ｛1
-Methyl-1- (2′-δ-valerolactonyl) ethyl} / 1-methyladamantyl (meth) acrylate /
(Meth) acrylic acid copolymer, (meth) acrylic acid ｛1
-Methyl-1- (2′-δ-valerolactonyl) propyl} / 1-methyladamantyl (meth) acrylate /
(Meth) acrylic acid copolymer, (meth) acrylic acid ｛1
-(2'-γ-butyrolactonyl) ethyl} / (meth)
Adamantylmethyl acrylate / (meth) acrylic acid copolymer, {1-methyl-1- (2 ′) acrylate)
-Γ-butyrolactonyl) ethyl} / adamantylmethyl (meth) acrylate / (meth) acrylic acid copolymer,
(1-methyl-1- (2′-γ-butyrolactonyl) propyl) (meth) acrylate / adamantylmethyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid {1- (2) '-Δ-valerolactonyl)
Ethyl｝ / adamantyl methyl acrylate /
(Meth) acrylic acid copolymer, (meth) acrylic acid ｛1
-Methyl-1- (2′-δ-valerolactonyl) ethyl} / adamantylmethyl (meth) acrylate / (meth) acrylic acid copolymer; {1-methyl-1- (2′-δ) (meth) acrylate -Valerolactonyl) propyl
/ Adamantylmethyl (meth) acrylate / (meth) acrylic acid copolymer,

(Meth) acrylic acid {1- (2'-γ-butyrolactonyl) ethyl} / tricyclodecanyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, (meth) acrylic acid ｛1-methyl-1-
(2'-γ-butyrolactonyl) ethyl} / tricyclodecanyl (meth) acrylate / 2- (meth) acrylate
Hydroxypropyl copolymer, (meth) acrylic acid # 1
-Methyl-1- (2 '-[gamma] -butyrolactonyl) propyl} / tricyclodecanyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1- (2') methacrylate -Δ-valerolactonyl)
Ethyl｝ / tricyclodecanyl (meth) acrylate /
(Meth) acrylic acid 2-hydroxypropyl copolymer,
(Meth) acrylic acid {1-methyl-1- (2′-δ-valerolactonyl) ethyl} / tricyclodecanyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, (meth) acrylic Acid 1-methyl-1-
(2′-δ-valerolactonyl) propyl} / (meth)
Tricyclodecanyl acrylate / (meth) acrylic acid 2
-Hydroxypropyl copolymer, {1- (2′-γ-butyrolactonyl) ethyl} (meth) acrylate / adamantyl (meth) acrylate / 2- (meth) acrylate
Hydroxypropyl copolymer, (meth) acrylic acid # 1
-Methyl-1- (2′-γ-butyrolactonyl) ethyl} / adamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1-methyl-1- (2) -methacrylate) '-Γ-butyrolactonyl) propyl} / adamantyl (meth) acrylate /
(Meth) acrylic acid 2-hydroxypropyl copolymer,
{1- (2 '-[delta] -valerolactonyl) ethyl} (meth) acrylate / adamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1-methyl-1 (meth) acrylate] -(2′-δ-valerolactonyl) ethyl} / adamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1-methyl-1- (2′-δ) methacrylate
-Valerolactonyl) propyl} / adamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer,

(Meth) acrylic acid {1- (2′-γ-butyrolactonyl) ethyl} / (meth) acrylic acid 1-methyladamantyl / (meth) acrylic acid 2-hydroxypropyl copolymer, (meth) acrylic acid ｛1-methyl-
1- (2′-γ-butyrolactonyl) ethyl} / 1-methyladamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1-methyl-1- (2) -methacrylate) '-Γ-butyrolactonyl) propyl} / 1-methyladamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1- (2′-δ-valerolactonyl) ethyl} (meth) acrylate / 1-methyl adamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1-methyl-1- (meth) acrylate]
(2′-δ-valerolactonyl) ethyl} / 1-methyladamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1-methyl-1- (2′-meth) acrylate δ-valerolactonyl) propyl} / 1-methyladamantyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, (meth) acrylate {1- (2′-γ-butyrolactonyl) ethyl} / ( Adamantylmethyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1-methyl-1- (2 ′-) (meth) acrylate
γ-butyrolactonyl) ethyl / adamantylmethyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid {1-methyl-1- (2′-γ-butyrolactonyl) propyl} /
Adamantylmethyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1- (2′-δ-valerolactonyl) ethyl} (meth) acrylate
/ Adamantyl methyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer, {1-methyl-1- (2'-δ-valerolactonyl) ethyl (meth) acrylate} / (meth) acrylic acid Adamantyl methyl / 2-hydroxypropyl (meth) acrylate copolymer, {1-methyl-1- (2′-δ) (meth) acrylate
-Valerolactonyl) propyl} / adamantylmethyl (meth) acrylate / 2-hydroxypropyl (meth) acrylate copolymer,

A homopolymer of a compound represented by the following formula (5) (hereinafter referred to as "polymerizable unsaturated monomer (5)"):

[0036]

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[In the general formula (5), R ⁶ represents a hydrogen atom or a methyl group, and W ¹ represents

[0038]

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Where i is 0 or 1. ] Polymerizable unsaturated monomer (5) / tricyclodecanyl methacrylate copolymer, polymerizable unsaturated monomer (5) / adamantyl methacrylate copolymer, polymerizable unsaturated monomer (5)
(Meth) acrylic resins such as 1 / methyl adamantyl methacrylate copolymer and polymerizable unsaturated monomer (5) / adamantyl methyl methacrylate copolymer.

Next, since the resin (A-II) has an alicyclic skeleton in its main chain, it is possible to obtain a radiation-sensitive resin composition which is particularly excellent in radiation transparency and dry etching resistance as a resist. Can be. Resin (A-I
As I), for example, a resin containing at least one type of a repeating unit represented by the following general formula (6) (hereinafter, referred to as “repeating unit (6)”) in which an unsaturated bond of a norbornene derivative is cleaved is exemplified. be able to.

[0041]

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[In the general formula (6), α and β are
A hydrogen atom, a halogen atom, a carbon number of 1 to 10
X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 10 carbon atoms,
10 halogenated hydrocarbon groups or groups -COOZ, and at least one of X and Y is a group -COOZ
｛Wherein Z represents an acid dissociable group (1). ｝ And i are 0 or 1. ]

The resin (A-II) may be optionally
Group -COOZ 'wherein Z' represents an acid-dissociable group other than Z (hereinafter, referred to as "another acid-dissociable group (ii)"). ｝. Other acid dissociable groups (ii) include:
For example, t-butyl group, t-butoxycarbonyl group, acetyl group, 1-methoxyethyl group, 1-ethoxyethyl group, tetrahydropyranyl group, methyltetrahydropyranyl group, tetrahydrofuranyl group, methyltetrahydrofuranyl group, carbobutoxy group Methyl group, 2-carbobutoxyethyl group, 3-carbobutoxypropyl group, 3-oxo-1,1-dimethylbutyl group, 3-oxo-1-i
-Propylbutyl group, 3-oxo-1-methylbutyl group, lactone group (3), trialkylsilyl group and the like. Among these other acid dissociable groups (ii), t-butyl, t-butoxycarbonyl, 1-ethoxyethyl, 1-butoxyethyl, tetrahydropyranyl, methyltetrahydropyranyl, tetrahydrofuranyl Group, methyltetrahydrofuranyl group, 3-
Oxo-1,1-dimethylbutyl group, 3-oxo-1-
Preferred are an i-propylbutyl group, a 3-oxo-1-methylbutyl group, a lactone group (3) and the like.

The resin (A-II) is, for example, (d) one or more kinds of alkali-soluble resins prepared in advance containing a repeating unit in which Z of the group —COOZ in the repeating unit (6) corresponds to a hydrogen atom. A method of introducing an acid dissociable group (1), (e)
It can be produced by, for example, a method of (co) polymerizing a polymerizable unsaturated monomer having one or more groups -COOZ. Examples of the alkali-soluble resin used in the method (d) include a norbornene derivative (hereinafter, referred to as a “carboxyl group-containing norbornene”) in which Z of the group —COOZ in the repeating unit (6) gives a repeating unit corresponding to a hydrogen atom. 1) is a repeating unit in which the unsaturated bond is cleaved.
There can be mentioned an addition polymerization type resin having at least one kind.

As the carboxyl group-containing norbornene derivative, for example, 5-carboxybicyclo [2.2.1]
Hept-2-ene, 5-methyl-5-carboxybicyclo [2.2.1] hept-2-ene, 5-ethyl-5-carboxybicyclo [2.2.1] hept-2-ene, 5-
n-propyl-5-carboxybicyclo [2.2.1] hept-2-ene, 6-methyl-5-carboxybicyclo
[2.2.1] Hept-2-ene, 6-ethyl-5-carboxybicyclo [2.2.1] Hept-2-ene, 6-n
Bipropyl [2.2.1] hept-2-ene derivatives such as -propyl-5-carboxybicyclo [2.2.1] hept-2-ene; 8-carboxytetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-
8-carboxytetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene, 8-ethyl-8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8-n-propyl-8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 9-methyl-8-carboxytetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 9-ethyl-8-carboxytetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodeca-3-ene, 9-n-propyl-8-carboxytetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] tetracyclo such as dodeca-3-ene [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene derivatives and the like.

Among these norbornene derivatives, 5-
Carboxycyclo [2.2.1] hept-2-ene, 5
-Methyl-5-carboxybicyclo [2.2.1] hept-2-ene, 8-carboxytetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-
8-carboxytetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene and the like are preferred.

The alkali-soluble resin used in the method (d) may be composed of only a repeating unit derived from a carboxyl group-containing norbornene derivative. The repeating unit in which the polymerizable unsaturated bond of the polymerizable unsaturated monomer (hereinafter referred to as “other polymerizable unsaturated monomer (ii)”) is 1
More than one species can be contained. Examples of the other polymerizable unsaturated monomer (ii) include norbornene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1] hept-2. -Ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-
Hydroxy-5-methylbicyclo [2.2.1] hept-
2-ene, 5-hydroxymethylbicyclo [2.2.1]
Norbornene or derivatives thereof such as hept-2-ene;

Tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene, 8-methyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8
-Ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene,
8-hydroxytetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene, 8-hydroxy-8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8-hydroxymethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-fluoro-tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-ene, 8-fluoromethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene, 8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-
Ene, 8-pentafluoroethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8,8-
Difluorotetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodeca-3-ene, 8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8,8-bis (trifluoromethyl) tetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene,
8,9-bis (trifluoromethyl) tetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8
-Methyl-8-trifluoromethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8,8,
9-trifluorotetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodec-3-ene, 8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] dodeca-3-ene, 8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene, 8,8-difluoro-9,9
-Bis (trifluoromethyl) tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodeca-3-ene, 8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene, 8,8,9-trifluoro-
9-pentafluoropropoxytetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene, 8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene, 8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8- (2,2,2-trifluorocarboxyethyl) tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene, 8-methyl-8- (2,2,
2-trifluorocarboxyethyl) tetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene or derivatives thereof;

Dicyclopentadiene, tricyclo [5.
2.1.0 ^2,6 ] dec-8-ene, tricyclo [5.2.
1.0 ^2,6 ] dec-3-ene, tricyclo [4.4.0.
1 ^2,5] undec-3-ene, tricyclo [6.2.1.
0 ^1,8 ] undec-9-ene, tricyclo [6.2.1.
0 ^1,8] undec-4-ene, tetracyclo [4.4.
0.1 ^2,5 . ^17,10 . 0 ^1,6 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . ^17,10 . 0
^1,6 ] dodec-3-ene, 8-ethylidenetetracyclo
[4.4.0.1 ^2,5 . 1 ^7,12 ] Dodeca-3-ene, 8
-Ethylidenetetracyclo [4.4.0.1 ^2,5 . 1
^7,10 . 0 ^1,6 ] dodeca-3-ene, pentacyclo [6.
5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-4-ene, pentacyclo [7.4.0.1 ^{2,5. 19,12} . 0
^8,13] pentadeca-3 other alicyclic monomers such as ene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2-hydroxypropyl, 3-hydroxypropyl (meth) acrylate,
Methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, n-propyl α-hydroxymethyl acrylate, n-butyl α-hydroxymethyl acrylate, and (meth) acrylic acid as a compound having an alicyclic skeleton Norbornyl, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate,
Tetracyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, 1-methyladamantyl (meth) acrylate, adamantyl methyl (meth) acrylate, (meth)
Carboxytricyclodecanyl acrylate, carboxytetracyclodecanyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth)
Cyclohexenyl acrylate, 4- (meth) acrylic acid
Methoxycyclohexyl, 2-cyclopropyloxycarbonylethyl (meth) acrylate, 2-cyclopentyloxycarbonylethyl (meth) acrylate, 2-cyclohexyloxycarbonylethyl (meth) acrylate, 2-cyclohexenyloxy (meth) acrylate In addition to (meth) acrylates such as carbonylethyl and 2- (4′-methoxycyclohexyl) oxycarbonylethyl (meth) acrylate,

Vinyl acetate, vinyl propionate, vinyl butyrate, (meth) acrylonitrile, α-chloroacrylonitrile, crotonitrile, maleinitrile, fumaronitrile, mesaconitrile, citraconitrile,
Itaconitrile, maleic anhydride, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itaconamide, N-vinyl-ε-caprolactam, N-vinylpyrrolidone , Vinylpyridine, vinylimidazole and the like.

Among these other polymerizable unsaturated monomers (ii), norbornene, 5-methoxycarbonylbicyclo
[2.2.1] Hept-2-ene, 5-hydroxybicyclo [2.2.1] Hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] Hept-2-ene, 8-
Methoxycarbonyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodeca-3-ene, 8-hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3
-Ene, 8-hydroxymethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2- (meth) acrylate Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, (meth) Tetracyclodecanyl acrylate, dicyclopentenyl (meth) acrylate, adamantyl (meth) acrylate, maleinitrile, fumaronitrile, maleic anhydride, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, Maleamide, fumaramide, mesaconamide, citraconic , Itakon'amido, N- vinyl -ε- caprolactam, N- vinyl pyrrolidone, vinyl pyridine, vinyl imidazole, and the like are preferable.

Although the content of the repeating unit derived from the carboxyl group-containing norbornene derivative in the alkali-soluble resin used in the method (d) cannot be specified unconditionally depending on the type of the repeating unit and the other repeating units, usually, It is 10 to 100 mol%, preferably 15 to 100 mol%. The introduction of the acid dissociable group (1) in the method (d) can be carried out by esterifying a carboxyl group in the alkali-soluble resin by, for example, the tertiary alcohol (4) by a conventional method. Also,
As the polymerizable unsaturated monomer having a group -COOZ used in the method (e), for example, a hydrogen atom of a carboxyl group in the carboxyl group-containing norbornene derivative exemplified in the method (d) may be replaced with an acid. Compounds substituted with a dissociable group (1) can be mentioned. In the method (e),
In addition to the polymerizable unsaturated monomer having the group -COOZ, the other polymerizable unsaturated monomer (ii) may be used in an amount of usually 90 mol% or less, preferably 85 mol% or less. it can.

The polymerization in the production of the alkali-soluble resin in the method (d) and the polymerization in the method (e) are carried out, for example, by radical polymerization of hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds and the like. It can be carried out in a suitable solvent using a polymerization catalyst. As the solvent used for the polymerization, for example, n-pentane, n-hexane, n-heptane, n-
Alkanes such as octane, n-nonane and n-decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; benzene,
Aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene; halogenated hydrocarbons such as chlorobutane, bromohexanes, dichloroethane, hexamethylene dibromide, chlorobenzene; ethyl acetate, acetic acid n
Saturated carboxylic esters such as -propyl, i-propyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; and ethers such as tetrahydrofuran, 1,2-dimethoxyethane and 1,2-diethoxyethane. Can be mentioned. These solvents can be used alone or in combination of two or more.

In the resin (A-II), the content of the repeating unit (6) was determined based on the total repeating units in the resin.
Usually, it is at least 20 mol%, preferably at least 30 mol%, more preferably at least 40 mol%. In this case, when the content of the repeating unit (4) is 20 mol% or less, transparency to radiation and dry etching resistance tend to decrease. Further, the introduction ratio of the group -COOZ in the resin (A-II) (the group -COOZ, the group -COOZ 'and the group -COOZ in the resin).
(Ratio of the number of groups -COOZ to the total number of COOH)
Cannot be unconditionally defined by the type of the group -COOZ or the constituent monomer of the resin, but is usually 15 to 100 mol%, more preferably 20 to 100 mol%.

Specific examples of the preferred resin (A-II) in the present invention are as follows. A homopolymer of a norbornene derivative represented by the following general formula (7) (hereinafter, referred to as “norbornene derivative (7)”);

[0057]

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[In the general formula (7), W ² is

[0059]

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Where i is 0 or 1. Norbornene derivative (7) / 5-carboxybicyclo
[2.2.1] Hept-2-ene copolymer, norbornene derivative (7) / 8-carboxytetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene copolymer, norbornene derivative (7) / 5-methyl-5-carboxybicyclo [2.2.1] hept-2-ene copolymer, norbornene derivative (7) / 8-methyl-8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-
Ene copolymer, norbornene derivative (7) / maleic anhydride copolymer, norbornene derivative (7) / maleic anhydride / tricyclodecanyl (meth) acrylate copolymer, norbornene derivative (7) / maleic anhydride / 2-hydroxypropyl (meth) acrylate copolymer, norbornene derivative (7) / maleic anhydride / 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene copolymer, norbornene derivative (7) / maleic anhydride / 5-hydroxybicyclocyclo [2.2.1] hept-2-ene copolymer, norbornene derivative (7) / Maleic anhydride / 8-hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-
Ene copolymer, norbornene derivative (7) / maleic anhydride / 5-hydroxymethylbicyclocyclo [2.2.
1] Norbornene derivative (7) such as hept-2-ene copolymer / maleic anhydride / 8-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene copolymer, norbornene derivative (7) / maleic anhydride / 5-hydroxymethyl-5-methylbicyclocyclo
[2.2.1] Hept-2-ene copolymer, norbornene derivative (7) / maleic anhydride / 8-hydroxymethyl-8-methyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodeca-3-ene copolymer.

The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) of the resin (A) measured by gel permeation chromatography varies depending on the desired properties as a resist, but is preferably 2,000. -10
000, more preferably 3,000 to 60,00.
0. In this case, if Mw is less than 2,000, the film-forming property tends to decrease, while if it exceeds 100,000, developability, resolution and the like tend to decrease. Further, the dispersity of the resin (A) (Mw / Mn; Mn is a number average molecular weight in terms of polystyrene measured by gel permeation chromatography) is preferably 1 to 5,
More preferably, it is 1-3.

Acid Generator (B) The component (B) in the present invention comprises a radiation-sensitive acid generator that generates an acid upon exposure (hereinafter, referred to as “acid generator (B)”). The acid generator (B) dissociates the acid dissociable group (1) itself and / or the lactone ring in the acid dissociable group (1) present in the resin (A) by the action of an acid generated by exposure. As a result, the exposed portion of the resist film becomes easily soluble in the alkali developing solution, and has an effect of forming a positive resist pattern. Examples of such an acid generator (B) include an onium salt, a halogen-containing compound, a diazoketone compound, a sulfone compound, and a sulfonic acid compound. Examples of these acid generators (B) include the following.

Onium salt: Examples of the onium salt include an iodonium salt, a sulfonium salt (including a tetrahydrothiophenium salt), a phosphonium salt, a diazonium salt, a pyridinium salt and the like. Specific examples of preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro n-butanesulfonate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium hexafluoroantimonate, bis (4-
t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro n-butanesulfonate, bis (4
-T-butylphenyl) iodonium dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium naphthalene sulfonate, bis (4-t-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nona Fluoro n-
Butanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, triphenylsulfonium camphorsulfonate, (4-hydroxyphenyl) benzenemethylsulfonium toluenesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl ( 2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (4-hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonate Trifluoromethanesulfonate 4-cyano-1-naphthyl dimethyl sulfonium trifluoromethane sulfonate, 4-cyano-1-naphthyl diethyl sulfonium trifluoromethane sulfonate, 4-nitro-1-naphthyl dimethyl sulfonium trifluoromethane sulfonate, 4-nitro-1-
Naphthyl diethylsulfonium trifluoromethanesulfonate, 4-methyl-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1
-Naphthyl diethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate,

4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
-Methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxy-1-
Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-propoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxymethoxy-1- Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (1-methoxyethoxy) -1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4- (2- Methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxycarbonyloxy-1-naphth Tetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-propoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-i-propoxy Carbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-t
-Butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4
-(2-tetrahydrofuranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2-tetrahydropyranyloxy) -1
-Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate and the like.

Halogen-containing compound: Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Specific examples of preferred halogen-containing compounds include phenyl-bis (trichloromethyl) -s-triazine, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine and the like. (Trichloromethyl) -s
-Triazine derivatives and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane. Diazoketone compound: Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, and a diazonaphthoquinone compound. Specific examples of preferred diazoketones include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, and 1,2-naphtho of 2,3,4,4'-tetrahydroxybenzophenone. Quinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-
5-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, and the like. Can be. Sulfone compound: Examples of the sulfone compound include β
-Ketosulfone, β-sulfonylsulfone and α-diazo compounds of these compounds. Specific examples of preferable sulfone compounds include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenylsulfonyl) methane. Sulfonic acid compound: Examples of the sulfonic acid compound include an alkylsulfonic acid ester, an alkylsulfonic acid imide, a haloalkylsulfonic acid ester, an arylsulfonic acid ester, and an iminosulfonate. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, tristrifluoromethanesulfonate of pyrogallol, and nitrobenzyl-9.1.
0-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-hydroxysuccinimide trifluoromethanesulfonate,
Examples thereof include 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate.

Among these acid generators (B), diphenyliodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) ) Sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dimethyl (2-oxocyclohexyl)
Sulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate, trifluoromethane Sulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-hydroxysuccinimide trifluoromethanesulfonate,
1,8-Naphthalenedicarboxylic acid imide trifluoromethanesulfonate is preferred.

In the present invention, the acid generator (B) can be used alone or in combination of two or more. The amount of the acid generator (B) used is usually 0.1 to 10 parts by weight, preferably 0.5 part by weight, based on 100 parts by weight of the resin (A) from the viewpoint of securing the sensitivity and developability as a resist.
７7 parts by weight. In this case, if the amount of the acid generator (B) used is less than 0.1 part by weight, sensitivity and developability tend to decrease, while if it exceeds 10 parts by weight, transparency to radiation decreases, and Tends to be difficult to obtain.

Various Additives In the present invention, the acid generator (B) is further exposed to light.
An acid diffusion controller having an action of controlling the diffusion phenomenon of the acid generated from the above in the resist film and suppressing undesired chemical reactions in the non-exposed area can be blended. By using such an acid diffusion controlling agent, the storage stability of the composition is improved, the resolution as a resist is improved, and the resist pattern due to the fluctuation of the delay time (PED) from exposure to development is increased. Can be suppressed, and the process stability becomes extremely excellent. As the acid diffusion controller, a nitrogen-containing organic compound whose basicity does not change by exposure or heat treatment during the resist pattern forming step is preferable. As such a nitrogen-containing organic compound, for example, the following general formula (8)

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[In the general formula (8), R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group, an aryl group or an alkyl group. (Hereinafter, referred to as "nitrogen-containing compound (I)"), a diamino compound having two nitrogen atoms in the same molecule (hereinafter, referred to as "nitrogen-containing compound (II)"), and a nitrogen atom (Hereinafter, referred to as "nitrogen-containing compound (III)"), an amide group-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, and the like. Examples of the nitrogen-containing compound (I) include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine;
n-butylamine, di-n-pentylamine, di-n-
Dialkylamines such as hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, and di-n-decylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, -N-pentylamine, tri-n-hexylamine,
Trialkylamines such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline And aromatic amines such as 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine and 1-naphthylamine. As the nitrogen-containing compound (II), for example,
Ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 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 a polymer of polyethyleneimine, polyallylamine, dimethylaminoethylacrylamide, and the like. Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide,
N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N
-Methylpyrrolidone and the like. Examples of the urea compound include urea, methylurea, 1,
1-dimethylurea, 1,3-dimethylurea, 1,
Examples thereof include 1,3,3-tetramethylurea, 1,3-diphenylurea, and tributylthiourea. Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole and 4-methyl-2-phenylimidazole; pyridine, 2-methylpyridine, 4-methylpyridine and 2-ethylpyridine , 4-ethylpyridine,
2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, nicotine, nicotinic acid,
In addition to pyridines such as nicotinamide, quinoline, 8-oxyquinoline and acridine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, , 4-diazabicyclo [2.2.2] octane and the like.

Among these nitrogen-containing organic compounds, nitrogen-containing compounds (I), nitrogen-containing heterocyclic compounds and the like are preferable. Further, among the nitrogen-containing compounds (I), trialkylamines are particularly preferable, and among the nitrogen-containing heterocyclic compounds, pyridines are particularly preferable. The acid diffusion controllers can be used alone or in combination of two or more. The compounding amount of the acid diffusion controller is usually 15 parts by weight or less, preferably 10 parts by weight or less, more preferably 5 parts by weight or less, per 100 parts by weight of the resin (A). In this case, if the amount of the acid diffusion controller exceeds 15 parts by weight, the sensitivity as a resist and the developability of an exposed portion tend to decrease. In addition,
When the compounding amount of the acid diffusion controller is less than 0.001 part by weight, depending on the process conditions, there is a possibility that the pattern shape and the dimensional accuracy as a resist may be reduced.

Further, the radiation-sensitive resin composition of the present invention may contain other various additives as required. Such additives include, for example, surfactants that have the effect of improving coatability, developability, and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether,
In addition to nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Polyflow No.
No. 75, the same No. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo), F-top EF301, EF303, EF352 (manufactured by Tochem Products), Megafax F171, F17
3 (manufactured by Dainippon Ink and Chemicals), Florad FC43
0, FC431 (manufactured by Sumitomo 3M), Asahigard AG710, Surflon S-382, SC-101,
SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass). These surfactants can be used alone or
A mixture of more than one species can be used. The compounding amount of the surfactant is 100 in total of the resin (A) and the acid generator (B).
It is usually 2 parts by weight or less based on parts by weight. In addition, examples of the additives other than the above include an antihalation agent, an adhesion aid, a storage stabilizer, and an antifoaming agent.

Preparation of Composition Solution The radiation-sensitive resin composition of the present invention is usually used such that the total solid content is, for example, 5 to 50% by weight, preferably 10 to 25% by weight, when used. After being dissolved in a solvent, for example, the composition is prepared as a composition solution by filtering through a filter having a pore size of about 0.2 μm. Examples of the solvent used for preparing the composition solution include 2-
Butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone,
Linear ketones such as -methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone; cyclopentanone, 3-methyl-2-cyclopentanone, cyclohexanone, 2-ketone Cyclic ketones such as methylcyclohexanone, 2,6-dimethylcyclohexanone, and isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate; Propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i-butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene Propylene glycol monoalkyl ether acetates such as recohol mono-t-butyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, 2 Alkyl 2-hydroxypropionates such as n-butyl hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, t-butyl 2-hydroxypropionate,

N-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-
Methyl hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, N-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone,
N, N-dimethylformamide, N, N-dimethylacetamide, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone,
Examples include ethylene carbonate and propylene carbonate.

These solvents can be used alone or in combination of two or more. Among them, cyclic ketones, linear ketones, propylene glycol monoalkyl ether acetates and 2-hydroxy Alkyl propionates are preferred.

Method for Forming Resist Pattern The radiation-sensitive resin composition of the present invention is particularly useful as a chemically amplified positive resist. In the chemically amplified positive resist, the acid generated from the acid generator (B) upon exposure causes the acid dissociable group (1) itself in the resin (A) and / or the acid dissociable group in the acid dissociable group. The lactone ring dissociates, causing a reaction that is converted to an acidic functional group such as a phenolic hydroxyl group and a carboxyl group, and as a result, the solubility of the exposed portion of the resist in an alkali developing solution increases,
The exposed portion is dissolved and removed by an alkali developing solution to obtain a positive resist pattern. When forming a resist pattern from the radiation-sensitive resin composition of the present invention,
A resist solution is formed by applying the composition solution onto a substrate such as a silicon wafer or a wafer coated with aluminum by a suitable coating means such as spin coating, casting coating, roll coating, etc. And then exposing the resist film to form a predetermined resist pattern. The radiation used at this time is an ArF excimer laser (wavelength 1).
93 nm) or KrF excimer laser (wavelength 24
8 nm) is preferred. In the present invention, it is preferable to perform a heat treatment (hereinafter, referred to as “post-exposure bake”) after the exposure. By the post-exposure bake, the acid dissociable group (1)
The dissociation reaction of the lactone ring itself and / or the acid dissociable group proceeds smoothly. The heating conditions for the post-exposure bake vary depending on the composition of the radiation-sensitive resin composition, but are usually 30 to 200 ° C, preferably 50 to 170 ° C. In the present invention, in order to maximize the potential of the radiation-sensitive resin composition, for example, JP-B-6-1245.
As disclosed in Japanese Unexamined Patent Publication No. 2 (1993) -1995, an organic or inorganic antireflection film can be formed on a substrate to be used, and the influence of basic impurities and the like contained in an environmental atmosphere can be reduced. To prevent this, for example, refer to Japanese Patent Application Laid-Open No. 5-188598.
As disclosed in Japanese Unexamined Patent Publication (Kokai) No. HEI 7 (1994), a protective film can be provided on a resist film, or these techniques can be used in combination. Next, a predetermined resist pattern is formed by developing the exposed resist film. Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propylamine. , Triethylamine, methyldiethylamine, dimethylethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4. An alkaline aqueous solution in which at least one alkaline compound such as 3.0] -5-nonene is dissolved. The concentration of the alkaline aqueous solution is usually 10% by weight.
It is as follows. In this case, the concentration of the alkaline aqueous solution is 10
If the content is more than 10% by weight, unexposed portions are also dissolved in the developer, which is not preferable. Further, for example, an organic solvent can be added to the developer composed of the alkaline aqueous solution. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 3-methyl-2-cyclopentanone,
Ketones such as 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol , 1,4-
Alcohols such as hexane dimethylol; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol and acetonylacetone. And dimethylformamide. These organic solvents can be used alone or in combination of two or more. The amount of the organic solvent used is preferably 100% by volume or less based on the alkaline aqueous solution. In this case, if the amount of the organic solvent used exceeds 100% by volume, the developability may be reduced and the undeveloped portion of the exposed portion may increase. In addition, an appropriate amount of a surfactant or the like can be added to a developer composed of an alkaline aqueous solution. After development with a developing solution composed of an alkaline aqueous solution, it is generally washed with water and dried.

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Embodiments of the present invention will be described below more specifically with reference to examples. However, the present invention is not limited to these embodiments. Here, parts and% are based on weight unless otherwise specified.
Each measurement and evaluation in Examples and Comparative Examples was performed in the following manner. Mw: Tosoh Corporation GPC column (G2000HXL 2
Gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analytical conditions of flow rate 1.0 ml / min, elution solvent tetrahydrofuran, column temperature 40 ° C. It was measured. Radiation transmittance: A 1 μm-thick resist film obtained by spin-coating the composition solution on quartz glass and baking on a hot plate maintained at 90 ° C. for 1 minute,
From the absorbance at a wavelength of 193 nm, the radiation transmittance was calculated and used as a measure of transparency in the far ultraviolet region. Relative etching rate: For a coating having a dry film thickness of 0.5 μm obtained by spin-coating a composition solution on a silicon wafer,
Using a dry etching apparatus (Pinnacle8000) manufactured by PMT, the etching gas is CF ₄ and the gas flow rate is 75 scc.
Dry etching was performed under the conditions of m, pressure 2.5 mTorr, and output 2500 W, the etching rate was measured, and the relative etching rate was evaluated based on the relative value to the etching rate of the film made of cresol novolak resin. The lower the etching rate, the better the dry etching resistance. Sensitivity: After the composition solution was spin-coated on a silicone wafer, prebaking was performed for 90 seconds on a hot plate maintained at the temperature shown in Table 1 to form a 0.5 μm-thick resist film. The resist film was exposed through a mask pattern using an ArF excimer laser exposure device (Nikon Corp., lens numerical aperture 0.55, exposure wavelength 193 nm). Next, after baking was performed for 90 seconds on a hot plate maintained at the temperature shown in Table 1, the film was developed with a 2.38% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute, washed with water, and dried. A positive resist pattern was formed. At this time, a line-and-space pattern (1 L
1S) was defined as an optimal exposure amount for forming a line width of 1: 1 and this optimal exposure amount was defined as sensitivity. Resolution: The minimum resist pattern size resolved when exposed at the optimal exposure amount was defined as the resolution. Developability: The degree of scum and residual development was examined using a scanning electron microscope. Pattern shape: lower side dimension L of a rectangular cross section of a line and space pattern (1L1S) having a line width of 0.20 μm
₁ and the upper and lower side dimensions L ₂ were measured by a scanning electron microscope. When the pattern satisfies 0.85 ≦ L ₂ / L ₁ ≦ 1 and the pattern shape did not have a tail, the pattern shape was “good”. It was assumed to be.

(1) Synthesis of tertiary alcohol having acid dissociable group (1) Synthesis Example 1 1-methyl-1- (2'-γ-butyrolactonyl) eta
9.5 g of synthetic zinc phenol and 1.1 g of iodine were placed in a flask, and the inside of the flask was purged with nitrogen. Subsequently, acetone / 2-bromo-γ-butyrolactone = 5.
After adding 0 g / 21.1 g of the mixed solution over 1 hour, the mixture was stirred and reacted at 70 ° C. for 5 hours. After the reaction,
After adding 50 ml of water and further adding 200 ml of ethyl acetate, the aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, after anhydrous magnesium sulfate was added to the organic layer and dried, ethyl acetate was distilled off under reduced pressure to give 1-methyl-1- (2′-γ-butyrolactonyl) represented by the following formula (9). 9.1 g of ethanol was obtained.

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Synthesis Example 2 1-methyl-1- (2′-δ-valerolactonyl) eta
9.5 g of synthetic zinc phenol and 1.1 g of iodine were placed in a flask, and the inside of the flask was purged with nitrogen. Subsequently, acetone / 2-bromo-δ-valerolactone = 5.
After a mixed solution of 0 g / 22.9 g was added over 1 hour, the mixture was stirred and reacted at 70 ° C. for 5 hours. After the reaction,
After adding 50 ml of water and further adding 200 ml of ethyl acetate, the aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, after anhydrous magnesium sulfate was added to the organic layer and dried, ethyl acetate was distilled off under reduced pressure to give 1-methyl-1- (2′-δ-valerolactonyl) represented by the following formula (10).
10 g of ethanol was obtained.

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(2) Synthesis of Polymerizable Unsaturated Monomer Synthesis Example 3 6-8.0 g of 1-methyl-1- (2′-γ-butyrolactonyl) ethanol, 8-carboxytetracycloacrylate [4.4.0] .1 ^2,5 . 1 ^7,10] dodecane sills 119 g, put trifluoroacetic anhydride 90.4g flask, anhydrous tetrahydrofuran 300m
1 and the inside is replaced with dry air.
For 80 minutes. Subsequently, the mixture was stirred and reacted at room temperature for 8 hours. After the completion of the reaction, a saturated aqueous solution of sodium hydrogen carbonate was added until the reaction solution became neutral. After adding 500 ml of ethyl acetate, the aqueous layer was separated using a separating funnel. Subsequently, an operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, anhydrous magnesium sulfate was added to the organic layer and dried, and then ethyl acetate was distilled off under reduced pressure to obtain 154 g of a compound represented by the following formula (11). This compound is referred to as an ester compound (a).

[0083]

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Synthesis Example 4 1-Methyl-1- (2′-γ-butyrolactonyl) ethanol 68.0 g, 8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-ene (87.9 g) and trifluoroacetic anhydride (90.4 g) were placed in a flask, and anhydrous tetrahydrofuran (50 ml) was added.
After the inside was replaced with dry air, the mixture was stirred at 10 ° C. for 80 minutes. Subsequently, the mixture was stirred and reacted at room temperature for 8 hours. After the completion of the reaction, a saturated aqueous solution of sodium hydrogen carbonate was added until the reaction solution became neutral.
After adding 00 ml, the aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, anhydrous magnesium sulfate was added to the organic layer and dried, and then ethyl acetate was distilled off under reduced pressure to obtain 115.0 g of a compound represented by the following formula (12). This compound is referred to as an ester compound (b).

[0085]

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Synthesis Example 5 11.6 g of 1-methyl-1- (2′-γ-butyrolactonyl) ethanol and 68 g of triethylamine were placed in a flask, dissolved in 200 ml of anhydrous dichloromethane, and stirred at 0 ° C. for 10 minutes. Subsequently, after 56 g of acrylic acid chloride was added over 2 hours, the reaction solution was returned to room temperature, and further reacted by stirring for 3 hours. After completion of the reaction, filtration was performed to remove triethylamine hydrochloride,
After adding 50 ml of water to the filtrate, the aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, anhydrous magnesium sulfate was added to the organic layer to dry it, and then dichloromethane was distilled off under reduced pressure to obtain {1-methyl-1- (2′-γ-acrylate) acrylate represented by the following formula (13). Butyrolactonyl) ethyl 6
7.4 g were obtained. This compound is referred to as an ester compound (c).

[0087]

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Synthesis Example 6 14.1 g of 1-methyl-1- (2′-δ-butyrolactonyl) ethanol, 119 g of a compound represented by the following formula (14), and 90.4 g of trifluoroacetic anhydride were placed in a flask. , Anhydrous tetrahydrofuran 300m
1 and the inside is replaced with dry air.
For 80 minutes. Subsequently, the mixture was stirred and reacted at room temperature for 8 hours. After the completion of the reaction, a saturated aqueous solution of sodium hydrogen carbonate was added until the reaction solution became neutral. After adding 500 ml of ethyl acetate, the aqueous layer was separated using a separating funnel. Subsequently, an operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, anhydrous magnesium sulfate was added to the organic layer and dried, and then ethyl acetate was distilled off under reduced pressure to obtain 155.5 g of a compound represented by the following formula (15). This compound is referred to as an ester compound (d).

[0089]

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[0090]

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Synthesis Example 7 14.1 g of 1-methyl-1- (2′-δ-butyrolactonyl) ethanol, 8-carboxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca-3-ene (87.9 g) and trifluoroacetic anhydride (90.4 g) were placed in a flask, and anhydrous tetrahydrofuran (50 m) was added.
1 and the inside is replaced with dry air.
For 80 minutes. Subsequently, the mixture was stirred and reacted at room temperature for 8 hours. After the completion of the reaction, a saturated aqueous solution of sodium hydrogen carbonate was added until the reaction solution became neutral, and 200 ml of ethyl acetate was further added. Then, an aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, anhydrous magnesium sulfate was added to the organic layer and dried, and then ethyl acetate was distilled off under reduced pressure to obtain 135.0 g of a compound represented by the following formula (16). This compound is referred to as an ester compound (e).

[0092]

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Synthesis Example 8 18.9 g of 1-methyl-1- (2′-δ-butyrolactonyl) ethanol and 68 g of triethylamine were put in a flask, dissolved in 200 ml of anhydrous dichloromethane, and stirred at 0 ° C. for 10 minutes. Subsequently, after 56 g of acrylic acid chloride was added over 2 hours, the reaction solution was returned to room temperature, and further reacted by stirring for 3 hours. After completion of the reaction, filtration was performed to remove triethylamine hydrochloride,
After adding 50 ml of water to the filtrate, the aqueous layer was separated using a separating funnel. Subsequently, the operation of adding 50 ml of water to the organic layer and separating the aqueous layer was performed three times, and the organic layer was sufficiently washed. Subsequently, anhydrous magnesium sulfate was added to the organic layer and dried, and then dichloromethane was distilled off under reduced pressure to give {1-methyl-1- (2′-δ-acrylate) acrylate represented by the following formula (17). Valerolactonyl) ethyl｝ 70
g was obtained. This compound is referred to as an ester compound (f).

[0094]

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(3) Production of Resin (A) Polymerization Example 1 27.8 g of ester compound (a), 15 g of tricyclodecanyl acrylate, 0.2 g of azoisobutyronitrile, 0.1 g of t-dodecyl mercaptan Was dissolved in 100 ml of 2,2-diethoxyethane, and stirred at a reaction temperature of 65 ° C. for 5 hours to react. After completion of the reaction, the reaction solution was administered in a large amount of methanol to reprecipitate the resin, followed by drying under reduced pressure to obtain 36 g of a white resin having an Mw of 17,000. In this resin, the content of the repeating unit derived from the ester compound (a) and the content of the repeating unit derived from tricyclodecanyl acrylate were 45 mol% and 55 mol%, respectively. This resin is referred to as a resin (A1).

Polymerization Example 2 34.8 g of the ester compound (b), 9.4 g of maleic anhydride and 3.3 g of azoisobutyronitrile were dissolved in 40 ml of 1,2-diethoxyethane. The mixture was stirred for an hour to react. After the reaction,
The reaction solution was administered in a large amount of methanol to reprecipitate the resin, and then dried under reduced pressure to obtain 22 g of a white resin having an Mw of 5,000. This resin is an ester compound (b)
Are 50 mol% and 50 mol%, respectively.
Mole%. This resin is referred to as a resin (A2).

Polymerization Example 3 22.6 g of the ester compound (c), 21.9 g of tricyclodecanyl acrylate, 0.2 g of azoisobutyronitrile, 0.1 g of t-dodecylmercaptan and 100 ml of 1,2-diethoxyethane And reacted by stirring at a reaction temperature of 65 ° C. for 5 hours. After completion of the reaction, the reaction solution was administered in a large amount of methanol to reprecipitate the resin, and then dried under reduced pressure to obtain 17.3 g of a white resin having an Mw of 14,000. In this resin, the content of the repeating unit derived from the ester compound (c) and the content of the repeating unit derived from tricyclodecanyl acrylate were 55 mol% and 45 mol%, respectively. This resin is referred to as a resin (A3).

Polymerization Example 4 28.7 g of the ester compound (d), 15 g of tricyclodecanyl acrylate, 0.2 g of azoisobutyronitrile and 0.1 g of t-dodecylmercaptan were dissolved in 100 ml of 1,2-diethoxyethane. Then, the mixture was reacted by stirring at a reaction temperature of 65 ° C. for 5 hours. After completion of the reaction, the reaction solution was administered in a large amount of methanol to reprecipitate the resin, and then dried under reduced pressure to obtain 34.3 g of a white resin having an Mw of 13,000. In this resin, the content of the repeating unit derived from the ester compound (d) and the content of the repeating unit derived from tricyclodecanyl acrylate were 50 mol% and 50 mol%, respectively. This resin is referred to as a resin (A4).

Polymerization Example 5 36.3 g of the ester compound (e), 9.4 g of maleic anhydride and 3.3 g of azoisobutyronitrile were dissolved in 40 ml of 1,2-diethoxyethane. The mixture was stirred for an hour to react. After the reaction,
The reaction solution was administered in a large amount of methanol to reprecipitate the resin, and then dried under reduced pressure to obtain 19.3 g of a white resin having Mw of 4,000. In this resin, the content of the repeating unit derived from the ester compound (e) and the content of the repeating unit derived from maleic anhydride were 50 mol% and 50 mol%, respectively. This resin is referred to as a resin (A5).

Polymerization Example 6 24.0 g of ester compound (f), 21.9 g of tricyclodecanyl acrylate, 0.2 g of azoisobutyronitrile, 0.1 g of t-dodecyl mercaptan, and 100 ml of 1,2-diethoxyethane And reacted by stirring at a reaction temperature of 65 ° C. for 5 hours. After completion of the reaction, the reaction solution was administered in a large amount of methanol to reprecipitate the resin, and then dried under reduced pressure to obtain 13.5 g of a white resin having an Mw of 12,000. In this resin, the content of the repeating unit derived from the ester compound (f) and the content of the repeating unit derived from tricyclodecanyl acrylate were 50 mol% and 50 mol%, respectively. This resin is referred to as a resin (A6).

(4) Production of Comparative Resin Comparative Polymerization Example 1 15 g of t-butyl acrylate, 25 g of tricyclodecanyl acrylate, 0.2 g of azoisobutyronitrile and 0.1 g of t-dodecyl mercaptan were added to 1,2 -Dissolved in 100 ml of diethoxyethane, and reacted by stirring at a reaction temperature of 65 ° C for 5 hours. After completion of the reaction, the reaction solution was poured into a large amount of methanol to reprecipitate the resin, and then dried under reduced pressure to obtain 15 g of a white resin having an Mw of 20,000. This resin is referred to as a resin (a1).

[0102]

EXAMPLES Examples 1 to 7 and Comparative Examples 1 and 2 The resins produced in the above polymerization examples were mixed with the following acid generator (B) and a solvent to form a uniform solution. Table 1
Were prepared and various evaluations were made. Table 2 shows the evaluation results. The residual film ratios in Examples 1 to 7 and Comparative Examples 1 and 2 were all 96% or more. Acid generator (B) B1: cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate B2: triphenylsulfonium trifluoromethanesulfonate B3: 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate B4: 4- Hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate B5: 4-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate Solvent C1: 2-Heptanone C2: Ethyl 2-hydroxypropionate

[0103]

[Table 1]

[0104]

[Table 2]

[0105]

The radiation-sensitive resin composition of the present invention, as a chemically amplified resist, is excellent in radiation transparency and resolution and has a good balance of properties including sensitivity, developability, pattern shape, dry etching resistance and the like. And it can be used very suitably in the manufacture of semiconductor devices that are expected to be further miniaturized in the future.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tohru Kajita 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation

Claims (1)

[Claims] (A) An acid dissociable group represented by the following general formula (1):
An alkali-insoluble or alkali-insoluble resin having a group represented by the formula: 1) [In the general formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms or a 5- to 8-membered cyclic alkyl group; Or R ¹ and R ² are mutually bonded to form a 5- to 8-membered cyclic alkyl group, or R ³ and R ⁴ are mutually bonded to form a 5- to 8-membered cyclic alkyl group. And n is an integer of 1 to 4. And (B) a radiation-sensitive acid generator.