JP2001188347A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition excellent in shelf stability, having high transparency to radiation and excellent also in basic physical properties as a resist such as dry etching resistance, sensitivity, resolution and pattern shape. SOLUTION: The radiation sensitive resin composition contains (A) an acid- dissociable group-containing resin having repeating units derived from a (meth) acrylic acid derivative having an alicyclic skeleton containing an oxygen- or nitrogen-containing polar group typified by 3-hydroxy-1-adamantyl (meth)acrylate or 3-(8'-cyanotetracyclo[4.4.0.12,5.17,10]dodecyl (meth)acrulate and repeating units derived from another (meth)acrylic acid derivative having an alicyclic skeleton typified by 2-methyl-2-adamantyl (meth)acrylate and convertible to an alkali- soluble resin when the acid-dissociable group is dissociated and (B) a radiation sensitive acid generating agent.

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, and more particularly, to charged particles such as X-rays such as KrF excimer laser or ArF excimer laser, synchrotron radiation, and X-rays, and electron beams. The present invention relates to a radiation-sensitive resin composition that can be suitably used as a chemically amplified resist useful for fine processing using various radiations such as lines.

[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 fine processing at a sub-quarter micron level or less with near-ultraviolet rays. Therefore, in order to enable fine processing at a level of 0.20 μm or less, use of radiation having a shorter wavelength is being studied. Examples of such short-wavelength radiation include the emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, X-rays, and electron beams. Of these, a KrF excimer laser (wavelength: 248 nm) is particularly preferable. ) Or an ArF excimer laser (wavelength 193 nm) has attracted attention. As the radiation-sensitive resin composition suitable for the short-wavelength radiation, a component having an acid-dissociable functional group and a radiation-sensitive acid generator that generates an acid by irradiation with radiation (hereinafter, referred to as “exposure”). There have been proposed many compositions utilizing the chemical amplification effect between them (hereinafter, referred to as “chemically amplified radiation-sensitive compositions”). 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 a radiation-sensitive composition. Compositions containing an acid generator have been proposed. This composition is:
By the action of the acid generated by the exposure, the t-butyl ester group or t-butyl carbonate group present in the polymer is dissociated, so that the polymer has an acidic group consisting of a carboxyl group or a phenolic hydroxyl group. As a result, the phenomenon that the exposed area of the resist film becomes easily soluble in an alkali developing solution is used. By the way, many of the conventional chemically amplified radiation-sensitive compositions are based on phenolic resins, but in the case of such resins,
When far-ultraviolet rays are used as radiation, the far-ultraviolet rays are absorbed due to the aromatic ring in the resin, so that there is a drawback that the exposed far-ultraviolet rays cannot sufficiently reach the lower layer of the resist film. The amount is large in the upper layer portion of the resist film and smaller in the lower layer portion, and the resist pattern after development becomes thicker and trapezoidal as the upper portion is narrower and lower, resulting in a problem that sufficient resolution cannot be obtained. . Further, when the resist pattern after development has a trapezoidal shape, a desired dimensional accuracy cannot be achieved in the next step, that is, in performing 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 a resist pattern can be improved by increasing the radiation transmittance of a resist film. For example, a (meth) acrylate resin represented by polymethyl methacrylate has high transparency even with far ultraviolet rays and is a very preferable resin from the viewpoint of radiation transmittance. Has proposed a chemically amplified radiation-sensitive composition using a methacrylate resin. However, although this composition is excellent in terms of fine processing performance, it does not have an aromatic ring, and thus has a drawback that dry etching resistance is low. In this case, it is difficult to perform high-precision etching processing. However, it cannot be said that both the transparency to radiation and the resistance to dry etching are combined. Further, for a resist composed of a chemically amplified radiation-sensitive composition,
As one of the measures for improving the dry etching resistance without impairing the transparency to radiation, a method of introducing an alicyclic ring instead of an aromatic ring to the resin component of the composition is known, for example, JP-A-7-234511 discloses that
A chemically amplified radiation-sensitive composition using a (meth) acrylate resin having an alicyclic ring has been proposed. However, in a conventional chemically amplified radiation-sensitive composition into which a conventional alicyclic ring is introduced, as an acid-dissociable functional group, a group which is relatively easily dissociated by an acid (for example, an acetal-based functional group such as a tetrahydropyranyl group). Alternatively, a group which is relatively difficult to dissociate with an acid (for example, a t-butyl-based functional group such as a t-butyl ester group or a t-butyl carbonate group) is generally used, and the former resin component having an acid-dissociable functional group. In the case of using, the basic physical properties of the resist, particularly sensitivity and pattern shape are good, but there is a problem in storage stability as a composition, and when using the latter resin component having an acid dissociable functional group, the reverse Although the storage stability is good, there is a drawback that the basic physical properties of the resist, particularly the sensitivity and the pattern shape are impaired. In addition, in these compositions, since the resin component has an alicyclic ring, the hydrophobicity of the resin itself is extremely high, and there is also a problem with the substrate adhesion. Therefore, it has high transparency to radiation and excellent storage stability, dry etching resistance, sensitivity, resolution, pattern shape, etc.
There is also a need for the development of a chemically amplified radiation-sensitive composition having good substrate adhesion.

[0004]

An object of the present invention is to provide an actinic radiation, for example, a KrF excimer laser or Ar radiation.
As a chemically amplified resist that is sensitive to far ultraviolet rays typified by F excimer laser, it has excellent storage stability as a composition, high transparency to radiation, and dry etching resistance, sensitivity, resolution, pattern shape, etc. It is to provide a radiation-sensitive resin composition having excellent basic physical properties as a resist.

[0005]

According to the present invention, the object is to provide (A) a repeating unit (I) represented by the following general formula (1) and a repeating unit (I) represented by the following general formula (2): An alkali-insoluble or sparingly alkali-soluble resin containing an acid-dissociable group having II), which contains an alkali-soluble resin when the acid-dissociable group is dissociated, and (B) a radiation-sensitive acid generator. A radiation-sensitive resin composition comprising:

[0006]

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[In the general formula (1), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxyl group having 1 to 4 carbon atoms or a carbon atom. A represents a linear or branched hydroxyalkyl group of 1 to 4, A represents a single bond or a linear or branched alkylene group having a main chain carbon number of 1 to 4,
R ² is represented by the following formula (i) (where R ³ is 2 of 4 to 20 carbon atoms)
X ¹ represents a monovalent oxygen-containing polar group or a monovalent nitrogen-containing polar group. ), Formula (ii)
(However, R ⁴ represents a trivalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and X ² represents a divalent oxygen-containing polar group or a divalent nitrogen-containing polar group.) Or a formula (iii) ) (wherein, R ⁵ represents a tetravalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, X ³
Represents a trivalent oxygen-containing polar group or a trivalent nitrogen-containing polar group. )

[0008]

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And a group represented by the formula: ]

[0010]

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[In the general formula (2), R ⁶ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkoxyl group having 1 to 4 carbon atoms or a carbon atom. R ⁷ represents a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, and R ⁷ represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or the following formula (iv):

[0012]

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(However, each R ⁸ independently has 1 to 1 carbon atoms.
4 linear or branched alkyl group or 4 carbon atoms
A monovalent alicyclic hydrocarbon group having 20, and wherein at least one R ⁸ is a linear or branched alkyl group having 1 to 4 carbon atoms, or any two of R ⁸ mutual To form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms together with the carbon atoms to which each is bonded, and the remaining R ⁸ is a linear or branched C 1 to C 4 hydrocarbon group. Is an alkyl group. ). ] Is achieved.

Hereinafter, the present invention will be described in detail. (A) Component The component (A) in the present invention is a repeating unit represented by the general formula (1) (hereinafter, referred to as “repeating unit (1)”) and a repeating unit represented by the general formula (2). An alkali-insoluble or sparingly alkali-soluble acid-dissociable group-containing resin having a unit (hereinafter, referred to as “repeating unit (2)”) as an essential constituent unit, the resin being alkali-soluble when the acid-dissociable group is dissociated. (Hereinafter, referred to as “resin (A)”). The repeating unit (1) and the repeating unit (2) in the resin (A) have a carboxylic acid ester group having an acid dissociation property, and an acid generator (B) described later.
It is a unit showing an action of making the resin (A) alkali-soluble by dissociating under the action of an acid generated from to form a carboxyl group. In the present invention, by containing the resin (A), a radiation-sensitive resin composition excellent in transparency to radiation and dry etching resistance, in particular, can be obtained as a resist.

In the general formula (1), R ¹ has 1 to ¹ carbon atoms.
Examples of the linear or branched alkyl group of 4 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t -Butyl group and the like.
Examples of the linear or branched alkoxyl group having 1 to 4 carbon atoms for R ¹ include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group and a 2-methylpropoxy group. Group, 1-methylpropoxy group, t-butoxy group and the like. Also, R
The ^first linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, for example, hydroxymethyl group, 1
-Hydroxyethyl group, 2-hydroxyethyl group, 1-
Hydroxypropyl group, 2-hydroxypropyl group, 3
-Hydroxypropyl group, 1-hydroxybutyl group, 2
-Hydroxybutyl group, 3-hydroxybutyl group, 4-
Examples thereof include a hydroxybutyl group. Among these R ¹ , a hydrogen atom, a methyl group, a hydroxymethyl group and the like are particularly preferable.

In the general formula (1), the number of carbon atoms in the main chain of A is 1
As the linear or branched alkylene group of to 4,
For example, methylene group, ethylene group, 1-methyl-1,1
-Ethylene, propylene, trimethylene, tetramethylene and the like. Among these alkylene groups, a methylene group is particularly preferable.

In the general formula (1), each of the alicyclic hydrocarbon groups having 4 to 20 carbon atoms of R ³ , R ⁴ and R ⁵ includes:
For example, an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, or a group having a cycloalkane skeleton such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, or cyclooctane; these groups include, for example, a methyl group, Ethyl group, n-
One of linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms such as propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like. Groups having an alicyclic skeleton such as a group substituted by one or more species or one or more species can be exemplified. Among these alicyclic hydrocarbon groups, a group having an alicyclic skeleton selected from the group consisting of an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton, and a tetracyclododecane skeleton, and the above-described linear or branched groups And the like substituted with a cyclic or cyclic alkyl group, etc.
A group having an alicyclic skeleton selected from the group consisting of a norbornane skeleton, a tricyclodecane skeleton, and a tetracyclododecane skeleton, and a group obtained by substituting these groups with a methyl group or an ethyl group are preferable.

In the general formula (1), among X ¹ , X ² and X ³ , examples of the oxygen-containing polar group include a hydroxyl group; a carboxyl group; and an oxy group (ie, ＝ O
Ald group (i.e., -CHO group); hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy C1-C4 hydroxyalkyl groups such as butyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n- C1-C4 alkoxyl groups such as butoxy group, 2-methylpropoxy group, 1-methylpropoxy group and t-butoxy group can be mentioned. Examples of the nitrogen-containing polar group include cyano group; cyanomethyl A C2-C5 cyanoalkyl group such as a group, a 2-cyanoethyl group, a 3-cyanopropyl group, or a 4-cyanobutyl group; It can be mentioned. Among these oxygen-containing polar groups and nitrogen-containing polar groups, particularly, a hydroxyl group, an oxy group, an ald group, a hydroxymethyl group,
Preferred are a cyano group, a cyanomethyl group and the like.

The monomer giving the repeating unit (1) is, for example, a (meth) acrylic acid derivative represented by the following general formula (4) (hereinafter referred to as “(meth) acrylic acid derivative (4)”). Can be mentioned.

[0020]

Embedded image In [Formula (4), R ^1, R ² and A are each of general formula (1) the same as R ^1, R ² and A. )

Specific examples of the (meth) acrylic acid derivative (4) include compounds represented by the following formulas (4-1) to (4-127).

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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These (meth) acrylic acid derivatives (4)
Of the formulas (4-1), (4-2), and (4-
4), Formula (4-5), Formula (4-7), Formula (4-9), Formula (4-12), Formula (4-14), Formula (4-28), or Formula (4)
-35) and the like are preferred. In the resin (A), the repeating unit (4) may be used alone or in combination of two or more.

In the resin (A), the content of the repeating unit (1) is usually from 5 to 85 mol%, preferably from 10 to 80 mol%, more preferably from 1 to 80 mol%, based on all repeating units.
5 to 70 mol%. In this case, if the content of the repeating unit (1) is less than 5 mol%, the adhesiveness of the obtained resist to the substrate tends to decrease, while if it exceeds 85 mol%, the developability of the resist decreases. Tend to.

Next, in the general formula (2), examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R ⁶ include a methyl group, an ethyl group, an n-propyl group and an i-type group.
-Propyl group, n-butyl group, 2-methylpropyl group,
Examples thereof include a 1-methylpropyl group and a t-butyl group. Examples of the linear or branched alkoxyl group having 1 to 4 carbon atoms for R ⁶ include a methoxy group,
Ethoxy, n-propoxy, i-propoxy, n
-Butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group and the like.
Examples of the linear or branched hydroxyalkyl group having 1 to 4 carbon atoms for R ⁶ include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, and a 2-hydroxyethyl group. Examples include a hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
Among these R ⁶ , a hydrogen atom, a methyl group and the like are particularly preferable.

In the general formula (2), R ⁷ and R ^{8 each have} a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms and two R ⁸ groups having a carbon number of 4 to 20 formed by bonding to each other. Examples of the divalent alicyclic hydrocarbon group include an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, and a cycloalkane skeleton such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Groups; these groups include, for example, carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, etc. Examples thereof include groups having an alicyclic skeleton such as a group substituted with one or more of one to ten linear, branched, or cyclic alkyl groups, or one or more. Of these alicyclic hydrocarbon groups,
In particular, a group having an alicyclic skeleton selected from the group of an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton, and a tetracyclododecane skeleton, and these groups were substituted with the linear, branched, or cyclic alkyl group. And the like. Particularly, a group having an alicyclic skeleton selected from the group consisting of an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton, and a tetracyclododecane skeleton, and a group in which these groups are substituted with a methyl group or an ethyl group, etc. Is preferred.

Examples of the linear or branched alkyl group having 1 to 4 carbon atoms for R ⁸ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and a -Methylpropyl group, 1-methylpropyl group, t
-Butyl group and the like. Among these alkyl groups, a methyl group, an ethyl group and the like are particularly preferable.

Further, as the group represented by the formula (iv) in the general formula (2), any two R ⁸ are mutually bonded to form a divalent alicyclic hydrocarbon having 4 to 20 carbon atoms. Group, preferably a group having an alicyclic skeleton selected from the group consisting of an adamantane skeleton, a norbornane skeleton, a tricyclodecane skeleton and a tetracyclododecane skeleton, and a group obtained by substituting these groups with a methyl group or an ethyl group. A group which forms a group and the remaining R ⁸ is a chain alkyl group having 1 to 4 carbon atoms is preferred.

The monomer giving the repeating unit (2) is, for example, a (meth) acrylic acid derivative represented by the following general formula (5) (hereinafter referred to as “(meth) acrylic acid derivative (5)”). ].

[0062]

Embedded image In [Formula (5), R ⁶ and R ⁷ are each of general formula (2) as defined as R ⁶ and R ^7. ]

Specific examples of the (meth) acrylic acid derivative (5) include compounds represented by the following formulas (5-1) to (5-30).

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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These (meth) acrylic acid derivatives (5)
Of the formulas (5-1), (5-2), (5-3),
Compounds represented by the formula (5-5), the formula (5-6) or the formula (5-7) are preferable. In the resin (A), the repeating unit (2) may exist alone or in combination of two or more.

In the resin (A), the content of the repeating unit (2) is usually 5 to 70 mol%, preferably 5 to 60 mol%, more preferably 5 to 60 mol%, based on all repeating units.
50 mol%. In this case, if the content of the repeating unit (2) is less than 5 mol%, the resolution as a resist tends to decrease, while if it exceeds 70 mol%, the adhesion of the obtained resist to the substrate tends to decrease. There is.

Further, the resin (A) may have one or more kinds of repeating units derived from other polymerizable unsaturated monomers (hereinafter, referred to as “other repeating units”). As another preferable repeating unit, for example, the following general formula (3)
(Hereinafter, referred to as “repeating unit (3)”).

[0075]

Embedded image [In the general formula (3), R ⁹ , R ¹⁰ , R ¹¹ and R ¹²
Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted linear or branched C1-C6 alkyl group, a substituted or unsubstituted linear or branched C1 Represents an alkoxyl group having from 6 to 6 or an acid dissociable group having from 2 to 20 carbon atoms, and m is 0, 1 or 2
Is an integer. ]

In the general formula (3), R ⁹ , R ¹⁰ , R ¹¹
Examples of the halogen atom for R ¹² include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms for R ⁹ , R ¹⁰ , R ¹¹ and R ¹² include, for example, methyl group, ethyl group, n-propyl group, Examples thereof include i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, n-heptyl, and n-hexyl.

Examples of the substituted or unsubstituted linear or branched alkoxyl group having 1 to 6 carbon atoms for R ⁹ , R ¹⁰ , R ¹¹ and R ¹² include, for example, methoxy group, ethoxy group and n- Propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-heptyloxy group, n-
Hexyloxy group and the like can be mentioned.

Further, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each have an acid dissociable group having 2 to 20 carbon atoms (hereinafter referred to as “acid dissociable group (i)”).
That. ) Is, for example, a methoxycarbonyl group,
An ethoxycarbonyl group, an n-propoxycarbonyl group,
i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n
-Pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-decyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, 4-t-butylcyclohexyl (Cyclo) alkoxycarbonyl groups such as oxycarbonyl group, cycloheptyloxycarbonyl group and cyclooctyloxycarbonyl group; aryloxycarbonyl groups such as phenoxycarbonyl group, 4-t-butylphenoxycarbonyl group and 1-naphthyloxycarbonyl group; Aralkyloxycarbo such as benzyloxycarbonyl group, 4-t-butylbenzyloxycarbonyl group, phenethyloxycarbonyl group, 4-t-butylphenethyloxycarbonyl group; Le group; 1-methoxyethoxy group, 1-ethoxyethoxy group, 1
-N-propoxyethoxycarbonyl group, 1-i-propoxyethoxycarbonyl group, 1-n-butoxyethoxycarbonyl group, 1- (2'-methylpropoxy) ethoxycarbonyl group, 1- (1'-methylpropoxy) ethoxycarbonyl 1- (cyclo) alkyloxyethoxycarbonyl group such as 1-tert-butoxyethoxycarbonyl group, 1-cyclohexyloxyethoxycarbonyl group, 1- (4′-t-butylcyclohexyloxy) ethoxycarbonyl group; 1-phenoxy 1-aryloxyethoxycarbonyl groups such as ethoxycarbonyl group, 1- (4'-butylphenoxy) ethoxycarbonyl group, 1- (1'-naphthyloxy) ethoxycarbonyl group;
1-benzyloxyethoxycarbonyl group, 1- (4 ′
1-aralkyloxyethoxycarbonyl group such as -t-butylbenzyloxy) ethoxycarbonyl group;

Methoxycarbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonyl group, n-propoxycarbonylmethoxycarbonyl group, i-propoxycarbonylmethoxycarbonyl group, n-butoxycarbonylmethoxycarbonyl group, 2-methylpropoxycarbonylmethoxycarbonyl group, 1- (Cyclo) alkoxycarbonylmethoxycarbonyl groups such as methylpropoxycarbonylmethoxycarbonyl group, t-butoxycarbonylmethoxycarbonyl group, cyclohexyloxycarbonylmethoxycarbonyl group, 4-tert-butylcyclohexyloxycarbonylmethoxycarbonyl group; methoxycarbonylmethyl group, ethoxy Carbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl Group, n- butoxycarbonyl methyl group, 2-methyl propoxycarbonyl methyl group,
(Cyclo) alkoxycarbonylmethyl groups such as 1-methylpropoxycarbonylmethyl group, t-butoxycarbonylmethyl group, cyclohexyloxycarbonylmethyl group, 4-t-butylcyclohexyloxycarbonylmethyl group; phenoxycarbonylmethyl group, 4-t- Aryloxycarbonylmethyl groups such as butylphenoxycarbonylmethyl group and 1-naphthyloxycarbonylmethyl group; benzyloxycarbonylmethyl group, 4-t-butylbenzyloxycarbonylmethyl group, phenethyloxycarbonylmethyl group, 4-t-butylphenethyl An aralkyloxycarbonylmethyl group such as an oxycarbonylmethyl group;

2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propoxycarbonylethyl group, 2-i-propoxycarbonylethyl group, 2-n-butoxycarbonylethyl group, 2- (2 ′
-Methylpropoxy) carbonylethyl group, 2- (1 ′
2- (cyclo) such as -methylpropoxy) carbonylethyl group, 2-t-butoxycarbonylethyl group, 2-cyclohexyloxycarbonylethyl group, 2- (4'-t-butylcyclohexyloxycarbonyl) ethyl group
2-alkoxycarbonylethyl group; 2-phenyloxycarbonylethyl group, 2- (4′-t-butylphenoxycarbonyl) ethyl group, 2- (1′-naphthyloxycarbonyl) ethyl group and other 2-aryloxycarbonylethyl group; -Benzyloxycarbonylethyl group, 2-
(4′-t-butylbenzyloxycarbonyl) ethyl group, 2-phenethyloxycarbonylethyl group, 2-
A 2-aralkyloxycarbonylethyl group such as (4′-t-butylphenethyloxycarbonyl) ethyl group,
Examples thereof include a tetrahydrofuranyloxycarbonyl group and a tetrahydropyranyloxycarbonyl group.

Of these acid dissociable groups (i), the group -C
OOR '[where R' represents a (cyclo) alkyl group having 1 to 19 carbon atoms. Or a group -COOCH ₂ COOR ''
[However, R ″ represents a (cyclo) alkyl group having 1 to 17 carbon atoms. And particularly preferably a t-butoxycarbonyl group and a t-butoxycarbonylmethoxycarbonyl group. Further, m in the general formula (3) is preferably 0 or 1.

Examples of the monomer that gives the repeating unit (3) include a norbornene derivative represented by the following general formula (6) (hereinafter, referred to as “norbornene derivative (6)”).

[0083]

Embedded image In [Formula ^{(6), R 9, R} 10, R 11, R 12 and m are the general formula (3), respectively ^{R 9, R 10, R 11} , R 12
And m are synonymous. ]

In the norbornene derivative (6), m is 0
Specific examples of the compound having an acid dissociable group (i) include 5-methoxycarbonylbicyclo [2.2.1].
Hept-2-ene, 5-ethoxycarbonylbicyclo [
2.2.1] hept-2-ene, 5-n-propoxycarbonylbicyclo [2.2.1] hept-2-ene, 5
-I-propoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-n-butoxycarbonylbicyclo
[2.2.1] Hept-2-ene, 5- (2'-methylpropoxy) carbonylbicyclo [2.2.1] Hept-2-ene, 5- (1'-methylpropoxy) carbonylbicyclo [2 2.1] hept-2-ene, 5-t-
Butoxycarbonylbicyclo [2.2.1] hept-2
-Ene, 5-cyclohexyloxycarbonylbicyclo
[2.2.1] Hept-2-ene, 5- (4'-t-butylcyclohexyloxy) carbonylbicyclo [2.
2.1] Hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5- (1 ′
-Ethoxyethoxy) carbonylbicyclo [2.2.1
] Hept-2-ene, 5- (1'-cyclohexyloxyethoxy) carbonylbicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylmethoxycarbonylbicyclo [2.2.1] hept- 2-ene, 5-
1. Tetrahydrofuranyloxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-tetrahydropyranyloxycarbonylbicyclo [2.2.1] hept-2-
En,

5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5
-Ethoxycarbonylbicyclo [2.2.1] hept-
2-ene, 5-methyl-5-n-propoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-i-propoxycarbonylbicyclo [2.2.1]
] Hept-2-ene, 5-methyl-5-n-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5
-Methyl-5- (2'-methylpropoxy) carbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5- (1'-methylpropoxy) carbonylbicyclo
[2.2.1] Hept-2-ene, 5-methyl-5-t
-Butoxycarbonylbicyclo [2.2.1] hept-
2-ene, 5-methyl-5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-
Methyl-5- (4'-t-butylcyclohexyloxy) carbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-phenoxycarbonylbicyclo [
2.2.1] Hept-2-ene, 5-methyl-5
(1′-ethoxyethoxy) carbonylbicyclo [2.
2.1] Hept-2-ene, 5-methyl-5- (1′-
Cyclohexyloxyethoxy) carbonylbicyclo [
2.2.1] Hept-2-ene, 5-methyl-5-t-
Butoxycarbonylmethoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-methyl-5-tetrahydrofuranyloxycarbonylbicyclo [2.2.1]
Hept-2-ene, 5-methyl-5-tetrahydropyranyloxycarbonylbicyclo [2.2.1] hept-
2-ene,

5,6-di (methoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (ethoxycarbonyl) bicyclo [2.2.1] hept-2-ene
Ene, 5,6-di (n-propoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (i-
Propoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (n-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2 ′ -Methylpropoxycarbonyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-di (1′-methylpropoxycarbonyl) bicyclo [2.2.1] Hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [ 2.2.1] Hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-di (4′-t-butylcyclohexyloxycarbonyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-di (phenoxycarbonyl) bicyclo [2.2.1] hept-2-ene,
5,6-di (1′-ethoxyethoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (1′-cyclohexyloxyethoxycarbonyl) bicyclo [2.2.1] hept -2-ene, 5,6-di (t-butoxycarbonylmethoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (tetrahydrofuranyloxycarbonyl) bicyclo [2.
2.1] hept-2-ene, 5,6-di (tetrahydropyranyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like.

Further, among the norbornene derivatives (6),
Specific examples of the compound in which m is 1 and has an acid dissociable group (i) include 8-methoxycarbonyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-
Ethoxycarbonyltetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene, 8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1
^7,10 ] dodec-3-ene, 8-i-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-n-butoxycarbonyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-(2'-methylpropoxy) carbonyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-(1'-methylpropoxy) carbonyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-T-butoxycarbonyltetracyclo [4.4.0.
^12.5 . [ ^17,10 ] dodec-3-ene, 8-cyclohexyloxycarbonyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene, 8- (4'-t-
Butylcyclohexyloxy) carbonyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-Phenoxycarbonyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10] dodeca-3-ene, 8- (1'-ethoxyethoxy) carbonyl tetracyclo [4.4.0.1
^2,5 . [ ^17,10 ] dodec-3-ene, 8- (1'-cyclohexyloxyethoxy) carbonyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene, 8-
t-butoxycarbonylmethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-tetrahydropyranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-
Ene, 8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-Methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-Methyl-8-i-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8-methyl-8-n-butoxycarbonyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8
-Methyl-8- (2'-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8-methyl-8- (1′-methylpropoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-methyl-8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8-methyl-8-cyclohexyloxycarbonyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-
(4′-t-butylcyclohexyloxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8-methyl-8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-
Ene, 8-methyl-8- (1'-ethoxyethoxy) carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
Dodeca-3-ene, 8-methyl-8- (1′-cyclohexyloxyethoxy) carbonyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-methyl -8-t-butoxycarbonyl-methoxycarbonyltetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] Dodeca-3
-Ene, 8-methyl-8-tetrahydrofuranyloxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodeca-3-ene, 8-methyl-8-tetrahydropyranyloxycarbonyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] dodec-3-ene,

8,9-di (methoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-di (ethoxycarbonyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
9-di (n-propoxycarbonyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
9-di (i-propoxycarbonyl) tetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,
9-di (n-butoxycarbonyl) tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-
Di (2'-methylpropoxycarbonyl) tetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene,
8,9-di (1′-methylpropoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-
Ene, 8,9-di (t-butoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8,9-di (cyclohexyloxycarbonyl) tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] Dodeca-3
-Ene, 8,9-di (4'-t-butylcyclohexyloxycarbonyl) tetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene, 8,9-di (phenoxycarbonyl) tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] dodec-3-ene, 8,9-di (1 ′
-Ethoxyethoxycarbonyl) tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-
Di (1'-cyclohexyloxyethoxycarbonyl)
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] Dodeca
3-ene, 8,9-di (t-butoxycarbonylmethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] dodec-3-ene, 8,9-di (tetrahydrofuranyloxycarbonyl) tetracyclo [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene, 8,9-di (tetrahydropyranyloxy carbonyl) tetracyclo [
4.4.0.1 ^2,5 . [ ^1,7,10 ] dodec-3-ene and the like.

Further, among the norbornene derivatives (6),
Specific examples of the compound having no acid dissociable group (i) include:
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-
Hydroxymethylbicyclo [2.2.1] hept-2-
Ene, tetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-ethyl tetracyclo [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-hydroxymethyl-tetracyclo [4.4.0.1 ^{2, 5.} [ ^17,10 ] dodec-3-ene, 8- ^{fluorotetracyclo} [4.4.0.
^12.5 . 1 ^7,10] dodeca-3-ene, 8-fluoromethyl-tetracyclo [4.4.0.1 ^{2, 5.} [ ^17,10 ] dodec-3-ene, 8-difluoromethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10] dodeca-3-ene, 8-trifluoromethyl-tetracyclo [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
-En,

8,8-difluorotetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8,9-
Difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] Dodec-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- trifluoro tetracyclo [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.
^12.5 . 1 ^7,10] dodeca-3-ene, 8,8,9,9-
3. Tetrakis (trifluoromethyl) tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] dodec-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 ] dodec-3-ene, 8,8,
9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-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 ] dodec-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- trifluoro tetracyclo [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 ] dodec-3-ene,
8- (2 ′, 2 ′, 2′-trifluorocarboxyethyl) tetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] dodec-3-ene, 8-methyl-8- (2 ', 2', 2'-
3. trifluorocarboxyethyl) tetracyclo [4.
4.0.1 ^2,5 . [ ^1,7,10 ] dodec-3-ene and the like.

Among these norbornene derivatives (6), 5-t-butoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 8-t-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . [ ^17,10 ] dodec-3-ene and the like are preferred.

Further, other repeating units other than the repeating unit (3)
Examples of the monomer that gives a unit include dicyclopentene
Tadiene, tricyclo [5.2.1.0^2,6] Deca-8
-Ene, tricyclo [5.2.1.0^2,6] Deca-3-
Ene, tricyclo [4.4.0.1 ^2,5] Undeca-3
-Ene, tricyclo [6.2.1.0^1,8] Undeca
9-ene, tricyclo [6.2.1.0^1,8] Undeca
-4-ene, tetracyclo [4.4.0.1^2,5. 1
^7,10. 0^1,6] Dodeca-3-ene, 8-methyltetracy
Black [4.4.0.1^2,5. 1^7,10. 0^1,6] Dodeca
3-ene, 8-ethylidenetetracyclo [4.4.0.
1^2,5. 1^7,12 ] Dodeca-3-ene, 8-ethylidene
Toracyclo [4.4.0.1^2,5. 1^7,10. 0^1,6]
Deca-3-ene, pentacyclo [6.5.1.1^3,6.
0^2,7. 0^9,13 ] Pentadec-4-ene, pentacyclo
[7.4.0.1^2,5. 1^9,12. 0^8,13 ] Pentadeca
In addition to 3-ene,

Α- (meth) acryloyloxy-β-methoxycarbonyl-γ-butyrolactone, α- (meth)
Acryloyloxy-β-ethoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-
n-propoxycarbonyl-γ-butyrolactone, α-
(Meth) acryloyloxy-β-i-propoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-n-butoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β- (2-
Methylpropoxy) carbonyl-γ-butyrolactone,
α- (meth) acryloyloxy-β- (1-methylpropoxy) carbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-t-butoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β -Cyclohexyloxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β- (4
-T-butylcyclohexyloxy) carbonyl-γ-
Butyrolactone, α- (meth) acryloyloxy-β
-Phenoxycarbonyl-γ-butyrolactone, α-
(Meth) acryloyloxy-β- (1-ethoxyethoxy) carbonyl-γ-butyrolactone, α- (meth)
Acryloyloxy-β- (1-cyclohexyloxyethoxy) carbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-t-butoxycarbonylmethoxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-tetrahydrofuran Nyloxycarbonyl-γ-butyrolactone, α- (meth) acryloyloxy-β-tetrahydropyranyloxycarbonyl-γ-butyrolactone,

Α-methoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-ethoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-n-propoxycarbonyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-I-propoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-n-butoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α- (2-methylpropoxy) carbonyl-
β- (meth) acryloyloxy-γ-butyrolactone, α- (1-methylpropoxy) carbonyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-T-butoxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-cyclohexyloxycarbonyl-β- (meth) acryloyloxy-γ-
Butyrolactone, α- (4-t-butylcyclohexyloxy) carbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-phenoxycarbonyl-β
-(Meth) acryloyloxy-γ-butyrolactone,
α- (1-ethoxyethoxy) carbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-
(1-cyclohexyloxyethoxy) carbonyl-β
-(Meth) acryloyloxy-γ-butyrolactone,
α-t-butoxycarbonylmethoxycarbonyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
(Meth) acryloyloxy having an acid dissociable group such as -tetrahydrofuranyloxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone, α-tetrahydropyranyloxycarbonyl-β- (meth) acryloyloxy-γ-butyrolactone Lactone compounds;

Α- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-β-
Fluoro-γ-butyrolactone, α- (meth) acryloyloxy-β-hydroxy-γ-butyrolactone, α
-(Meth) acryloyloxy-β-methyl-γ-butyrolactone, α- (meth) acryloyloxy-β-ethyl-γ-butyrolactone, α- (meth) acryloyloxy-β, β-dimethyl-γ-butyrolactone, α −
(Meth) acryloyloxy-β-methoxy-γ-butyrolactone, β- (meth) acryloyloxy-γ-butyrolactone, α-fluoro-β- (meth) acryloyloxy-γ-butyrolactone, α-hydroxy-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-Methyl-β- (meth) acryloyloxy-γ-butyrolactone, α-ethyl-β- (meth) acryloyloxy-γ-butyrolactone, α, α-dimethyl-β-
(Meth) acryloyloxy-γ-butyrolactone, α
-Methoxy-β- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-δ-
(Meth) acryloyloxylactone compounds having no acid-dissociable group such as mevalonolactone;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n- (meth) acrylate
Other (meth) acrylates such as butyl and t-butyl (meth) acrylate; α-hydroxymethyl acrylates such as methyl α-hydroxymethyl acrylate and ethyl α-hydroxymethyl acrylate; vinyl acetate , Vinyl esters such as vinyl propionate and vinyl butyrate; unsaturated nitrile compounds such as (meth) acrylonitrile and α-chloroacrylonitrile; unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; N-vinyl-ε-caprolactam, N-vinylpyrrolidone, 2-vinylpyridine,
-Other nitrogen-containing vinyl compounds such as -vinylpyridine, 4-vinylpyridine, N-vinylimidazole; unsaturated carboxylic acids (anhydrides) such as (meth) acrylic acid, crotonic acid, maleic acid, and maleic anhydride; (Meth) acrylic acid 2
Monofunctional monomers such as carboxyl group-containing esters of unsaturated carboxylic acids such as carboxyethyl, 2-carboxypropyl (meth) acrylate and 3-carboxypropyl (meth) acrylate; ) Acrylates, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, etc. Examples thereof include polyfunctional monomers.

Of the monomers giving a repeating unit other than these repeating units (3), maleic anhydride and (meth) acryloyloxylactone compounds are preferred.
Particularly, maleic anhydride, α- (meth) acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-β-methyl-γ-butyrolactone, β- (meth)
Acryloyloxy-γ-butyrolactone, α- (meth) acryloyloxy-δ-mevalonolactone and the like are preferred. The maleic anhydride has good copolymerizability with the norbornene derivative (6), and when the resin (A) has a repeating unit (3) derived from the norbornene derivative (6), the maleic anhydride is converted to the norbornene derivative. By copolymerizing with (6), the molecular weight of the obtained resin (A) can be increased to a desired value. The monomers giving a repeating unit other than the repeating unit (3) can be used alone or in combination of two or more.

In the resin (A), the content of the repeating unit (3) is usually 60 mol% or less, preferably 5 to 50 mol%, more preferably 10 mol%, based on all repeating units.
The content of the repeating unit other than the repeating unit (3) is usually at most 60 mol%, preferably at most 50 mol%, more preferably at most 40 mol%. In this case, when the content of each of the repeating unit (3) and the other repeating units exceeds 60 mol%, the resolution as a resist tends to decrease.

The resin (A) is, for example, a (meth) acrylic acid derivative (4) and a (meth) acrylic acid derivative (5)
Is copolymerized in a suitable solvent with a radical polymerization initiator such as a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, or an azo compound, together with a monomer that optionally provides another repeating unit. It can be manufactured by the following. Examples of the solvent used for the copolymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; cyclohexane, cycloheptane, cyclooctane, decalin, Cycloalkanes such as norbornane; benzene, toluene, xylene, ethylbenzene,
Aromatic hydrocarbons such as cumene; halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; ethyl acetate, n-butyl acetate, i-butyl acetate, methyl propionate, etc. Saturated carboxylic acid esters; and ethers such as tetrahydrofuran, dimethoxyethanes, and diethoxyethanes. These solvents are
They can be used alone or in combination of two or more.

The weight average molecular weight (hereinafter, referred to as “Mw”) of the resin (A) in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 3,0.
00 to 300,000, preferably 4,000 to 20
000, more preferably 5,000 to 100,0
00. In this case, the Mw of the resin (A) is 3,000
If it is less than 30, the heat resistance as a resist tends to decrease, while if it exceeds 300,000, the developability as a resist tends to decrease. In addition, the resin (A) in the present invention is preferably such that the amount of impurities such as halogen and metal is as small as possible, whereby the sensitivity, resolution, process stability, pattern shape, etc. of the radiation-sensitive resin composition as a resist are further improved. You. As a method for purifying the resin (A),
Examples include chemical purification methods such as washing with water and liquid-liquid extraction, and combinations of these chemical purification methods with physical purification methods such as ultrafiltration and centrifugation. In the present invention, the resin (A) can be used alone or in combination of two or more.

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 groups present in the resin (A) by the action of the acid generated by the exposure, and as a result, the exposed portion of the resist film becomes easily soluble in an alkali developing solution, It has the function of forming a mold 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 n-dodecylbenzenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium naphthalene sulfonate, Diphenyliodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodoniumpyrene Sulfonate, bis (4-t-butylphenyl) iodonium n-dode Le benzenesulfonate, bis (4-t- butylphenyl) iodonium hexafluoroantimonate, bis (4-t- butylphenyl) iodonium naphthalene sulfonate, bis (4-t- butylphenyl) iodonium 10-camphorsulfonate,

Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium pyrene sulfonate, triphenylsulfonium
n-dodecylbenzenesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, triphenylsulfonium 10-camphorsulfonate, 4-hydroxyphenylphenylmethylsulfonium p-toluenesulfonate, 4-hydroxyphenylbenzylmethyl Sulfonium toluenesulfonate, cyclohexylmethyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, dimethyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1 -Naphthyl diethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-methyl-1-
Naphthyl dimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-nitro-1-naphthyldiethylsulfonium trifluoromethanesulfonate, 4-methyl- 1-naphthyl diethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldiethylsulfonium trifluoromethanesulfonate,

4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
-Methoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxy-1-
Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-n-propoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-i-propoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-
n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-tert-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-methoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- Ethoxymethoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (1′-methoxyethoxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2′-methoxyethoxy) -1-naphthyltetrahydrothio Phenium trifluoromethanesulfonate, 4-methoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-ethoxy Aryloxycarbonyl-1-naphthyl tetrahydrothiophenium trifluoromethane sulfonate, 4-n-propoxycarbonyl-1-
Naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-i-propoxycarbonyloxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-n-butoxycarbonyloxy-1-naphthyltetrahydrothiopheniumtrifluoromethanesulfonate, 4-t -Butoxycarbonyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4- (2'-tetrahydrofuranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-
(2′-tetrahydropyranyloxy) -1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4-benzyloxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1
-(1'-naphthyl acetomethyl) tetrahydrothiophenium trifluoromethanesulfonate.

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 phenylbis (trichloromethyl) -s-triazine and 4-methoxyphenylbis (trichloromethyl)-
(Trichloromethyl) -s- such as s-triazine and 1-naphthylbis (trichloromethyl) -s-triazine
Examples thereof include a triazine derivative 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′-
Examples thereof include 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester of (hydroxyphenyl) ethane. Sulfone compound: Examples of the sulfone compound include β
-Ketosulfone, β-sulfonylsulfone and α-diazo compounds of these compounds. Specific examples of preferred sulfone compounds include 4-tolylphenacylsulfone, mesitylphenacylsulfone, and bis (phenylsulfonyl) methane. Sulfonic acid compound: Examples of the sulfonic acid compound include alkylsulfonic acid esters, alkylsulfonic acid imides, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-
9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.
1] hept-5-ene-2,3-dicarbodiimide, N
-Hydroxysuccinimide trifluoromethanesulfonate and 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate.

Among these acid generators (B), diphenyliodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n -Butanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, cyclohexylmethyl.
2-oxocyclohexylsulfonium trifluoromethanesulfonate, dicyclohexyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, dimethyl-2-oxocyclohexylsulfonium trifluoromethanesulfonate, 4-hydroxy-1
-Naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate,
-N-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 1- (1′-naphthylacetomethyl) tetrahydrothiophenium trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene −2,
3-Dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate and the like are preferable.

In the present invention, the acid generator (B) can be used alone or as a mixture 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, the sensitivity and developability as a resist tend to decrease, while if it exceeds 10 parts by weight, the transparency to radiation decreases. Therefore, it tends to be difficult to obtain a rectangular resist pattern as a resist.

Various Additives The radiation-sensitive resin composition of the present invention controls the diffusion phenomenon of the acid generated from the acid generator (B) in the resist film upon exposure, and suppresses undesired chemical reactions in the unexposed area. An acid diffusion controlling agent having an action of acting can be blended. By using such an acid diffusion controlling agent, the storage stability of the composition is further improved, the resolution as a resist is further improved, and the resist pattern due to the fluctuation of the withdrawal time from exposure to development (PED) is increased. Can be suppressed, and the process stability is further improved. As the acid diffusion controller, a nitrogen-containing organic compound whose basicity is not changed by exposure or heat treatment during a resist pattern forming step is preferable. As such a nitrogen-containing organic compound, for example, the following general formula (7)

[0111]

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[In the general formula (7), R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group. Is shown. (Hereinafter, referred to as "nitrogen-containing compound (a)"), a diamino compound having two nitrogen atoms in the same molecule (hereinafter, referred to as "nitrogen-containing compound (b)"), and a nitrogen atom 3
Examples thereof include diamino polymers having at least one compound (hereinafter, referred to as "nitrogen-containing compound (c)"), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. Examples of the nitrogen-containing compound (a) include mono- (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, and cyclohexylamine; di-n- Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. Di (cyclo) alkylamines; triethylamine,
Tri-n-propylamine, tri-n-butylamine,
Tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexyl Tri (cyclo) alkylamines such as amines; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline,
3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine,
And aromatic amines such as naphthylamine.

Examples of the nitrogen-containing compound (b) include ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4'-aminophenyl) propane, 2- (3'-aminophenyl) -2- (4′-aminophenyl) propane, 2- (4′-aminophenyl)
-2- (3'-hydroxyphenyl) propane, 2-
(4'-aminophenyl) -2- (4'-hydroxyphenyl) propane, 1,4-bis [1 '- ^(4''- aminophenyl) ^-1' - methylethyl] benzene, 1,3
- bis can be mentioned [1 ^'- (4'^'- - aminophenyl) ^-1' methylethyl] benzene, and the like. Examples of the nitrogen-containing compound (c) include polymers of polyethyleneimine, polyallylamine, and dimethylaminoethylacrylamide. Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, and N-methylpyrrolidone. Can be mentioned. Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tri-n-butyl Thiourea and the like can be mentioned. 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, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, In addition to pyridines such as 8-oxyquinoline and acridine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1- (2′-hydroxy Ethyl) piperazine, 1,4-diazabicyclo [2.2.2] octane and the like.

Among these nitrogen-containing organic compounds, a nitrogen-containing compound (a) and a nitrogen-containing heterocyclic compound are preferred. Among the nitrogen-containing compounds (a), tri (cyclo) alkylamines are particularly preferable, and among the nitrogen-containing heterocyclic compounds, pyridines and piperazines are particularly preferable. The acid diffusion controllers can be used alone or in combination of two or more. The amount of the acid diffusion controller is usually 15 parts by weight or less based on 100 parts by weight of the resin (A).
It is preferably at most 10 parts by weight, more preferably at most 5 parts by weight. 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. If the amount of the acid diffusion controller is less than 0.001 part by weight, the pattern shape and dimensional fidelity of the resist may be reduced depending on the process conditions.

The radiation-sensitive resin composition of the present invention further comprises an alicyclic additive having an acid-dissociable organic group, which has an effect of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like. Can be blended. Such alicyclic additives include, for example, t-butyl 1-adamantanecarboxylate and t-butyl 3-adamantanecarboxylate.
Butyl, 1,3-adamantane dicarboxylate di-t-butyl, 1-adamantane acetate t-butyl, 3-adamantane acetate t-butyl, 1,3-adamantane diacetate di-
Adamantane derivatives such as t-butyl; t-butyl deoxycholate, t-butoxycarbonylmethyl deoxycholate, 2-ethoxyethyl deoxycholate, 2-cyclohexyloxyethyl deoxycholate, 3-oxocyclohexyl deoxycholate, Deoxycholates such as tetrahydropyranyl deoxycholate and mevalonolactone deoxycholate; t-butyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid, 2-cyclohexyloxyethyl lithocholic acid And lithocholic acid esters such as 3-oxocyclohexyl lithocholic acid, tetrahydropyranyl lithocholic acid and mevalonolactone lithocholic acid. These alicyclic additives can be used alone or in combination of two or more. The amount of the alicyclic additive is usually 50 parts by weight or less based on 100 parts by weight of the resin (A).
Preferably it is 30 parts by weight or less. In this case, if the amount of the alicyclic additive exceeds 50 parts by weight, the heat resistance of the resist tends to decrease.

Further, as other additives, there may be mentioned surfactants having an effect of improving the coating property, the developing property and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene In addition to nonionic surfactants such as glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Polyflow No. No. 75, the same No. 95 (Kyoeisha Chemical Co., Ltd.)
EF301, EF303, EF3
52 (manufactured by Tochem Products Inc.), Megafax F171 and F173 (manufactured by Dainippon Ink and Chemicals, Inc.)
Florad FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahigard AG710, Surflon S-382, SC-101, SC-102, S
C-103, SC-104, SC-105, SC
-106 (manufactured by Asahi Glass Co., Ltd.).
These surfactants can be used alone or in combination of two or more. The amount of the surfactant is usually 2 parts by weight or less based on 100 parts by weight of the total of the resin (A) and the acid generator (B). 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 with a filter having a pore size of about 0.2 μm. As the solvent used for preparing the composition solution, for example, 2-
Butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone,
Linear or branched ketones such as -methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone and 2-octanone; cyclopentanone, 2-methylcyclopentanone, cyclohexanone, -Methylcyclohexanone, 2,6-dimethylcyclohexanone,
Cyclic ketones such as 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 glycol mono-t-
Propylene glycol monoalkyl ether acetates such as butyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate;
N-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, 2
-In addition to alkyl 2-hydroxypropionates such as t-butyl 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, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, 2- Alkyl hydroxypropionates are preferred.

Method for Forming Resist Pattern The radiation-sensitive resin composition of the present invention is particularly useful as a chemically amplified resist. In the chemically amplified resist, an acid dissociable group in the resin (A) is dissociated by the action of an acid generated from the acid generator (B) upon exposure, and is converted into an acidic functional group such as a carboxyl group. As a result, the solubility of the exposed portion of the resist in an alkali developing solution is increased, and the exposed portion is dissolved and removed by the alkali developing solution to obtain a positive resist pattern. When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the radiation-sensitive resin composition, by appropriate coating means such as spin coating, casting coating, roll coating, for example, silicon wafer, aluminum A resist film is formed by coating on a substrate such as a wafer coated with
It is called "PB". ), The resist film is exposed so as to form a predetermined resist pattern. As the radiation used at that time, far ultraviolet rays, X-rays, electron beams, or the like can be appropriately selected and used depending on the type of the acid generator (B). In particular, an ArF excimer laser (wavelength 193 nm) or a KrF excimer laser (wavelength 248 nm) is preferable. In the present invention, it is preferable to perform a heat treatment (hereinafter, referred to as “PEB”) after the exposure. By this PEB, the dissociation reaction of the acid dissociable group in the resin (A) proceeds smoothly. The heating conditions for PEB vary depending on the composition of the radiation-sensitive resin composition, but are usually 30 to 200 ° C, preferably 50 to 170 ° C.
It is. In the present invention, in order to maximize the potential of the radiation-sensitive resin composition, for example, Japanese Patent Publication No. 6-12
As disclosed in Japanese Patent No. 452,452, 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, see, for example, JP-A-5-1885.
As disclosed in Japanese Patent Application Publication No. 98-98, 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, ethyldimethylamine, triethanolamine,
Tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.
4.0] -7-undecene, 1,5-diazabicyclo-
An alkaline aqueous solution in which at least one kind of alkaline compound such as [4.3.0] -5-nonene is dissolved is preferable.
The concentration of the alkaline aqueous solution is usually 10% by weight or less. In this case, if the concentration of the alkaline aqueous solution exceeds 10% by weight, unexposed portions also dissolve in the developer, which is not preferable. Further, in the developer comprising the alkaline aqueous solution,
For example, an organic solvent can be added. Specific examples of the organic solvent include ketones such as acetone, 2-butanone, 4-methyl-2-pentanone, cyclopentanone, 2-methylcyclopentanone, cyclohexanone, and 2,6-dimethylcyclohexanone; methyl alcohol; Ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol,
Alcohols such as 1,4-hexanediol and 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; fragrances such as toluene and xylene Group hydrocarbons, phenol, acetonylacetone,
Dimethylformamide and the like can be mentioned. 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 area may be increased. 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.

[0121]

Embodiments of the present invention will now be described more specifically with reference to the following 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. Storage stability: A 1 μm-thick resist film formed by applying the composition solution on a silicon wafer by spin coating and performing PB on a hot plate maintained at 140 ° C. for 90 seconds to form 2.38% tetramethylammonium After developing with an aqueous hydroxide solution at 25 ° C. for 1 minute, washing with water and drying, the film thickness was measured. This is defined as the initial remaining film thickness. Further, the composition solution was held in a constant temperature bath at 50 ° C., and from the held composition solution, a resist film was formed, developed, washed with water and dried in the same manner as described above, and the remaining film thickness after holding was obtained. Was measured. At this time, the number of days required for the rate of change of the remaining film thickness after holding to the initial remaining film thickness to exceed 50% was determined and used as a measure of storage stability. The larger the number of days, the better the storage stability. Radiation transmittance: A 1 μm-thick resist film formed by applying the composition solution onto a quartz glass by spin coating and performing PB on a hot plate maintained at 90 ° C. for 60 seconds, and transmitting the composition from the absorbance at a wavelength of 193 nm. The rate was calculated and used as a measure of transparency in the deep ultraviolet region.

Relative etching rate: For a resist film having a dry film thickness of 0.5 μm obtained by spin-coating a composition solution on a silicon wafer, a dry etching apparatus (Pinnacle8000) manufactured by PMT was used, and the etching gas was CF ₄ . Dry etching was performed under the conditions of a gas flow rate of 75 sccm, a pressure of 2.5 mTorr, and an output of 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 relative etching rate, the better the dry etching resistance. Sensitivity: DeepUV30 with a thickness of 520mm on the surface as a substrate
(Manufactured by Brewer Science) Using a silicone wafer (ARC) having a film formed thereon, the composition solution was spin-coated on a substrate, and then PB was performed on a hot plate under the conditions shown in Table 2. And a film thickness of 0.4
A μm resist film was formed. To this resist film,
Exposure was performed through a mask pattern using an ArF excimer laser exposure apparatus manufactured by Nikon Corporation (lens numerical aperture 0.55, exposure wavelength 193 nm). Next, after performing PEB on a hot plate under the conditions shown in Table 2, 2.3.
Develop with an 8% aqueous solution of tetramethylammonium hydroxide (Examples 1 to 16) or a 2.38 × 1/50% aqueous solution of tetramethylammonium hydroxide (Comparative Example 1) at 25 ° C. for 1 minute, wash with water, and dry. Thus, a positive resist pattern was formed. At that time, line width 0.18μ
The exposure amount that forms the m line-and-space pattern (1L1S) with a line width of 1: 1 was defined as the optimal exposure amount, and the optimal exposure amount was defined as the sensitivity. Resolution: The minimum resist pattern dimension resolved when exposed at the optimal exposure amount was defined as the resolution. 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 side dimension L ₂ were measured with a scanning electron microscope,
When 0.85 ≦ L ₂ / L ₁ ≦ 1 is satisfied and the pattern shape does not have a tail, the pattern shape is determined to be “good”, and when at least one of these conditions is not satisfied, The pattern shape was determined to be "bad".

Synthesis Example 1 In a separable flask equipped with a reflux tube, under a nitrogen stream, 27 parts of 3-hydroxy-1-adamantyl methacrylate, 13 parts of 2-methyl-2-adamantyl methacrylate, and 5-t-butoxycarbonylbicyclo. [2.
2.1] 40 parts of hept-2-ene, maleic anhydride 20
Parts, 10 parts of azobisisobutyronitrile and 100 parts of tetrahydrofuran were charged and polymerized at 65 ° C. for 5 hours. After the polymerization, a large amount of n-hexane / i-
Pour into a mixed solvent of propyl alcohol (weight ratio = 3/1) to coagulate the resin, wash the coagulated resin several times with the same mixed solvent, vacuum dry, and contain each repeating unit represented by the following formula (A1-I) 20 mol%, (A1-II) 10 mol%, (A1-III) 35 mol%, (A1-IV) 35 mol%,
A copolymer having Mw of 12,000 was obtained in a yield of 60%. This copolymer is referred to as copolymer (A-1).

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Synthesis Example 2 As raw materials, 40 parts of 3-hydroxy-1-adamantyl methacrylate, 10 parts of 2-methyl-2-adamantyl methacrylate, 8-t-butoxycarbonyltetracyclo [4.4.0.12 ^{, 5} . 1 ^7,10 ] Dodeca-3
-Ene 35 parts, maleic anhydride 15 parts, azobisisobutyronitrile 10 parts and tetrahydrofuran 100 parts, except that the content of each repeating unit represented by the following formula was (A2 -I) 40 mol%, (A2-II)
10 mol%, (A2-III) 25 mol%, (A2-IV) 25 mol%
And a copolymer having Mw of 8,000 was obtained in a yield of 62%. This copolymer is referred to as copolymer (A-2).

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Synthesis Example 3 As a raw material, 2- (5′-hydroxybicyclo [
2.2.1] Heptyl) acrylate 25 parts, 2-methyl-2-adamantyl methacrylate 15 parts, 5-t-
Butoxycarbonylbicyclo [2.2.1] hept-2
In the same manner as in Synthesis Example 1 except that 40 parts of ene, 20 parts of maleic anhydride, 10 parts of azobisisobutyronitrile and 100 parts of tetrahydrofuran were used, the content of each repeating unit represented by the following formula was (A3 -I) 20 mol%, (A3-II)
10 mol%, (A3-III) 35 mol%, (A3-IV) 35 mol%
And a copolymer having Mw of 13,000 was obtained in a yield of 70%. This copolymer is referred to as copolymer (A-3).

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Synthesis Example 4 As a raw material, 2- (5′-hydroxybicyclo [
2.2.1] Heptyl) acrylate 40 parts, 2-methyl-2-adamantyl methacrylate 10 parts, 8-t-
Butoxycarbonyltetracyclo [4.4.0.
^12.5 . [1 ^7,10 ] Synthesis Example 1 except that 35 parts of dodeca-3-ene, 15 parts of maleic anhydride, 10 parts of azobisisobutyronitrile and 100 parts of tetrahydrofuran were used.
In the same manner as described above, the content of each repeating unit represented by the following formula is (A4-I) 40 mol%, (A4-II) 10 mol%, and (A4-III) 2
5 mol%, (A4-IV) 25 mol%, and Mw of 10.0
00 was obtained in a yield of 64%. This copolymer is
Let it be a copolymer (A-4).

[0130]

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[0131] Synthetic Example 5 feedstock, 3- (8'-hydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl) acrylate 30 parts, 2-methyl-2-adamantyl acrylate 12 parts, 5-t-butoxycarbonylbicyclo [2.
2.1] 38 parts of hept-2-ene, maleic anhydride 20
Part, azobisisobutyronitrile and 10 parts of tetrahydrofuran in the same manner as in Synthesis Example 1, except that the content of each repeating unit represented by the following formula was (A5-I) 2
0 mol%, (A5-II) 10 mol%, (A5-III) 35 mol%,
(A5-IV) A copolymer having 35 mol% and Mw of 12,000 was obtained at a yield of 67%. This copolymer is referred to as a copolymer (A-5).

[0132]

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[0133] Synthetic Example 6 feedstock, 3- (8'-hydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl) acrylate 50 parts, 2-methyl-2-adamantyl methacrylate 10 parts, 8-t-butoxycarbonyltetracyclo
[4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene 30
Part, maleic anhydride 10 parts, azobisisobutyronitrile 10 parts and tetrahydrofuran 100 parts, except that the content of each repeating unit represented by the following formula was (A6-I) in the same manner as in Synthesis Example 1. 40 mol%, (A6-II) 10 mol%, (A6-III) 25 mol%, (A6-IV) 25 mol%,
A copolymer having Mw of 8,000 was obtained at a yield of 58%. This copolymer is referred to as copolymer (A-6).

[0134]

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[0135] Synthetic Example 7 feedstock, 3- (8'-hydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl) acrylate 50 parts, 2-ethyl-2-adamantyl acrylate 10 parts, 8-t-butoxycarbonyltetracyclo [
4.4.0.1 ^2,5 . 1 ^7,10 ] dodeca-3-ene 30
Part, maleic anhydride 10 parts, azobisisobutyronitrile 10 parts and tetrahydrofuran 100 parts, in the same manner as in Synthesis Example 1, except that the content of each repeating unit represented by the following formula was (A7-I) 40 mol%, (A7-II) 10 mol%, (A7-III) 25 mol%, (A7-IV) 25 mol%,
A copolymer having Mw of 8,000 was obtained at a yield of 58%. This copolymer is referred to as a copolymer (A-7).

[0136]

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Synthesis Example 8 As raw materials used, 27 parts of 4-oxo-1-adamantyl acrylate, 13 parts of 2-methyl-2-adamantyl methacrylate, 5-t-butoxycarbonylbicyclo
[2.2.1] In the same manner as in Synthesis Example 1 except that 40 parts of hept-2-ene, 20 parts of maleic anhydride, 10 parts of azobisisobutyronitrile and 100 parts of tetrahydrofuran were used, the following formula was used. The content of each repeating unit shown is (A8
-I) 20 mol%, (A8-II) 10 mol%, (A8-III) 35 mol%, (A8-IV) 35 mol%, and Mw is 12,000.
Was obtained in a yield of 67%. This copolymer is referred to as a copolymer (A-8).

[0138]

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[0139] Synthetic Example 9 feedstock, 3- (8'-hydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl) acrylate 30 parts, (1-adamantyl-1-methyl ethyl)
Except that 16 parts of acrylate, 38 parts of 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 20 parts of maleic anhydride, 10 parts of azobisisobutyronitrile and 100 parts of tetrahydrofuran were used. Similarly to Synthesis Example 1, the content of each repeating unit represented by the following formula was (A9-I) 20 mol%, (A9-II) 10 mol%, and (A9-III) 3
5 mol%, (A9-IV) 35 mol%, and Mw of 12,0
00 was obtained in 67% yield. This copolymer is
Let it be a copolymer (A-9).

[0140]

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[0141] Synthetic Example 10 feedstock, 3- (8'-hydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl) acrylate 50 parts, 2-methyl-2-adamantyl methacrylate Except that 35 parts, β-acryloyloxy-γ-butyrolactone, 15 parts, azobisisobutyronitrile, 5 parts, and 100 parts of tetrahydrofuran were used, the content of each repeating unit represented by the following formula was obtained in the same manner as in Synthesis Example 1. (A1
0-I) 50 mol%, (A10-II) 30 mol%, (A10-III) 20
Mol%, and a copolymer having Mw of 9,000 was obtained in a yield of 67.
%. This copolymer is referred to as a copolymer (A-10).

[0142]

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Synthesis Example 11 As raw materials, 25 parts of 3-hydroxy-1-adamantyl acrylate, 50 parts of 4-hydroxycyclohexyl acrylate, 25 parts of 2-methyl-2-adamantyl methacrylate, 5 parts of azobisisobutyronitrile, and 5 parts of tetrahydrofuran Except that 100 parts were used, the content of each repeating unit represented by the following formula was (A11-I) 20 mol%, (A11-II) 60 mol%, and (A11-II).
I) A copolymer having 20 mol% and Mw of 9,000 was obtained at a yield of 67%. This copolymer is referred to as a copolymer (A-11).

[0144]

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Synthesis Example 12 As raw materials, 30 parts of 3-hydroxy-1-adamantyl methacrylate, 45 parts of 2-methyl-2-adamantyl methacrylate, α-methacryloyloxy-γ
-In the same manner as in Synthesis Example 1 except that 25 parts of butyrolactone, 5 parts of azobisisobutyronitrile and 100 parts of tetrahydrofuran were used, the content of each repeating unit represented by the following formula was (A12-I) 30 mol%. , (A12-II) 40 mol%,
(A12-III) A copolymer having 30 mol% and Mw of 8,500 was obtained at a yield of 70%. This copolymer is referred to as a copolymer (A-12).

[0146]

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Synthesis Example 13 As raw materials, 30 parts of 3-hydroxy-1-adamantyl methacrylate, 45 parts of 2-methyl-2-adamantyl methacrylate, β-acryloyloxy-γ-
Butyrolactone 25 parts, azobisisobutyronitrile 5
Parts and 100 parts of tetrahydrofuran,
Similarly to Synthesis Example 1, the content of each repeating unit represented by the following formula was (A13-I) 30 mol%, (A13-II) 40 mol%, (A1
3-III) A copolymer having 30 mol% and Mw of 8,900 was obtained at a yield of 72%. This copolymer was converted to a copolymer (A-1
3).

[0148]

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Comparative Polymerization Example 1 18.28 parts of tetrahydropyranyl acrylate, 25 parts of tricyclodecanyl acrylate, 0.2 parts of azoisobutyronitrile and 0.1 part of t-dodecyl mercaptan were mixed with 1,2-diethyl methacrylate. It was dissolved in 100 parts of ethoxyethane and polymerized at 65 ° C. for 5 hours. After the polymerization is completed, the reaction solution is poured into a large amount of methyl alcohol to coagulate the resin, and the coagulated resin is dried under reduced pressure, so that the content of each of tetrahydropyranyl acrylate and tricyclodecanyl acrylate is 5%.
0 mol%, and a copolymer having Mw of 20,000 was obtained in a yield of 35%. This copolymer is referred to as a resin (a-1).

[0150]

EXAMPLES Examples 1 to 18 and Comparative Example 1 After mixing the components shown in Table 1 to form a uniform solution, the mixture was filtered through a membrane filter having a pore diameter of 0.2 μm to prepare each composition solution. Was done. Table 3 shows the evaluation results.
Shown in Components other than the resin in each of the Examples and Comparative Examples were
It is as follows. Acid generator (B) B-1: Triphenylsulfonium trifluoromethanesulfonate B-2: Triphenylsulfonium nonafluoro-n-butanesulfonate B-3: 4-n-butoxy-1-naphthyltetrahydrothiophenium nonafluoro- n-butanesulfonate B-4: bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate B-5: trifluoromethanesulfonylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarbodiimide acid diffusion controller C-1: tri-n-octylamine C-2: methyldicyclohexylamine C-3: 1- (2'-hydroxyethyl) Piperazine C-4: 4-hydroxyquinoline Other additives D-1: t-butyl deoxycholate (see the following formula (8))

[0151]

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D-2: di-t-butyl 1,3-adamantanedicarboxylate solvent E-1: 2-heptanone E-2: ethyl 2-hydroxypropionate E-3: propylene glycol monoethyl ether acetate E-4 : Ethyl 3-ethoxypropionate E-5: Cyclohexanone

[0153]

[Table 1]

[0154]

[Table 2]

[0155]

[Table 3]

[0156]

The radiation-sensitive resin composition of the present invention can be used as a chemically amplified resist which is sensitive to actinic radiation, especially to deep ultraviolet rays typified by KrF excimer laser or ArF excimer laser. It has excellent transparency, high radiation transparency, and excellent basic physical properties as a resist such as dry etching resistance, sensitivity, resolution, and pattern shape. It can be suitably used.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tohru Kajita 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation (72) Inventor Tsutomu Shimokawa 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR F term (in reference) 2H025 AA01 AA02 AA03 AA09 AC04 AC05 AC06 AC08 AD03 BE00 BG00 FA03 FA12 FA17 4J002 BG041 BG051 BG071 BK001 EB006 EB126 EQ016 EU046 EU186 EV216 EV246 EV266 EV296 EV306 EW176 EY006 FD206 GP03

Claims (3)

[Claims] (A) An alkali-insoluble or poorly alkali-soluble acid-dissociable group-containing resin having a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2): A resin which becomes alkali-soluble when the acid-dissociable group is dissociated; and (B) a radiation-sensitive acid generator. Embedded image [In the general formula (1), R ¹ is a hydrogen atom and has 1 to 1 carbon atoms.
4 linear or branched alkyl groups, having 1 to 4 carbon atoms
Represents a straight-chain or branched alkoxyl group or a straight-chain or branched hydroxyalkyl group having 1 to 4 carbon atoms, and A represents a single bond or a straight-chain or branched chain having 1 to 4 carbon atoms in the main chain. R ² represents the following formula (i) (where R ³ represents a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms; X ¹ represents a monovalent oxygen-containing polar group or 1
It shows a valent nitrogen-containing polar group. ), Formula (ii) (provided that R ⁴
Represents a trivalent alicyclic hydrocarbon group having 4 to 20 carbon atoms;
² represents a divalent oxygen-containing polar group or a divalent nitrogen-containing polar group. ) Or formula (iii) (wherein R ⁵ has 4 to 2 carbon atoms)
X represents a tetravalent alicyclic hydrocarbon group, and X ³ represents a trivalent oxygen-containing polar group or a trivalent nitrogen-containing polar group. ) Represents a group represented by [Chemical formula 3] [In the general formula (2), R ⁶ is a hydrogen atom and has 1 to 1 carbon atoms.
4 linear or branched alkyl groups, having 1 to 4 carbon atoms
Represents a linear or branched alkoxyl group or a linear or branched hydroxyalkyl group having 1 to 4 carbon atoms, and R ⁷ represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or Formula (iv) (However, each R ⁸ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and at least one R 8 ⁸
Is a linear or branched alkyl group having 1 to 4 carbon atoms, or any two R ⁸ are mutually bonded,
Each having 4 to 2 carbon atoms
0 forms a bivalent alicyclic hydrocarbon group, and the remaining R ⁸ is a linear or branched alkyl group having 1 to 4 carbon atoms. ). ] 2. The alicyclic hydrocarbon group represented by R ³ , R ⁴ and R ^{5 in} the repeating unit represented by the general formula (1) in the component (A) and the repeating unit represented by the general formula (2) monovalent monovalent or divalent alicyclic hydrocarbon groups independently of one another alicyclic hydrocarbon group, and R ⁸ of R ⁷ in unit, adamantane skeleton, norbornane skeleton, tricyclodecane skeleton, and tetracyclo The radiation-sensitive resin composition according to claim 1, which is a group having an alicyclic skeleton selected from the group of dodecane skeletons. 3. The component (A) having a repeating unit represented by the general formula (1), a repeating unit represented by the general formula (2) and a repeating unit represented by the following general formula (3). The radiation-sensitive resin composition according to claim 1 or 2, wherein Embedded image [In the general formula (3), R ⁹ , R ¹⁰ , R ¹¹ and R ¹²
Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a substituted or unsubstituted linear or branched C1-C6 alkyl group, a substituted or unsubstituted linear or branched C1 Represents an alkoxyl group having from 6 to 6 or an acid dissociable group having from 2 to 20 carbon atoms, and m is 0, 1 or 2
Is an integer. ]