JP2001166478A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition useful as an excellent chemical amplification type resist which prevents a change of the line width of a resist pattern and the formation of T shape due to the time elapsed from exposure until heating after exposure [post-exposure delay(PED)], is not affected by a stationary wave due to reflection from a substrate and can be applied even in a very small pattern size. SOLUTION: The radiation sensitive resin composition contains (A) a copolymer containing repeating units of formula 1 (where R1 is H or methyl; and R2 is an acid releasable >=11C alicyclic alkyl having a tertiary carbon atom> and repeating units derived from hydroxystyrenes and (B) a radiation sensitive acid generating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a radiation-sensitive resin composition. More particularly, in particular KrF and Ar
The present invention relates to a radiation-sensitive resin composition useful for fine processing using various radiations such as charged particle beams such as electron beams and X-rays such as synchrotron radiation, in addition to far ultraviolet rays represented by an F excimer laser and the like.

[0002]

2. Description of the Related Art Far ultraviolet rays such as a KrF excimer laser,
As a resist suitable for X-rays such as charged particle beams such as electron beams and synchrotron radiation, a radiation-sensitive acid generator that generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”) is used. There has been proposed a "chemically amplified resist" in which the sensitivity of the resist is improved by the catalytic action of (1). Conventionally, as a problem peculiar to such a chemically amplified resist, a line width of a resist pattern is changed or a T-type is changed due to a delay time (hereinafter referred to as “PED”) from exposure to heat treatment after exposure. It has been pointed out that the polymer may have a shape. However, recently, the solubility of the polymer in a hydroxystyrene-based repeating unit, a repeating unit composed of t-butyl (meth) acrylate, and an alkali developing solution after exposure has been pointed out. Amplified Radiation-Sensitive Resin Composition Using a Polymer Consisting of Repeating Units for Reducing Amount
Various chemical amplification resists that can withstand application to device manufacturing have been proposed. However, with the miniaturization of current devices, a deprotecting group (such as a t-butyl protecting group) generally used in a chemically amplified resist cannot express a sufficient contrast, and a finer finer than ever. It has become difficult to apply it to the manufacture of pattern-sized devices.

[0003]

SUMMARY OF THE INVENTION In view of the above situation in the prior art, an object of the present invention is to prevent a resist pattern from causing a line width change or a T-shape due to PED, and from a An object of the present invention is to provide a radiation-sensitive resin composition useful as an excellent chemically amplified resist which is not affected by standing waves due to reflection and can be applied even in an ultra-fine pattern size. Another object of the present invention is to
High sensitivity (low exposure energy) and high resolution to various radiations such as deep ultraviolet rays such as KrF and ArF excimer lasers, charged particle beams such as electron beams, and X-rays such as synchrotron radiation. An object of the present invention is to provide an excellent radiation-sensitive resin composition. Still other objects and advantages of the present invention will become apparent from the following description.

[0004]

According to the present invention, the above objects and advantages of the present invention are as follows: (A) The following formula (1)

[0005]

Embedded image

Here, R ¹ is a hydrogen atom or a methyl group, and R ² is an alicyclic alkyl group having 11 or more carbon atoms which has a tertiary carbon atom and is acid-labile. And the following formula (2)

[0007]

Embedded image Wherein R ³ is a hydrogen atom or a methyl group,

This is achieved by a radiation-sensitive resin composition comprising a copolymer containing a repeating unit represented by the formula (I) and (B) a radiation-sensitive acid generator.

Hereinafter, the present invention will be described in detail. (A) Copolymer The component (A) in the present invention comprises a copolymer containing the repeating unit (1) and the repeating unit (2) (hereinafter, referred to as “(A) copolymer”). . In the formula (1) representing the repeating unit (1), examples of the alicyclic alkyl group having 11 or more carbon atoms which has a tertiary carbon atom of R ² and is acid-eliminable include, for example, 2-methyl-2 -Adamantyl group, 2-ethyl-2-adamantyl group, 2-n-propyl-2-adamantyl group, 2-isopropyl-2-adamantyl group, 2-methyl-2-tetracyclo [4.4.
0.1 ^2,5 .1 ^7,10] dodecyl group, and 2-ethyl-2-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecyl group. Among them, a 2-alkyl-2-adamantyl group is preferable.

As R ² , a 2-methyl-2-adamantyl group is particularly preferred. The alicyclic alkyl group needs to have a property capable of being eliminated by an acid generated from the radiation-sensitive acid generator, and when it is eliminated, the structure of the eliminated portion preferably has a planar structure. (A) The content of the repeating unit (1) in the copolymer is preferably 60% by weight or less, more preferably 50% by weight or less, and further preferably 5 to 45% by weight. As the formula (2) representing the repeating unit (2), a unit derived from p-hydroxystyrene or the like is particularly preferable.

The content of the repeating unit (2) in the copolymer (A) is preferably 30% by weight or more, more preferably 40% by weight or more, and further preferably 45 to 90% by weight. In the copolymer (A), the repeating unit (1) and the repeating unit (2) may be present alone or in combination of two or more. (A) The copolymer is composed of a repeating unit other than the repeating unit (1) and the repeating unit (2) (hereinafter, referred to as a repeating unit).
"Other repeating units").

[0012] The monomer giving another repeating unit includes
For example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o
-Vinyl aromatic compounds such as -methoxystyrene, m-methoxystyrene, p-methoxystyrene, ot-butoxystyrene, mt-butoxystyrene, pt-butoxystyrene; p- (1-methoxyethoxy) styrene , P- (1-ethoxyethoxy) styrene, p- (1
-N-propoxyethoxy) styrene, p- (1-i-
Propoxyethoxy) styrene, p- (1-n-butoxyethoxy) styrene, p- (1-t-butoxyethoxy) styrene, p- (1-n-pentyloxyethoxy) styrene, p- (1-n-hexyl) Oxyethoxy) styrene, p- (1-cyclopentyloxyethoxy) styrene, p- (1-cyclohexyloxyethoxy) styrene, p- (1-benzyloxyethoxy) styrene, p- {1- (1′-naphthylmethoxy) Ethoxy styrene,

P- (1-methoxypropoxy) styrene, p- (1-ethoxypropoxy) styrene, p-
(1-n-propoxypropoxy) styrene, p- (1
-I-propoxypropoxy) styrene, p- (1-n
-Butoxypropoxy) styrene, p- (1-t-butoxypropoxy) styrene, p- (1-n-pentyloxypropoxy) styrene, p- (1-n-hexyloxypropoxy) styrene, p- (1-cyclopentyl) Oxypropoxy) styrene, p- (1-cyclohexyloxypropoxy) styrene, p- (1-benzyloxypropoxy) styrene, p- {1- (1′-naphthylmethoxy) propoxy} styrene, p- (1-methoxybutoxy) ) Styrene, p- (1-ethoxybutoxy)
Styrene, p- (1-n-propoxybutoxy) styrene, p- (1-i-propoxybutoxy) styrene, p
-(1-n-butoxybutoxy) styrene, p- (1-
t-butoxybutoxy) styrene, p- (1-n-pentyloxybutoxy) styrene, p- (1-n-hexyloxybutoxy) styrene, p- (1-cyclopentyloxybutoxy) styrene, p- (1-cyclohexyl) Oxybutoxy) styrene, p- (1-benzyloxybutoxy) styrene, p- {1- (1′-naphthylmethoxy) butoxy} styrene,

P- (1-methoxy-2-methylpropoxy) styrene, p- (1-ethoxy-2-methylpropoxy) styrene, p- (1-n-propoxy-2-methylpropoxy) styrene, p- ( 1-i-propoxy-
2-methylpropoxy) styrene, p- (1-n-butoxy-2-methylpropoxy) styrene, p- (1-t
-Butoxy-2-methylpropoxy) styrene, p-
(1-n-pentyloxy-2-methylpropoxy) styrene, p- (1-n-hexyloxy-2-methylpropoxy) styrene, p- (1-cyclopentyloxy-2-methylpropoxy) styrene, p- ( 1-cyclohexyloxy-2-methylpropoxy) styrene, p
-(1-benzyloxy-2-methylpropoxy) styrene, p- {1- (1′-naphthylmethoxy) -2-methylpropoxy} styrene,

P- (1-methoxypentyloxy) styrene, p- (1-ethoxypentyloxy) styrene,
p- (1-n-propoxypentyloxy) styrene,
p- (1-i-propoxypentyloxy) styrene,
p- (1-n-butoxypentyloxy) styrene, p
-(1-t-butoxypentyloxy) styrene, p-
(1-n-pentyloxypentyloxy) styrene,
p- (1-n-hexyloxypentyloxy) styrene, p- (1-cyclopentyloxypentyloxy)
Styrene, p- (1-cyclohexyloxypentyloxy) styrene, p- (1-benzyloxypentyloxy) styrene, p- {1- (1′-naphthylmethoxy) pentyloxy} styrene,

P- (1-methoxy-2,2-dimethylpropoxy) styrene, p- (1-ethoxy-2,2-dimethylpropoxy) styrene, p- (1-n-propoxy-2,2-dimethylpropoxy) ) Styrene, p- (1
-I-propoxy-2,2-dimethylpropoxy) styrene, p- (1-n-butoxy-2,2-dimethylpropoxy) styrene, p- (1-t-butoxy-2,2-
Dimethylpropoxy) styrene, p- (1-n-pentyloxy-2,2-dimethylpropoxy) styrene, p
-(1-n-hexyloxy-2,2-dimethylpropoxy) styrene, p- (1-cyclopentyloxy-
2,2-dimethylpropoxy) styrene, p- (1-cyclohexyloxy-2,2-dimethylpropoxy) styrene, p- (1-benzyloxy-2,2-dimethylpropoxy) styrene, p- {1- (1 '-Naphthylmethoxy) -2,2-dimethylpropoxy styrene, p
-(1-methyl-1-methoxyethoxy) styrene, p
-(1-methyl-1-ethoxyethoxy) styrene, p
-(1-methyl-1-n-propoxyethoxy) styrene, p- (1-methyl-1-i-propoxyethoxy)
Styrene, p- (1-methyl-1-n-butoxyethoxy) styrene, p- (1-methyl-1-t-butoxyethoxy) styrene, p- (1-methyl-1-n-pentyloxyethoxy) styrene , P- (1-methyl-1-
n-hexyloxyethoxy) styrene, p- (1-methyl-1-cyclopentyloxyethoxy) styrene,
p- (1-methyl-1-cyclohexyloxyethoxy) styrene, p- (1-methyl-1-benzyloxyethoxy) styrene, p- {1-methyl-1- (1′-
Naphthylmethoxy) ethoxy｝ styrene,

P- (1-methyl-1-methoxypropoxy) styrene, p- (1-methyl-1-ethoxypropoxy) styrene, p- (1-methyl-1-n-propoxypropoxy) styrene, p- ( 1-methyl-1-i-
Propoxypropoxy) styrene, p- (1-methyl-
1-n-butoxypropoxy) styrene, p- (1-methyl-1-t-butoxypropoxy) styrene, p-
(1-methyl-1-n-pentyloxypropoxy) styrene, p- (1-methyl-1-n-hexyloxypropoxy) styrene, p- (1-methyl-1-cyclopentyloxypropoxy) styrene, p- ( 1-methyl-1-cyclohexyloxypropoxy) styrene, p
-(1-methyl-1-benzyloxypropoxy) styrene, p- {1-methyl-1- (1′-naphthylmethoxy) propoxy} styrene,

P- (1-methyl-1-methoxybutoxy) styrene, p- (1-methyl-1-ethoxybutoxy) styrene, p- (1-methyl-1-n-propoxybutoxy) styrene, p- ( 1-methyl-1-i-propoxybutoxy) styrene, p- (1-methyl-1-n
-Butoxybutoxy) styrene, p- (1-methyl-1)
-T-butoxybutoxy) styrene, p- (1-methyl-1-n-pentyloxybutoxy) styrene, p-
(1-methyl-1-n-hexyloxybutoxy) styrene, p- (1-methyl-1-cyclopentyloxybutoxy) styrene, p- (1-methyl-1-cyclohexyloxybutoxy) styrene, p- (1- Methyl-1
-Benzyloxybutoxy) styrene, p- {1-methyl-1- (1′-naphthylmethoxy) butoxy} styrene,

P- (1-Methyl-1-methoxy-2-methylpropoxy) styrene, p- (1-methyl-1-ethoxy-2-methylpropoxy) styrene, p- (1-methyl-1-methoxy-2-methylpropoxy) styrene
Methyl-1-n-propoxy-2-methylpropoxy)
Styrene, p- (1-methyl-1-i-propoxy-2)
-Methylpropoxy) styrene, p- (1-methyl-1)
-N-butoxy-2-methylpropoxy) styrene, p
-(1-methyl-1-t-butoxy-2-methylpropoxy) styrene, p- (1-methyl-1-n-pentyloxy-2-methylpropoxy) styrene, p- (1-
Methyl-1-n-hexyloxy-2-methylpropoxy) styrene, p- (1-methyl-1-cyclopentyloxy-2-methylpropoxy) styrene, p- (1-
Methyl-1-cyclohexyloxy-2-methylpropoxy) styrene, p- (1-methyl-1-benzyloxy-2-methylpropoxy) styrene, p- {1-methyl-1- (1′-naphthylmethoxy)- 2-methylpropoxydistyrene,

P- (1-methyl-1-methoxypentyloxy) styrene, p- (1-methyl-1-ethoxypentyloxy) styrene, p- (1-methyl-1-n-
Propoxypentyloxy) styrene, p- (1-methyl-1-i-propoxypentyloxy) styrene, p
-(1-methyl-1-n-butoxypentyloxy) styrene, p- (1-methyl-1-t-butoxypentyloxy) styrene, p- (1-methyl-1-n-pentyloxypentyloxy) styrene , P- (1-methyl-1-n-hexyloxypentyloxy) styrene,
p- (1-methyl-1-cyclopentyloxypentyloxy) styrene, p- (1-methyl-1-cyclohexyloxypentyloxy) styrene, p- (1-methyl-1-benzyloxypentyloxy) styrene, p
-{1-methyl-1- (1'-naphthylmethoxy) pentyloxy} styrene,

P- (1-methyl-1-methoxy-2,2
-Dimethylpropoxy) styrene, p- (1-methyl-
1-ethoxy-2,2-dimethylpropoxy) styrene, p- (1-methyl-1-n-propoxy-2,2-
Dimethylpropoxy) styrene, p- (1-methyl-1)
-I-propoxy-2,2-dimethylpropoxy) styrene, p- (1-methyl-1-n-butoxy-2,2-
Dimethylpropoxy) styrene, p- (1-methyl-1)
-T-butoxy-2,2-dimethylpropoxy) styrene, p- (1-methyl-1-n-pentyloxy-2,
2-dimethylpropoxy) styrene, p- (1-methyl-1-n-hexyloxy-2,2-dimethylpropoxy) styrene, p- (1-methyl-1-cyclopentyloxy-2,2-dimethylpropoxy) styrene , P-
(1-methyl-1-cyclohexyloxy-2,2-dimethylpropoxy) styrene, p- (1-methyl-1-
Benzyloxy-2,2-dimethylpropoxy) styrene, p- {1-methyl-1- (1′-naphthylmethoxy) -2,2-dimethylpropoxy} styrene,

Methoxycarbonyloxystyrene, ethoxycarbonyloxystyrene, n-propyloxycarbonyloxystyrene, i-propyloxycarbonyloxystyrene, n-butoxycarbonyloxystyrene, i-butoxycarbonyloxystyrene, t-butoxycarbonyloxystyrene, Cyclohexyloxycarbonyloxystyrene, methoxycarbonylmethoxystyrene, ethoxycarbonylmethoxystyrene,
n-propyloxycarbonylmethoxystyrene, i-
Propyloxycarbonylmethoxystyrene, n-butoxycarbonylmethoxystyrene, i-butoxycarbonylmethoxystyrene, t-butoxycarbonylmethoxystyrene, cyclohexyloxycarbonylmethoxystyrene,

Unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, mesaconic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride and their acid anhydrides; Saturated carboxylic acid methyl ester, ethyl ester, n-propyl ester, i-propyl ester, n-butyl ester, i-butyl ester, sec-butyl ester, t
-Butyl ester, n-amyl ester, n-hexyl ester, cyclohexyl ester, 2-hydroxyethyl ester, 2-hydroxypropyl ester, 3-
Hydroxypropyl ester, 2,2-dimethyl-3-
Hydroxypropyl ester, benzyl ester, isobornyl ester, tricyclodecanyl ester, 1-
Esters such as adamantyl ester; unsaturated nitriles such as (meth) acrylonitrile, maleinitrile, fumaronitrile, mesaconnitrile, citraconitrile, itaconitrile;

(Meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide,
Unsaturated amides such as citraconamide and itaconamide; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; bicyclo [2.2.1] hept-2-ene (norbornene), tetracyclo [4 .4.0.1 ^2,5 .1 ^7,10] dodeca-3-ene, cyclobutene, cyclopentene, cyclooctene,
Dicyclopentadiene, tricyclo [5.2.1.0 ^2,6 ]
Compounds having an alicyclic skeleton such as decene; unsaturated alcohols such as (meth) allyl alcohol; N-vinylaniline, vinylpyridines, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, N-vinylimidazole , N-vinylcarbazole and the like.

Among these monofunctional monomers, styrene, pt-butoxystyrene, t-butyl (meth) acrylate, p- (1-methoxyethoxy) styrene,
p- (1-ethoxyethoxy) styrene, p- (1-benzyloxyethoxy) styrene, p- {1- (1′-
Naphthylmethoxy) ethoxy)｝ styrene, p- (1-
Methyl-1-methoxyethoxy) styrene, p- (1-
Methoxypropoxy) styrene, p- (1-ethoxypropoxy) styrene, p- (1-benzyloxypropoxy) styrene, p- {1- (1′-naphthylmethoxy) propoxy)} styrene, p- (1-cyclohexyloxy Preference is given to ethoxy) styrene. (A) The content of the other repeating unit in the copolymer is preferably 40% by weight or less, more preferably 5 to 35% by weight.

In addition, the copolymer (A) may have, in addition to these repeating units, 2 units in the molecule as other repeating units.
One or more polyfunctional monomers having at least two polymerizable unsaturated groups can be contained. Examples of the polyfunctional monomer having two or more polymerizable unsaturated groups in a molecule include, for example, 2
Esters of a compound having two or more hydroxyl groups in the molecule of a polyhydric alcohol, polyether diol, polyester diol or the like having a valence of 2 or more with (meth) acrylic acid; Adducts of a compound having an epoxy group with (meth) acrylic acid; condensates of a compound having two or more amino groups in the molecule with (meth) acrylic acid; Is
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, trimethylolpropane di (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol In addition to di (meth) acrylate and N, N'-methylenebis (meth) acrylamide, (poly) alkylene glycol (derivative) di (meth) such as di (meth) acrylate of ethylene glycol adduct or propyl glycol adduct of bisphenol A A) acrylates, epoxy (meth) acrylates such as (meth) acrylic acid diadduct of bisphenol A diglycidyl ether, and the like.

Among these polyfunctional monomers, ethylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and 2,5-
Dimethyl-2,5-hexanediol di (meth) acrylate, (meth) acrylic acid diadduct of bisphenol A diglycidyl ether and the like are preferable. By using a polyfunctional monomer as a monomer giving another repeating unit, an appropriate crosslinked structure is introduced into the copolymer (A),
It can reduce the mobility of the polymer molecular chains, thereby suppressing thermal deformation and improving heat resistance and the like. Also,
When the crosslinked structure introduced by the polyfunctional monomer has an acid dissociation property, the molecular weight decrease due to exposure is larger than in the case of a linear resin or the case where the crosslinked structure has no acid dissociation property. As a result, the difference in the dissolution rate of the exposed portion and the unexposed portion in the developer is increased, so that the resolution can be further improved. The content of the polyfunctional monomer in the copolymer (A) is preferably 10% by weight or less, more preferably 1 to 7% by weight.
It is.

(A) The copolymer is, for example, the following (A) to
It can be manufactured by the method (c) or the like. (A) acetoxystyrenes and repeating units (1), together with monomers corresponding to other repeating units, if necessary, for example, by appropriately selecting a radical polymerization initiator, for example, bulk polymerization, solution polymerization, precipitation polymerization, After copolymerization by an appropriate method such as emulsion polymerization, suspension polymerization, or bulk-suspension polymerization, the acetyl group in the copolymer is selectively hydrolyzed and / or solvolyzed using a basic catalyst. Manufacturing method.

(B) T-butoxystyrenes and repeating units (1), together with monomers corresponding to other repeating units, if necessary, for example, a radical polymerization initiator are appropriately selected, and bulk polymerization and solution polymerization are carried out. After copolymerization by a suitable method such as precipitation polymerization, emulsion polymerization, suspension polymerization, or bulk-suspension polymerization, or living anion polymerization, the t-butyl group in the copolymer is entirely removed using an acidic catalyst. A method for producing by selective or selective hydrolysis and / or solvolysis.

(C) The radical unit (1) and the repeat unit (2) are optionally selected together with a monomer corresponding to another repeat unit, for example, a radical polymerization initiator is appropriately selected, and the bulk polymerization, solution A method for producing the polymer by an appropriate method such as polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization, or bulk-suspension polymerization.

(A) The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) of the copolymer determined by gel permeation chromatography (GPC) is as follows. Mw of the copolymer (A) having no cross-linked structure by the polyfunctional monomer is preferably from 1,000 to 1
00,000, more preferably 3,000 to 40,00
0, and more preferably 3,000 to 30,000.
In this case, if the Mw of the copolymer (A) is less than 1,000, the sensitivity and heat resistance as a resist tend to decrease, while if it exceeds 100,000, the solubility in a developer decreases. Tend.

The ratio of the Mw of the copolymer (A) having no cross-linked structure due to the polyfunctional monomer to the number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) (hereinafter referred to as “Mn”). (Mw / Mn)
Is preferably 1.0 to 5.0, more preferably 1.0 to 5.0
4.0, more preferably 1.0 to 3.0. Also,
Mw of the copolymer (A) having a crosslinked structure by a polyfunctional monomer is preferably from 3,000 to 500,000, more preferably from 5,000 to 400,000, and still more preferably from 8,000 to 300. , 000. In this case, (A)
When the Mw of the copolymer is less than 3,000, the sensitivity and heat resistance as a resist tend to decrease.
If it exceeds 0.00000, the developability as a resist tends to decrease, and development defects tend to be promoted. Mw / Mn of (A) copolymer having cross-linked structure by polyfunctional monomer
Is preferably 1.5 to 20.0, more preferably 1.5.
１５15.0.

(B) Radiation-Sensitive Acid Generator (B) The radiation-sensitive acid generator (hereinafter referred to as “acid generator”) used in the present invention comprises a compound that generates an acid upon exposure. Such acid generators include:
Onium salts, sulfone compounds, sulfonate compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds and the like can be mentioned. Examples of these acid generators are shown below.

Onium salt: Examples of the onium salt include an iodonium salt, a sulfonium salt, a phosphonium salt, a diazonium salt, an ammonium salt, a pyridinium salt and the like. Specific examples of the onium salt compound include bis (4-t-butylphenyl) iodonium nonafluorobutanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, and bis (4-t-butylphenyl) iodonium perfluoro Octanesulfonate, bis (4-t-butylphenyl) iodonium pyrene sulfonate, bis (4-t-butylphenyl) iodonium dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t −
Butylphenyl) iodoniumbenzenesulfonate,
Bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium octanesulfonate, bis (4-t
-Butylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, 4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium perfluorobenzenesulfonate,

Diphenyliodonium nonafluorobutanesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium perfluorooctanesulfonate, diphenyliodonium pyrene sulfonate, diphenyliodonium dodecylbenzenesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium benzenesulfonate, diphenyliodonium 10- Camphorsulfonate, diphenyliodonium octanesulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate, diphenyliodonium 4-
Trifluoromethylbenzenesulfonate, diphenyliodonium perfluorobenzenesulfonate,

Di (p-toluyl) iodonium nonafluorobutanesulfonate, di (p-toluyl) iodonium trifluoromethanesulfonate, di (p-toluyl) iodonium perfluorooctanesulfonate,
Di (p-toluyl) iodonium pyrene sulfonate,
Di (p-toluyl) iodonium dodecylbenzenesulfonate, di (p-toluyl) iodonium p-toluenesulfonate, di (p-toluyl) iodoniumbenzenesulfonate, di (p-toluyl) iodonium 1
0-camphorsulfonate, di (p-toluyl) iodonium octanesulfonate, di (p-toluyl) iodonium 2-trifluoromethylbenzenesulfonate, di (p-toluyl) iodonium 4-trifluoromethylbenzenesulfonate, di (p-toluyl) ) Iodonium perfluorobenzenesulfonate,

Di (3,4-dimethylphenyl) iodonium nonafluorobutanesulfonate, di (3,4-dimethylphenyl) iodonium trifluoromethanesulfonate, di (3,4-dimethylphenyl) iodonium perfluorooctanesulfonate, di (3 , 4-Dimethylphenyl) iodonium pyrene sulfonate, di (3,4-dimethylphenyl) iodonium dodecylbenzenesulfonate, di (3,4-dimethylphenyl)
Iodonium p-toluenesulfonate, di (3,4-
Dimethylphenyl) iodoniumbenzenesulfonate, di (3,4-dimethylphenyl) iodonium 10
-Camphorsulfonate, di (3,4-dimethylphenyl) iodonium octanesulfonate, di (3,4
-Dimethylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (3,4-dimethylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, di (3,4-dimethylphenyl) iodonium perfluorobenzenesulfonate,

P-nitrophenyl / phenyliodonium nonafluorobutanesulfonate, p-nitrophenyl / phenyliodonium trifluoromethanesulfonate, p-nitrophenyl / phenyliodonium perfluorooctanesulfonate, p-nitrophenyl /
Phenyliodonium pyrene sulfonate, p-nitrophenyl / phenyliodonium dodecylbenzenesulfonate, p-nitrophenyl / phenyliodonium p-toluenesulfonate, p-nitrophenyl / phenyliodonium benzenesulfonate, p-nitrophenyl / phenyliodonium 10-camphorsulfonate, p-nitrophenyl / phenyliodonium octanesulfonate, p-nitrophenyl / phenyliodonium 2-trifluoromethylbenzenesulfonate, p-nitrophenyl / phenyliodonium 4-trifluoromethylbenzenesulfonate, p-nitrophenyl / phenyliodonium perfluorobenzene Sulfonate,

Di (m-nitrophenyl) iodonium nonafluorobutanesulfonate, di (m-nitrophenyl) iodonium trifluoromethanesulfonate, di (m-nitrophenyl) iodonium perfluorooctanesulfonate, di (m-nitrophenyl) iodoniumpyrene Sulfonate, di (m-nitrophenyl) iodonium dodecylbenzenesulfonate, di (m-nitrophenyl) iodonium p-toluenesulfonate, di (m-nitrophenyl) iodoniumbenzenesulfonate, di (m-nitrophenyl) iodonium 1
0-camphorsulfonate, di (m-nitrophenyl) iodonium octanesulfonate, di (m-nitrophenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (m-nitrophenyl) iodonium 4-trifluoromethylbenzenesulfonate, di ( m-nitrophenyl) iodonium perfluorobenzenesulfonate,

Methoxyphenyl phenyliodonium nonafluorobutanesulfonate, methoxyphenyl
Phenyliodonium trifluoromethanesulfonate, methoxyphenyl phenyliodonium perfluorooctane sulfonate, methoxyphenyl phenyliodonium pyrene sulfonate, methoxyphenyl phenyliodonium dodecylbenzenesulfonate, methoxyphenyl phenyliodonium p-toluenesulfonate, methoxyphenyl phenyliodonium benzenesulfonate Methoxyphenyl phenyliodonium 10-camphorsulfonate, methoxyphenyl phenyliodonium octane sulfonate, methoxyphenyl phenyliodonium 2-trifluoromethylbenzenesulfonate, methoxyphenyl phenyliodonium 4-trifluoromethylbenzenesulfonate, Tokishifeniru-iodonium perfluoro sulfonate,

Di (p-chlorophenyl) iodonium nonafluorobutanesulfonate, di (p-chlorophenyl) iodonium trifluoromethanesulfonate, di (p-chlorophenyl) iodonium perfluorooctane sulfonate, di (p-chlorophenyl) iodonium pyrene sulfonate, di ( p-chlorophenyl) iodonium dodecylbenzenesulfonate, di (p-chlorophenyl) iodonium p-toluenesulfonate, di (p-chlorophenyl) iodoniumbenzenesulfonate, di (p-chlorophenyl) iodonium 1
0-camphorsulfonate, di (p-chlorophenyl) iodonium octanesulfonate, di (p-chlorophenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (p-chlorophenyl) iodonium 4-trifluoromethylbenzenesulfonate, di (p-chlorophenyl) ) Iodonium perfluorobenzenesulfonate,

Di (p-trifluoromethylphenyl) iodonium nonafluorobutanesulfonate, di (p-
Trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (p-trifluoromethylphenyl) iodonium perfluorooctane sulfonate, di (p-trifluoromethylphenyl) iodonium pyrene sulfonate, di (p-trifluoromethylphenyl) iodonium dodecylbenzene Sulfonate,
Di (p-trifluoromethylphenyl) iodonium p
-Toluenesulfonate, di (p-trifluoromethylphenyl) iodoniumbenzenesulfonate, di (p
-Trifluoromethylphenyl) iodonium 10-camphorsulfonate, di (p-trifluoromethylphenyl) iodonium octanesulfonate, di (p-
Trifluoromethylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, di (p-trifluoromethylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, di (p-trifluoromethylphenyl) iodonium perfluorobenzenesulfonate,

Dinaphthyliodonium nonafluorobutanesulfonate, dinaphthyliodonium trifluoromethanesulfonate, dinaphthyliodonium perfluorooctanesulfonate, dinaphthyliodonium pyrenesulfonate, dinaphthyliodonium dodecylbenzenesulfonate, dinaphthyliodonium p-toluenesulfonate, dinaphthyliodonium Benzenesulfonate, dinaphthyliodonium 10-camphorsulfonate, dinaphthyliodonium octanesulfonate, dinaphthyliodonium 2-trifluoromethylbenzenesulfonate, dinaphthyliodonium 4-
Trifluoromethylbenzenesulfonate, dinaphthyliodonium perfluorobenzenesulfonate,

Biphenylene iodonium nonafluorobutanesulfonate, biphenyleneiodonium trifluoromethanesulfonate, biphenyleneiodonium perfluorooctanesulfonate, biphenyleneiodonium pyrenesulfonate, biphenyleneiodonium dodecylbenzenesulfonate, biphenyleneiodonium p-toluenesulfonate, biphenyleneiodoniumbenzene10 Camphor sulfonate, biphenylene iodonium octane sulfonate, biphenylene iodonium 2-trifluoromethylbenzene sulfonate, biphenylene iodonium 4-trifluoromethylbenzene sulfonate, biphenylene iodonium perfluorobenzene sulfonate ,

2-chlorobiphenylene iodonium nonafluorobutane sulfonate, 2-chlorobiphenylene iodonium trifluoromethanesulfonate, 2-chlorobiphenylene iodonium perfluorooctane sulfonate, 2-chlorobiphenylene iodonium pyrene sulfonate, 2-chlorobiphenylene iodonium dodecylbenzene sulfonate, 2 -Chlorobiphenylene iodonium p-toluenesulfonate, 2-chlorobiphenylene iodonium benzenesulfonate,
Chlorobiphenylene iodonium 10-camphor sulfonate, 2-chlorobiphenylene iodonium octane sulfonate, 2-chlorobiphenylene iodonium 2-trifluoromethylbenzene sulfonate, 2-chlorobiphenylene iodonium 4-trifluoromethylbenzene sulfonate, 2-chlorobiphenylene iodonium perfluorobenzene Sulfonate,

Triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorooctanesulfonate, triphenylsulfonium pyrenesulfonate, triphenylsulfonium dodecylbenzenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium Benzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium octanesulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-trifluoromethylbenzenesulfonate, triphenylsulfonium hexafluoroantimonate, Li triphenylsulfonium naphthalenesulfonate, triphenylsulfonium perfluoro sulfonate,

4-t-butylphenyl / diphenylsulfonium nonafluorobutanesulfonate, 4-t-butylphenyl / diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl / diphenylsulfonium perfluorooctanesulfonate,
-T-butylphenyl / diphenylsulfonium pyrene sulfonate, 4-t-butylphenyl / diphenylsulfonium dodecylbenzenesulfonate, 4-t-butylphenyl / diphenylsulfonium p-toluenesulfonate, 4-t-butylphenyl / diphenylsulfoniumbenzenesulfonate, 4-t-butylphenyl / diphenylsulfonium 10-camphorsulfonate, 4-t-butylphenyl / diphenylsulfonium octanesulfonate, 4-t-butylphenyl / diphenylsulfonium 2-trifluoromethylbenzenesulfonate, 4-t-butylphenyl / Diphenylsulfonium 4-trifluoromethanebenzenesulfonate, 4-t-butylphenyl / diphenylsulfonium perfluoroben Nsuruhoneto,

4-t-butoxyphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-
Butoxyphenyl diphenylsulfonium nonafluorobutanesulfonate, 4-t-butoxyphenyl diphenylsulfonium perfluorooctanesulfonate, 4-t-butoxyphenyl diphenylsulfonium pyrene sulfonate, 4-t-butoxyphenyl diphenylsulfonium p-toluenesulfonate, 4-
t-butoxyphenyl diphenylsulfonium benzenesulfonate, 4-t-butoxyphenyl diphenylsulfonium 10-camphorsulfonate, 4-t
-Butoxyphenyl diphenylsulfonium octanesulfonate, 4-t-butoxyphenyl diphenylsulfonium 2-trifluoromethylbenzenesulfonate, 4-t-butoxyphenyl diphenylsulfonium 4-trifluoromethylbenzenesulfonate,
-T-butoxyphenyl diphenylsulfonium perfluorobenzenesulfonate,

4-hydroxyphenyl / diphenylsulfonium trifluoromethanesulfonate, 4-hydroxyphenyl / diphenylsulfonium nonafluorobutanesulfonate, 4-hydroxyphenyl / diphenylsulfonium perfluorooctanesulfonate,
-Hydroxyphenyl diphenylsulfonium pyrene sulfonate, 4-hydroxyphenyl diphenylsulfonium p-toluenesulfonate, 4-hydroxyphenyl diphenylsulfonium benzenesulfonate, 4-hydroxyphenyl diphenylsulfonium 10-camphorsulfonate, 4-hydroxyphenyl diphenylsulfonium Octanesulfonate, 4
-Hydroxyphenyl diphenylsulfonium 2-trifluoromethylbenzenesulfonate, 4-hydroxyphenyldiphenylsulfonium 4-trifluoromethylbenzenesulfonate, perfluorobenzenesulfonate,

Tri (p-methoxyphenyl) sulfonium nonafluorobutanesulfonate, tri (p-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (p-methoxyphenyl) sulfonium perfluorooctanesulfonate, tri (p-methoxyphenyl) sulfoniumpyrene Sulfonate, tri (p-
Methoxyphenyl) sulfonium p-toluenesulfonate, tri (p-methoxyphenyl) sulfoniumbenzenesulfonate, tri (p-methoxyphenyl) sulfonium 10-camphorsulfonate, tri (p-methoxyphenyl) sulfoniumoctanesulfonate,
Tri (p-methoxyphenyl) sulfonium 2-trifluoromethylbenzenesulfonate, tri (p-methoxyphenyl) sulfonium 4-trifluoromethylbenzenesulfonate, tri (p-methoxyphenyl) sulfonium perfluorobenzenesulfonate,

Di (methoxyphenyl) .p-tolylsulfonium nonafluorobutanesulfonate, di (methoxyphenyl) .p-tolylsulfonium trifluoromethanesulfonate, di (methoxyphenyl) .p-
Toluylsulfonium perfluorooctanesulfonate, di (methoxyphenyl) -p-tolylsulfonium pyrene sulfonate, di (methoxyphenyl) .p-
Toluylsulfonium p-toluenesulfonate, di (methoxyphenyl) .p-tolylsulfoniumbenzenesulfonate, di (methoxyphenyl) .p-tolylsulfonium 10-camphorsulfonate, di (methoxyphenyl) .p-tolylsulfonium octanesulfonate, di ( Methoxyphenyl) .p-toluylsulfonium 2-trifluoromethylbenzenesulfonate, di (methoxyphenyl) .p-toluylsulfonium 4-trifluoromethylbenzenesulfonate, di (methoxyphenyl) .p-toluylsulfonium perfluorobenzenesulfonate,

Phenyl tetramethylene sulfonium nonafluorobutane sulfonate, phenyl tetramethylene sulfonium trifluoromethane sulfonate, phenyl tetramethylene sulfonium perfluorooctane sulfonate, phenyl tetramethylene sulfonium pyrene sulfonate, phenyl tetramethylene sulfonium p-toluene sulfonate, Phenyl tetramethylene sulfonium benzene sulfonate, phenyl tetramethylene sulfonium 10-camphor sulfonate, phenyl tetramethylene sulfonium octane sulfonate, phenyl tetramethylene sulfonium 2-trifluoromethylbenzene sulfonate, phenyl tetramethylene sulfonium 4-trifluoromethylbenzene S Honeto, phenyl tetramethylene sulfonium perfluoro sulfonate,

P-hydroxyphenyl tetramethylene sulfonium nonafluorobutane sulfonate, p-hydroxyphenyl tetramethylene sulfonium trifluoromethane sulfonate, p-hydroxyphenyl
Tetramethylene sulfonium perfluorooctane sulfonate, p-hydroxyphenyl / tetramethylene sulfonium pyrene sulfonate, p-hydroxyphenyl / tetramethylene sulfonium p-toluene sulfonate, p-hydroxyphenyl / tetramethylene sulfonium benzene sulfonate, p-hydroxyphenyl / tetramethylene Sulfonium 10-camphorsulfonate, p-hydroxyphenyl / tetramethylenesulfonium octanesulfonate, p-hydroxyphenyl / tetramethylenesulfonium 2-trifluoromethylbenzenesulfonate, p-hydroxyphenyl / tetramethylenesulfonium 4-trifluoromethylbenzenesulfonate, p -Hydroxyphenyl tetramethylene sulfonium Perfluoro sulfonate,

Phenyl biphenylene sulfonium nonafluorobutane sulfonate, phenyl biphenylene sulfonium trifluoromethane sulfonate, phenyl biphenylene sulfonium perfluorooctane sulfonate, phenyl biphenylene sulfonium pyrene sulfonate, phenyl biphenylene sulfonium p-toluene sulfonate, phenyl biphenylene sulfonium benzene sulfonate, phenyl biphenylene -Camphorsulfonate, phenylbiphenylenesulfonium octanesulfonate, phenylbiphenylenesulfonium 2-trifluoromethylbenzenesulfonate, phenylbiphenylenesulfonium 4-trifluoromethylbenzenesulfonate, phenylbiphenylenesulfonate Arm perfluoro sulfonate,

(4-phenylthiophenyl) diphenylsulfonium nonafluorobutanesulfonate, (4
-Phenylthiophenyl) diphenylsulfonium trifluoromethanesulfonate, (4-phenylthiophenyl) diphenylsulfonium perfluorooctanesulfonate, (4-phenylthiophenyl) diphenylsulfonium pyrene sulfonate, (4-phenylthiophenyl) diphenylsulfonium p-toluenesulfonate, (4-phenylthiophenyl) diphenylsulfonium benzenesulfonate, (4-phenylthiophenyl) diphenylsulfonium 10-camphorsulfonate, (4-phenylthiophenyl)
-Diphenylsulfonium octane sulfonate, (4
-Phenylthiophenyl) diphenylsulfonium 2
-Trifluoromethylbenzenesulfonate, (4-phenylthiophenyl) diphenylsulfonium 4-trifluoromethylbenzenesulfonate, (4-phenylthiophenyl) diphenylsulfonium perfluorobenzenesulfonate,

4,4'-bis (diphenylsulfoniophenyl) sulfidedinonafluorobutanesulfonate, 4,4'-bis (diphenylsulfoniophenyl)
Sulfide ditrifluoromethanesulfonate, 4,
4'-bis (diphenylsulfoniophenyl) sulfide diperfluorooctanesulfonate, 4,4'-bis (diphenylsulfoniophenyl) sulfidedipyrene sulfonate, 4,4'-bis (diphenylsulfoniophenyl) sulfidedi-p-toluene Sulfonate,
4,4'-bis (diphenylsulfoniophenyl) sulfidedibenzenesulfonate, 4,4'-bis (diphenylsulfoniophenyl) sulfidedi10-camphorsulfonate, 4,4'-bis (diphenylsulfoniophenyl) sulfidedioctane Sulfonate,
4,4'-bis (diphenylsulfoniophenyl) sulfide di-2-trifluoromethylbenzenesulfonate, 4,4'-bis (diphenylsulfoniophenyl)
Sulfide di-4-trifluoromethylbenzenesulfonate, 4,4′-bis (diphenylsulfoniophenyl) sulfide diperfluorobenzenesulfonate,
And the like.

Sulfone compound: Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof. Specific examples of the sulfone compound include phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, 4-trisphenacylsulfone, and the like.

Sulfonate compound: Examples of the sulfonic acid ester compound include alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates. Specific examples of the sulfonic acid ester compound include benzoin tosylate, pyrogallol tristrifluoromethane sulfonate, pyrogallol trisnonafluorobutane sulfonate, pyrogallol methanesulfonic acid triester, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, α -Methylol benzoin tosylate, α-methylol benzoin octane sulfonate, α-methylol benzoin trifluoromethanesulfonate, α-methylol benzoindodecyl sulfonate, and the like.

Sulfonimide compound: As the sulfonimide compound, for example, the following formula (8)

[0060]

Embedded image (Wherein, R ⁶ represents a divalent group such as an alkylene group, an arylene group, or an alkoxylene group, and R ⁷ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group. Are shown below.).

Specific examples of the sulfonimide compound include:
N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy)
Phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (tri Fluoromethylsulfonyloxy)
Bicyclo [2.2.1] heptane-5,6-oxy-2,3
-Dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10
-Camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy)
-7-oxabicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane-
5,6-oxy-2,3-dicarboximide, N- (1
0-camphorsulfonyloxy) naphthylimide,

N- (octanesulfonyloxy) succinimide, N- (octanesulfonyloxy) phthalimide, N- (octanesulfonyloxy) diphenylmaleimide, N- (octanesulfonyloxy) bicyclo [2.2.1] hept-5- Ene-2,3-dicarboximide, N- (octanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (octanesulfonyloxy)
Bicyclo [2.2.1] heptane-5,6-oxy-2,3
-Dicarboxyimide, N- (octanesulfonyloxy) naphthylimide, N- (p-toluenesulfonyloxy) succinimide, N- (p-toluenesulfonyloxy) phthalimide, N- (p-toluenesulfonyloxy) diphenylmaleimide, N -(P-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) -7-oxabicyclo [2.2.1] ]
Hept-5-ene-2,3-dicarboximide, N-
(P-Toluenesulfonyloxy) bicyclo [2.2.
1] heptane-5,6-oxy-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide,

N- (2-trifluoromethylbenzenesulfonyloxy) succinimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide,
N- (2-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N-
(2-trifluoromethylbenzenesulfonyloxy)
-7-oxabicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.
1] Heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4-trifluoromethylbenzenesulfonyloxy) succinimide, N-
(4-trifluoromethylbenzenesulfonyloxy)
Phthalimide, N- (4-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (4-
Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2 .1] hept-5-ene-2,3-dicarboximide, N- (4
-Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide,

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

N- (naphthalenesulfonyloxy) succinimide, N- (naphthalenesulfonyloxy) phthalimide, N- (naphthalenesulfonyloxy) diphenylmaleimide, N- (naphthalenesulfonyloxy)
Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (naphthalenesulfonyloxy)
-7-oxabicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (naphthalenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-
Oxy-2,3-dicarboximide, N- (naphthalenesulfonyloxy) naphthylimide, N- (nonafluorobutylsulfonyloxy) succinimide, N-
(Nonafluorobutylsulfonyloxy) phthalimide, N- (nonafluorobutylsulfonyloxy) diphenylmaleimide, N- (nonafluorobutylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (nonafluorobutylsulfonyloxy) -7-oxabicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- (nonafluorobutylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (nonafluorobutylsulfonyloxy) naphthylimide

N- (perfluorooctanesulfonyloxy) succinimide, N- (perfluorooctanesulfonyloxy) phthalimide, N- (perfluorooctanesulfonyloxy) diphenylmaleimide, N- (perfluorooctanesulfonyloxy) diphenylmaleimide
(Perfluorooctanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluorooctanesulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (perfluorooctanesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N
-(Perfluorooctanesulfonyloxy) naphthylimide N- (benzenesulfonyloxy) succinimide, N- (benzenesulfonyloxy) phthalimide,
N- (benzenesulfonyloxy) diphenylmaleimide, N- (benzenesulfonyloxy) bicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide N- (benzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (benzenesulfonyloxy)
Naphthyl imide and the like can be mentioned.

Diazomethane compound: As the diazomethane compound, for example, the following formula (9)

[0068]

Embedded image (Wherein R ⁸ and R ⁹ may be the same or different and each represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, and a halogen-substituted aryl group). Can be mentioned.

Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethyl Benzenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, bis (p-
t-butylphenylsulfonyl) diazomethane, bis (p-chlorobenzenesulfonyl) diazomethane, cyclohexylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1
-Dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane,
Bis (1-methylethylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5,
5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4,5] decane-7-sulfonyl) diazomethane and the like.

Disulfonylmethane compound: As the disulfonylmethane compound, for example, the following formula (10)

[0071]

Embedded image

[In the formula, R ¹⁰ and R ¹¹ may be the same or different from each other, and may be a monovalent linear or branched aliphatic hydrocarbon group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group. Represents another monovalent organic group having an atom, V and W may be the same or different from each other, and may be an aryl group, a hydrogen atom, a monovalent linear or branched aliphatic hydrocarbon group or a heterocyclic group. Represents another monovalent organic group having an atom, and at least one of V and W is an aryl group, or V and W are interconnected to form a monocyclic or polycyclic group having at least one unsaturated bond. It forms a ring or V and W are interconnected to form a group of formula 8. ]

[0073]

Embedded image

(However, V ′ and W ′ may be the same or different from each other, and a plurality of V ′ and W ′ may be the same or different, respectively, and include a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl A group, an aryl group or an aralkyl group, or V ′ and W ′ bonded to the same or different carbon atoms are connected to each other to form a carbon monocyclic structure, and n is an integer of 2 to 10. is there.)

The above-mentioned acid generators can be used alone or in combination of two or more. In the present invention, the amount of the acid generator used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 1 part by weight per 100 parts by weight of the copolymer (A).
5 parts by weight.

Acid Diffusion Control Agent In the present invention, an acid having an action of controlling the diffusion phenomenon of an acid generated from an acid generator upon exposure in a resist film and suppressing an undesired chemical reaction in a non-exposed area. It is preferable to add a diffusion controlling agent. By using such an acid diffusion controller, the storage stability of the composition is improved, the resolution as a resist is improved, and the line width change of the resist pattern due to the fluctuation of the PED can be suppressed. It is extremely excellent in properties. 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 formula (12)

[0078]

Embedded image

[Wherein, R ¹² , R ¹³ and R ¹⁴ may be the same or different from each other and represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group (an alkyl group, an aryl group,
A hydrogen atom such as an aralkyl group is substituted with a functional group such as a hydroxy group). ]

(Hereinafter, referred to as "nitrogen-containing compound (I)"), a diamino compound having two nitrogen atoms in the same molecule (hereinafter, referred to as "nitrogen-containing compound (II)"), Examples thereof include diamino polymers having three or more nitrogen atoms (hereinafter, referred to as “nitrogen-containing compound (III)”), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds.

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

As the nitrogen-containing compound (II), for example,
Ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-
Diaminodiphenylamine, 2,2'-bis (4-aminophenyl) propane, 2- (3-aminophenyl)-
2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1, 4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-
Bis [1- (4-aminophenyl) -1-methylethyl] benzene and the like can be mentioned. Examples of the nitrogen-containing compound (III) include polymers of polyethyleneimine, polyallylamine, and dimethylaminoethylacrylamide.

Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-
Examples thereof include dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, and N-methylpyrrolidone. Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tributylthiourea. be able to.

Examples of the nitrogen-containing heterocyclic compound include imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole,
Imidazoles such as 2-phenylbenzimidazole;
Pyridine, 2-methylpyridine, 4-methylpyridine,
2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-
In addition to pyridines such as phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline and acridine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4
-Dimethylpiperazine, 1,4-diazabicyclo [2.
2.2] octane. Among these nitrogen-containing organic compounds, a nitrogen-containing compound (I), a nitrogen-containing heterocyclic compound and the like are preferable. Further, among the nitrogen-containing compounds (I), trialkylamines are particularly preferable, and among the nitrogen-containing heterocyclic compounds, pyridines are particularly preferable.

The acid diffusion controllers can be used alone or in combination of two or more. The amount of the acid diffusion controller is preferably 1 to 100 parts by weight of the copolymer (A).
It is 5 parts by weight or less, more preferably 0.001 to 10 parts by weight, even more preferably 0.005 to 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. The amount of the acid diffusion controller was 0.001.
If the amount is less than the weight part, the pattern shape and dimensional fidelity as a resist may be reduced depending on the process conditions.

Other Additives The radiation-sensitive resin composition of the present invention may contain a surfactant having an effect of improving the coating properties, striation, and developability as a resist of the composition. Such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Examples thereof include polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyethylene glycol dilaurate, and polyethylene glycol distearate. Commercially available products include, for example, EFTOP EF301, EF303, and EF352 ( Tokam Products Co., Ltd.), Megafax F171, F1
73 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard F
C430, FC431 (manufactured by Sumitomo 3M Limited), Asahi Guard AG710, Surflon S-382, SC1
01, SC102, SC103, SC104, SC10
5, SC106 (manufactured by Asahi Glass Co., Ltd.), KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, No. 95
(Manufactured by Kyoeisha Chemical Co., Ltd.).

The blending amount of the surfactant is as follows: (A) copolymer 1
It is preferably at most 2 parts by weight per 00 parts by weight. Further, the radiation-sensitive resin composition of the present invention has an effect of absorbing radiation energy, transmitting the energy to the acid generator, thereby increasing the amount of acid generated, and apparent sensitivity of the resist. And a sensitizer having an effect of improving the sensitizer.

Preferred sensitizers include benzophenones, rose bengals, anthracenes and the like. The compounding amount of the sensitizer is (A) copolymer 10
It is usually 50 parts by weight or less per 0 parts by weight. In addition, by blending a dye and / or a pigment, the latent image in the exposed area can be visualized and the effect of halation during exposure can be reduced, and the adhesion to the substrate can be further improved by blending an adhesion aid. can do. Further, as other additives, an antihalation agent such as 4-hydroxy-4′-methylchalcone, a shape improver, a storage stabilizer, an antifoaming agent, and the like can be blended.

Solvent The radiation-sensitive resin composition of the present invention may be used,
The composition is obtained by uniformly dissolving in a solvent so that the concentration of the total solid content is, for example, 1 to 50% by weight, preferably 5 to 40% by weight, and then filtering through, for example, a filter having a pore size of about 0.2 μm. Prepared as a solution.

Examples of the solvent used for preparing the composition solution include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate. Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol dimethyl ether; Propylene glycol diethyl ether, propylene glycol di-n-
Propylene glycol dialkyl ethers such as propyl ether and propylene glycol di-n-butyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate and the like Propylene glycol monoalkyl ether acetates; methyl lactate, ethyl lactate,
Lactic acid esters such as n-propyl lactate and i-propyl lactate; n-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate;
Aliphatic carboxylic acid esters such as i-butyl acetate, n-amyl acetate, i-amyl acetate, i-propyl propionate, n-butyl propionate and i-butyl propionate; ethyl hydroxyacetate, 2-hydroxy-2 -Ethyl methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate,
Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-
Ethyl ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate,
3-methyl-3-methoxybutyl propionate, 3-
Other esters such as methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl propyl ketone, methyl butyl Ketone, 2-heptanone, 3-
Ketones such as heptanone, 4-heptanone and cyclohexanone; amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Lactones such as γ-butyrolactone can be mentioned. These solvents can be used alone or in combination of two or more.

Formation of Resist Pattern When forming a resist pattern from the radiation-sensitive resin composition of the present invention, the composition solution prepared as described above is applied by spin coating, casting coating, roll coating, or the like. By an appropriate coating means, for example, a resist film is formed by coating on a substrate such as a silicon wafer, a wafer coated with aluminum, etc.
Heat treatment at a temperature of about 160 ° C (hereinafter “pre-bake”)
That. ), Exposure is performed through a predetermined mask pattern. The radiation used at that time is, for example, an ArF excimer laser (wavelength 193 nm) or a KrF excimer laser (wavelength 2) depending on the type of the acid generator.
X such as deep ultraviolet rays such as 48 nm) and synchrotron radiation
A charged particle beam such as a beam or an electron beam is appropriately selected and used. Exposure conditions such as the amount of exposure are appropriately selected according to the composition of the radiation-sensitive resin composition, the type of each additive, and the like.
In the present invention, in order to stably form a high-precision fine pattern, a temperature of 70 to 160 ° C.
It is preferable to perform a heat treatment (hereinafter, referred to as “post-exposure bake”) for at least two seconds. In this case, if the temperature of the post-exposure bake is lower than 70 ° C., the variation in sensitivity depending on the type of the substrate may be widened.

Thereafter, an alkali developer is used at 10 to 50 ° C.
10 to 200 seconds, preferably 15 to 30 ° C, 15 to 10
A predetermined resist pattern is formed by developing at 0 seconds, particularly preferably at 20 to 25 ° C. and 15 to 90 seconds. Examples of the alkali developer include alkali metal hydroxide, aqueous ammonia, mono-, di- or tri-alkylamines, mono-, di- or tri-amine.
Alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5
-Diazabicyclo- [4.3.0] -5-nonene in an amount of usually 1 to 10% by weight, preferably 1% by weight.
An alkaline aqueous solution dissolved to a concentration of 〜5% by weight, particularly preferably 1-3% by weight, is used. Also,
A water-soluble organic solvent such as methanol or ethanol or a surfactant can be appropriately added to the developer composed of the alkaline aqueous solution. In forming the resist pattern, a protective film may be provided on the resist film in order to prevent the influence of basic impurities and the like contained in the environmental atmosphere.

[0093]

EXAMPLES Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these embodiments.

Examples 1 to 10 and Comparative Example 1 The components shown in Table 1 (parts are based on weight) were mixed to form a homogeneous solution, which was then filtered through a Teflon membrane filter having a pore size of 0.2 μm. Thus, a composition solution was prepared. Next, each composition solution was spin-coated on a silicon wafer, and baked (PB) before exposure at the temperature and time shown in Table 2 to form a resist film having a thickness of 0.5 μm. This resist film is coated with Nikon KrF
Excimer laser irradiation equipment (trade name: NSR-2205)
EX12A) and a KrF excimer laser (wavelength 2).
48 nm) was exposed through a mask pattern while changing the exposure amount. After the exposure, post-exposure bake (PEB) was performed at the temperature and time shown in Table 2. Then, after developing using an aqueous solution of tetramethylammonium hydroxide, the resultant is developed with water for 30 minutes.
After washing for 2 seconds and drying, a resist pattern was formed. Table 3 shows the evaluation results of the examples and the comparative examples.
Here, the measurement of Mw and Mw / Mn and the evaluation of each resist were performed in the following manner.

Mw and Mw / Mn GPC columns (Two G2000H _XL, manufactured by Tosoh Corporation)
G3000H _XL and G4000H _XL ) using gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of flow rate 1.0 ml / min, elution solvent tetrahydrofuran, and column temperature of 40 ° C. It was measured.

Sensitivity Design When a line-and-space pattern (1L1S) having a line width of 0.22 μm is formed, an exposure amount formed in a one-to-one line width is defined as an optimum exposure amount, and the optimum exposure amount is evaluated.
did. When a line-and-space pattern (1L1S) having a resolution design line width of 0.22 μm is formed, the minimum size of a resist pattern (μ
m) was taken as the resolution.

Standing Wave Design When a line and space pattern (1L1S) having a line width of 0.22 μm is formed, the line width between the peaks and valleys of rattling (standing wave) caused by the interference of light formed on the side walls. (Lsw: see FIG. 1) was measured with a scanning electron microscope and evaluated according to the following criteria. 0.02 ≧ Lsw: good 0.02 <Lsw: bad

PED stability A sample exposed at the optimum exposure amount when PEB was performed and developed immediately after exposure was performed by adjusting the ammonia concentration in the atmosphere to 5 ppb.
After leaving for 2 hours in a controlled chamber, PE
B, develop and apply a 0.22μm
When the and space pattern (1L1S) was formed, the line width (Ltop) at the top of the pattern was measured with a scanning electron microscope and evaluated according to the following criteria. 0.22 × 0.85 <Ltop <0.22 × 1.1: good 0.22 × 0.85 ≧ Ltop: poor thinning 0.22 × 1.1 ≦ Ltop: poor fat

Each component used in each of Examples and Comparative Examples was
It is as follows. (A) Copolymer A-1: Copolymer with 4-hydroxystyrene / 2-methyl-2-adamantyl acrylate (copolymerization ratio = 75
/ 25: Mw = 14000) A-2: Copolymer with 4-hydroxystyrene / 2-methyl-2-adamantyl acrylate / styrene (copolymerization ratio = 75/15/10: Mw = 32000) A-3: Copolymer with 4-hydroxystyrene / 2-methyl-2-adamantyl acrylate / pt-butoxystyrene (copolymerization ratio = 70/10/20: Mw = 15
000) A-4: Copolymer with 4-hydroxystyrene / 2-methyl-2-adamantyl acrylate / t-butyl acrylate (copolymerization ratio = 70/10/20: Mw = 130
00) A-5: 4-hydroxystyrene / 2-methyl-2-adamantyl acrylate / pt-butoxystyrene /
Copolymer with 2,5-dimethyl-2,5-hexanediol diacrylate (copolymerization ratio = 80/5/15/3: M
w = 33000) A-6: 4-hydroxystyrene / 2-methyl-2-adamantyl acrylate / t-butyl acrylate /
Copolymer with 2,5-dimethyl-2,5-hexanediol diacrylate (copolymerization ratio = 80/5/15/3: M
w = 31000) A-7: Copolymer with 4-hydroxystyrene / 2-methyl-2-adamantyl acrylate / 4- (1-ethoxyethoxy) styrene (copolymerization ratio = 70/10/2)
0) A-8: Copolymer with 4-hydroxystyrene / styrene / t-butyl acrylate (copolymerization ratio = 60/20)
/ 20: Mw = 13000)

(B) Acid generator B-1: triphenylsulfonium trifluoromethanesulfonate B-2: N- (trifluoromethylsulfonyloxy)
Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide B-3: bis (4-t-butylphenyl) iodonium 10-camphorsulfonate B-4: bis (4-t-butyl Phenyl) iodonium nonafluoro-n-butanesulfonate B-5: bis (1,4-dioxaspiro [4.5] decane-7-sulfonyl) diazomethane

(C) Acid diffusion controller C-1: N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine C-2: 2-phenylbenzimidazole C-3: trioctylamine C- 4: Triethanolamine C-5: 4-Phenylpyridine (D) Solvent D-1: Ethyl lactate D-2: Ethyl-3-ethoxypropionate D-3: Propylene glycol monomethyl ether acetate D-4: Methylamyl Ketone

[0102]

[Table 1]

[0103]

[Table 2]

[0104]

[Table 3]

[0105]

The radiation-sensitive resin composition of the present invention has a composition of PE
The resist pattern does not change the line width or become T-shaped due to D, and is not affected by standing waves due to reflection from the substrate. Therefore, it can be applied to ultra-fine pattern sizes. Provided is a radiation-sensitive resin composition useful as an excellent chemically amplified resist.
Therefore, the radiation-sensitive resin composition of the present invention can be used very suitably as a chemically amplified resist for a semiconductor device, which is expected to be further miniaturized in the future.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a line width between rattle peaks and valleys caused by interference of light formed on side walls of a line and space pattern.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Takeo Shioya 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Corporation (72) Inventor Tsutomu Shimokawa 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR In-house F term (reference) 2H025 AA01 AA02 AA03 AB16 AC04 AC08 AD03 BE07 BE10 BF14 BF15 CB14 CB52 FA12 FA17 4J002 BC121 BG031 EB116 EN136 EQ016 EU046 EV216 EV246 EV256 EV296 EW176 GP03

Claims (1)

[Claims] (A) The following formula (1): Here, R ¹ is a hydrogen atom or a methyl group and R ²
Is an alicyclic alkyl group having 11 or more carbon atoms which has a tertiary carbon atom and is acid-eliminable, and a repeating unit represented by the following formula (2): Wherein R ³ is a hydrogen atom or a methyl group, and a copolymer comprising a repeating unit represented by the formula: and (B) a radiation-sensitive acid generator. object.