JP2007206551A - Positive radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive radiation-sensitive resin composition excellent in line roughness, etching resistance, sensitivity, and resolution and capable of accurately and stably forming a fine pattern as a positive resist material for EB, X-ray or EUV. <P>SOLUTION: The positive radiation-sensitive resin composition is prepared by dissolving a composition containing an acid-dissociable group-containing resin (A) which is alkali-insoluble or slightly alkali-soluble and becomes readily alkali-soluble under the action of an acid and a radiation-sensitive acid generator (B) in a solvent containing an alcohol compound, wherein the acid-dissociable group-containing resin (A) contains a repeating unit (i) and a repeating unit (ii) and the alcohol compound is a 3-20C mono- to tetrahydric saturated alcohol compound having a boiling point of ≥190°C. The repeating unit (i) is represented by a vinylphenol (hydroxystyrene) unit and the repeating unit (ii) is one containing the acid-dissociable group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a radiation sensitive resin composition suitable for fine processing. In particular, the present invention relates to a positive radiation-sensitive resin composition suitable for forming a fine pattern with an electron beam (hereinafter abbreviated as EB), X-rays, or extreme ultraviolet rays (hereinafter abbreviated as EUV).

  In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration of integrated circuits, miniaturization of design rules in lithography is progressing rapidly, and microfabrication is performed stably. The development of lithography processes that can do this is strongly promoted. However, since it is difficult to form a fine pattern of 100 nm or less with high accuracy by the conventional method using KrF or ArF excimer laser, a method using EB or EUV has been proposed.

Various types of radiation-sensitive resin compositions used as such positive resist materials for electron beams or extreme ultraviolet rays used in such ultrafine processing have been proposed.
(1) A methacrylic main chain-cutting radiation sensitive resin composition such as PMMA (polymethyl methacrylate):
Although the resolution is excellent, there are problems in etching resistance and sensitivity, and it is difficult to put it to practical use. Poly t-butyl α-chloromethylstyrene (see Patent Document 1) having a good balance between resolution and sensitivity, and patent application (see Patent Document 2) in which atoms (N, O, S) that are easily cut by an electron beam are introduced at the resin terminal ) Has been. However, although improvement in sensitivity is recognized, sensitivity and etching resistance have not reached a practical level.
(2) Chemically amplified radiation-sensitive resin composition having polyhydroxystyrene resin (resin for KrF excimer) and novolak (resin for i-line) partially protected with an acid-dissociable functional group and an acid generator:
Excellent balance of sensitivity, resolution and etching resistance, partially acetal protected polyhydroxystyrene resin + acid generator (see Patent Document 3), various acid dissociable partially protected polyhydroxystyrene resins + fluorine-containing aromatic sulfonic acid generated onium salt + Fluorine-based or silicon-based surfactant (see Patent Document 4), onium salt having at least one electron-withdrawing group (F, cyano group, nitro group) as a cation moiety substituent (see Patent Document 5), disulfonyl group Various patents have been filed, such as a resin having an N-oxyimide sulfonyl group (see Patent Document 7), and the like. However, the film surface roughness (hereinafter referred to as roughness), sensitivity, and resolution at the time of forming a fine pattern has not reached a practical level.
In particular, when patterning using a KrF excimer laser, if the acid generator exceeds about 20 parts by weight with respect to 100 parts by weight of the acid-dissociable group-containing resin, the sensitivity is improved, but the pattern shape is reduced, There are problems such as deterioration of edge roughness.
In addition, for EB or EUV applications, high sensitivity and high resolution higher than those of a KrF excimer laser are required. Therefore, a chemically amplified radiation sensitive resin composition is a solvent that dissolves these together with a resin component and an acid generator component. The combination with has also become important.
With respect to the solvent, an example of using a C2-C20 divalent to tetravalent alcohol compound having a boiling point of 180 ° C. or higher at normal pressure of 760 mmHg (see Patent Document 8), a solvent having a boiling point of 160 ° C. or higher in the total solvent is 0. Examples containing 1 to 30% by mass (see Patent Document 9) are known.
However, the solvent is also related to compatibility with other components, and considering the high sensitivity and high resolution for EB or EUV applications, the conventional combination is not sufficient.

JP 2000-147777 A JP 11-29612 A JP-A-6-194842 JP 2000-187330 A JP 2001-075283 A JP 2002-072483 A JP 2002-107920 A Japanese Patent No. 3546913 JP 2005-257484 A

  The present invention has been made to address the above problems, and is excellent in nano edge roughness, etching resistance, sensitivity, and resolution for EB, X-ray, and EUV that are effectively sensitive to electron beams or extreme ultraviolet rays. An object of the present invention is to provide a positive-type radiation-sensitive resin composition that can be stably formed with high accuracy.

式（１）において、Ｒは水素原子またはメチル基を表し、Ｒ¹は１価の有機基を表し、ｐは０〜３の整数であり、ｑは１〜３の整数であり、複数存在するＲ¹はそれぞれ相互に同一でも異なっていてもよい。
繰り返し単位（ｉｉ）は、下記式（２−１）、式（２−２）、および式（２−３）で表される繰り返し単位から選ばれる少なくとも１つの繰り返し単位である。

式（２−１）〜式（２−３）において、ＲおよびＲ’はそれぞれ水素原子またはメチル基を表し；式（２−１）において、Ｒ²は１価の有機基（ただし、−ＯＲ³に相当する基を除く）を表し、Ｒ³は１価の酸解離性基を表し、ｓは０〜３の整数であり、ｔは１〜３の整数であり、複数存在するＲ²および複数存在するＲ³はそれぞれ相互に同一でも異なっていてもよく；式（２−２）において、Ｒ⁴は１−エチルシクロペンチル基、１−メチルシクロペンチル基、ｔ−ブチル基または２−メチル−２−アダマンチル基を表し；式（２−３）において、Ｒ⁵は２価の酸解離性基を表す。
また、酸解離性基含有樹脂（Ａ）は、下記式（３）で表される繰り返し単位（ｉｉｉ）をさらに含むことを特徴とする。

式（３）において、Ｒ⁶は１価の有機基（ただし、式（２−１）における−ＯＲ³に相当する基を除く）を表し、ｒは０〜３の整数であり、複数存在するＲ⁶はそれぞれ相互に同一でも異なっていてもよい。 The positive-type radiation-sensitive resin composition of the present invention comprises an acid-dissociable group-containing resin (A) that is alkali-insoluble or alkali-insoluble and easily alkali-soluble by the action of an acid, and a radiation-sensitive acid generator (B ) Is dissolved in a solvent containing an alcohol compound,
The acid-dissociable group-containing resin (A) includes the following repeating unit (i) and repeating unit (ii), and the alcohol compound is 1 to 3 having a boiling point of 190 ° C. or higher and a carbon number of 3 to 20 at normal pressure of 760 mmHg. It is a tetravalent saturated alcohol compound.
The repeating unit (i) is represented by the following formula (1).

In Formula (1), R represents a hydrogen atom or a methyl group, R ¹ represents a monovalent organic group, p is an integer of 0 to 3, q is an integer of 1 to 3, and there are a plurality of them. R ¹ may be the same or different from each other.
The repeating unit (ii) is at least one repeating unit selected from repeating units represented by the following formula (2-1), formula (2-2), and formula (2-3).

In Formula (2-1) to Formula (2-3), R and R ′ each represent a hydrogen atom or a methyl group; in Formula (2-1), R ² represents a monovalent organic group (provided that —OR represents excluded) the corresponding group ^3, R ³ represents a monovalent acid-dissociable group, s is an integer of 0 to 3, t is an integer from 1 to 3, R ² and there are multiple A plurality of R ³ may be the same or different from each other; in the formula (2-2), R ⁴ represents 1-ethylcyclopentyl group, 1-methylcyclopentyl group, t-butyl group or 2-methyl-2. - represents an adamantyl group; in the formula (2-3), R ⁵ represents a divalent acid-dissociable group.
Moreover, acid dissociable group containing resin (A) is characterized by further including the repeating unit (iii) represented by following formula (3).

In the formula (3), R ⁶ represents a monovalent organic group (excluding a group corresponding to —OR ³ in the formula (2-1)), r is an integer of 0 to 3, and there are a plurality of them. R ⁶ may be the same or different from each other.

The C1-C4 monovalent saturated alcohol compound having a boiling point of 190 ° C. or higher and used as a solvent in the positive radiation sensitive resin composition is glycerin, diethylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, 1,3-butane. It is at least one selected from diol, 1,4-butanediol, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether.
The radiation sensitive acid generator (B) contains at least one compound selected from a sulfonimide compound, a disulfonyldiazomethane compound or an onium salt compound.

  When the positive radiation sensitive resin composition of the present invention is patterned using EB, X-rays or EUV, the specific resin component and 1-4 C 1-4 having a boiling point of 190 ° C. or higher. Since it is combined with a valent saturated alcohol compound, it is excellent in nano edge roughness, etching resistance, sensitivity and resolution, and a fine pattern can be formed with high accuracy and stability.

Hereinafter, embodiments of the present invention will be described in detail.
Acid-dissociable group-containing resin (A)
The resin component (A) in the present invention is an alkali-insoluble or alkali-insoluble resin having an acid-dissociable group, and is made of a resin that becomes readily alkali-soluble when the acid-dissociable group is dissociated.
The term “alkali-insoluble or alkali-insoluble” as used herein is employed when a resist pattern is formed from a resist film formed using a radiation-sensitive resin composition containing the acid-dissociable group-containing resin (A). When developing a film using only the acid dissociable group-containing resin (A) instead of the resist film under alkaline development conditions, 50% or more of the initial film thickness of the film remains after development. means.

The acid dissociable group-containing resin (A) is a resin containing the repeating unit (i) and the repeating unit (ii), and may further contain the repeating unit (iii).
The repeating unit (i) is represented by the above formula (1), and R ¹ in this formula (1) represents a monovalent organic group.
Examples of the monovalent organic group include a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a monovalent oxygen atom-containing organic group. Groups, monovalent nitrogen atom-containing organic groups, and the like.
Examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, cyclopentyl, and cyclohexyl. Groups and the like.

  Examples of the monovalent aromatic hydrocarbon group include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, 2,6-xylyl group, 3,5- A xylyl group, a mesityl group, an o-cumenyl group, an m-cumenyl group, a p-cumenyl group, a benzyl group, a phenethyl group, a 1-naphthyl group, a 2-naphthyl group, and the like can be given.

  Examples of the monovalent oxygen atom-containing organic group include, for example, carboxyl group; 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-hydroxybutyl group, 3-hydroxycyclopentyl group, 4-hydroxycyclohexyl group, etc. Or a cyclic hydroxyalkyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyl C1-C8 straight, branched or cyclic such as oxy group A linear alkoxycarbonyloxy group having 2 to 9 carbon atoms such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, and an n-butoxycarbonyloxy group; (1-methoxyethoxy) methyl Group, (1-ethoxyethoxy) methyl group, (1-n-propoxyethoxy) methyl group, (1-n-butoxyethoxy) methyl group, (1-cyclopentyloxyethoxy) methyl group, (1-cyclohexyloxyethoxy) A linear, branched or cyclic (1-alkoxyalkoxy) alkyl group having 3 to 10 carbon atoms such as a methyl group, (1-methoxypropoxy) methyl group, (1-ethoxypropoxy) methyl group; methoxycarbonyloxymethyl Group, ethoxycarbonyloxymethyl group, n-propo 3 to 10 carbon atoms such as a sicarbonyloxymethyl group, i-propoxycarbonyloxymethyl group, n-butoxycarbonyloxymethyl group, t-butoxycarbonyloxymethyl group, cyclopentyloxycarbonyloxymethyl group, cyclohexyloxycarbonyloxymethyl group, etc. And a straight-chain, branched or cyclic alkoxycarbonyloxyalkyl group.

  Examples of the monovalent nitrogen atom-containing organic group include cyano group; cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 1-cyanopropyl group, 2-cyanopropyl group, 3-cyanopropyl group, 1- C2-C9 linear, branched or cyclic cyanoalkyl groups such as cyanobutyl group, 2-cyanobutyl group, 3-cyanobutyl group, 4-cyanobutyl group, 3-cyanocyclopentyl group, 4-cyanocyclohexyl group, etc. Can be mentioned.

In the formula (1), p is an integer of 0 to 3, preferably 0, q is an integer of 1 to 3, preferably 1, and (p + q) is 5 or less. A plurality of R ¹ may be the same or different from each other.

Preferred repeating units (1) in the present invention include, for example, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy -Α-methylstyrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene , 3,4-dihydroxystyrene, 2,4,6-trihydroxystyrene and the like, which are repeating units having a polymerizable unsaturated bond cleaved.
In the resin (A), the repeating unit (1) can be present alone or in combination of two or more.

The repeating unit (ii) is at least one repeating unit selected from the repeating units represented by the above formula (2-1), formula (2-2), and formula (2-3).
In the formula (2-1), R represents a hydrogen atom or a methyl group, and R ² represents a monovalent organic group (excluding a group corresponding to —OR ³ ). Examples of the monovalent organic group include the groups exemplified as R ¹ in the formula (1).
In formula (2-1), examples of R ³ that is a monovalent acid-dissociable group include a substituted methyl group, a 1-branched alkyl group, an alkoxycarbonyl group, and an acyl group.
Examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, (2-methoxyethoxy) methyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, and bromophenacyl group. , Methoxyphenacyl group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group Ethoxybenzyl group, ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, t- Butoxycarbonyl methyl group, and the like.

Examples of the 1-branched alkyl group include i-propyl group, 1-methylpropyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group and the like. be able to.
As said alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, i-propoxycarbonyl group, t-butoxycarbonyl group etc. can be mentioned, for example.
Examples of the acyl group include acetyl, propionyl, butyryl, heptanoyl, hexanoyl, valeryl, pivaloyl, isovaleryl, lauroyl, myristoyl, palmitoyl, stearoyl, oxalyl, malonyl, Succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canphoroyl group, benzoyl Group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isoni Chinoiru group, p- toluenesulfonyl group, and mesyl group.

  Of these monovalent acid dissociable groups, a t-butyl group, a benzyl group, a t-butoxycarbonyl group, a t-butoxycarbonylmethyl group, and the like are preferable.

Preferred repeating units (2-1) in the present invention include, for example, 4-t-butoxystyrene, 4-t-butoxy-α-methylstyrene, 4-t-butoxycarbonyloxystyrene, 4-t-butoxycarbonyloxy. Examples thereof include a repeating unit in which a polymerizable unsaturated bond is cleaved, such as -α-methylstyrene, 4-t-butoxycarbonylstyrene, 4-t-butoxycarbonyl-α-methylstyrene.
In the resin (A), the repeating unit (2-1) can be used alone or in combination of two or more.

As repeating unit (2-2) in the present invention, t-butyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate and 1-ethylcyclopentyl (meth) acrylate, 2-methyl (meth) acrylate And a repeating unit in which a polymerizable unsaturated bond such as -2-adamantyl is cleaved.
In the resin (A), the repeating unit (2-2) may be used alone or in combination of two or more.

In Formula (2-3), R represents a hydrogen atom or a methyl group, and R ⁵ represents a divalent acid dissociable group. Examples of the divalent acid dissociable group include 2,3-dimethyl-2,3-butanediyl group, 2,3-diethyl-2,3-butanediyl group, 2,3-di-n-propyl-2, 3-butanediyl group, 2,3-diphenyl-2,3-butanediyl group, 2,4-dimethyl-2,4-pentanediyl group, 2,4-diethyl-2,4-pentanediyl group, 2,4-di- n-propyl-2,4-pentanediyl group, 2,4-diphenyl-2,4-pentanediyl group, 2,5-dimethyl-2,5-hexanediyl group, 2,5-diethyl-2,5-hexanediyl Group, 2,5-di-n-propyl-2,5-hexanediyl group, 2,5-diphenyl-2,5-hexanediyl group, 2,6-dimethyl-2,6-heptanediyl group, 2,6 -Diethyl-2,6-heptanedi Group, 2,6-di-n-propyl-2,6-heptanediyl group, 2,6-diphenyl-2,6-heptanediyl group, 2,4-dimethyl-3- (2-hydroxypropyl-2,4- Pentanediyl group, 2,4-diethyl-3- (2-hydroxypropyl) -2,4-pentanediyl group, 2,5-dimethyl-3- (2-hydroxypropyl) -2,5-hexanediyl group, 2, 5-diethyl-3- (2-hydroxypropyl) -2,5-hexanediyl group, 2,4-dimethyl-3,3-di (2-hydroxypropyl) -2,4-pentanediyl group, 2,4- Diethyl-3,3-di (2-hydroxypropyl) -2,4-pentanediyl group, 2,5-dimethyl-3,4-di (2-hydroxypropyl) -2,5-hexanediyl group, 2,5 -Diechi 3,4-di (2-hydroxypropyl) -2,4-hexanediyl group, and a 2,7-dimethyl-2,7-Okutanjiru group.

Moreover, the functional group shown below can be mentioned.

樹脂（Ａ）において、繰り返し単位（２−３）は、単独でまたは２種以上が存在することができる。 As the repeating unit (2-3) in the present invention, preferred examples of the monomer (ii) include 2,5-dimethylhexane-2,5-diacrylate, 2,6-dimethylheptane-2,6- Examples thereof include a repeating unit in which a polymerizable unsaturated bond is cleaved, such as diacrylate and 2,7-dimethyloctane-2,7-diacrylate.
A compound having the following structure is also preferred.

In the resin (A), the repeating unit (2-3) can be present alone or in combination of two or more.

The acid dissociable group-containing resin (A) can contain the repeating unit (iii) represented by the above formula (3) together with the repeating unit (i) and the repeating unit (ii).
In the formula (3), R ⁶ represents a monovalent organic group (excluding a group corresponding to —OR ³ in the formula (2-1)).
Examples of the monovalent organic group include the same organic groups as those for R ¹ . R is an integer of 0 to 3, preferably r is 0.

Examples of the repeating unit (3) in the present invention include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, and the like. And a unit in which the polymerizable unsaturated bond of the vinyl aromatic compound is cleaved.
In the resin (A), the repeating unit (3) can be present alone or in combination of two or more.

  The resin of the present invention can contain other repeating units. Other repeating units include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) 2-methylpropyl acrylate, 1-methylpropyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2- (meth) acrylic acid 2- Ethylhexyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-n-propyl (meth) acrylate, 3-hydroxy-n-propyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic acid Benzyl, 1-methyladamantyl (meth) acrylate, 1-ethyladamantyl (meth) acrylate, (meth) 8-methyl-8-tricyclodecyl crylate, 8-ethyl-8-tricyclodecyl (meth) acrylate, 3-methyl-3-tetracyclododecenyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as 3-ethyl-3-tetracyclododecenyl and 2,5-dimethylhexane-2,5-di (meth) acrylate;

Unsaturated carboxylic acids (anhydrides) such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, cinnamic acid; 2-carboxyethyl (meth) acrylate, (meth) acrylic acid 2 -Carboxyalkyl esters of unsaturated carboxylic acids such as carboxy-n-propyl and (meth) acrylic acid 3-carboxy-n-propyl; (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, etc. Unsaturated nitrile compounds; unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide and fumaramide; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide Compound; N-vinyl-ε-cap Units in which a polymerizable unsaturated bond such as loractam, N-vinylpyrrolidone, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, 4-vinylimidazole, or other nitrogen-containing vinyl compounds is cleaved Can be mentioned.
In the resin (A), other repeating units may be present alone or in combination of two or more.

  Particularly preferable resins (A) in the present invention include, for example, 4-hydroxystyrene / 4-t-butoxystyrene copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / acrylic acid 1-methylcyclopentyl copolymer. 4-hydroxystyrene / 4-t-butoxystyrene / 1-ethylcyclopentyl acrylate copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / styrene copolymer, 4-hydroxystyrene / t-butyl acrylate / Styrene copolymer, 4-hydroxystyrene / 1-methylcyclopentyl acrylate / styrene copolymer, 4-hydroxystyrene / 1-ethylcyclopentyl acrylate / styrene copolymer, 4-hydroxystyrene / 4-t-butoxy Styrene / 2,5-dimethylhexane-2 5-diacrylate copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / 2,5-dimethylhexane-2,5-diacrylate / styrene copolymer, 4-hydroxystyrene / 2-methyl acrylate 2-adamantyl copolymer, 4-hydroxystyrene / t-butyl acrylate / 2,5-dimethylhexane-2,5-diacrylate / styrene copolymer, 4-hydroxystyrene / t-butyl acrylate / 2, Examples thereof include 5-dimethylhexane-2,5-diacrylate copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / t-butyl acrylate copolymer, and the like.

  In the acid dissociable group-containing resin (A), the acid dissociable group introduction rate (acid dissociation property relative to the total number of unprotected acidic functional groups and acid dissociable groups in the acid dissociable group-containing resin (A)) The ratio of the number of groups) cannot be defined unconditionally depending on the acid-dissociable group or the type of resin into which the group is introduced, but is preferably 10 to 100%, more preferably 15 to 100%.

In the resin (A), the proportion of the repeating unit (i) is 60 to 80 mol%, preferably 65 to 75 mol%, and the proportion of the repeating unit (ii) is 15 to 40 with respect to all repeating units. The proportion of the repeating unit (iii) is 1 to 30 mol%, preferably 5 to 25 mol%.
The content of other repeating units is usually 25 mol% or less, preferably 10 mol% or less.
If the content of the repeating unit (i) is less than 60 mol%, the adhesion of the resist pattern to the substrate tends to be reduced, whereas if it exceeds 80 mol%, the contrast after development tends to be reduced.
If the content of the repeating unit (ii) is less than 15 mol%, the resolution tends to be lowered, whereas if it exceeds 40 mol%, the adhesion of the resist pattern to the substrate tends to be lowered, and the repeating unit (iii) ) Content of less than 1 mol%, the etching resistance tends to decrease, whereas when it exceeds 30 mol%, the resolution tends to decrease.
If the other repeating unit exceeds 25 mol%, the resolution tends to decrease.

The polystyrene-reduced weight molecular weight (hereinafter referred to as “Mw”) of the acid-dissociable group-containing resin (A) measured by gel permeation chromatography (GPC) is preferably 1,000 to 150,000, more preferably 3,000. ˜100,000, more preferably 5,000 to 30,000.
Further, the ratio (Mw / Mn) of Mw of the acid-dissociable group-containing resin (A) and polystyrene-reduced number molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC) is usually 1 -10, preferably 1-5.
In this invention, acid dissociable group containing resin (A) can be used individually or in mixture of 2 or more types.

式（４）において、Ｒ⁷はアルキレン基、アリーレン基、アルコキシレン基等の２価の基を表し、Ｒ⁸はアルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を表す。 Radiation sensitive acid generator (B)
The radiation-sensitive acid generator (B) in the present invention contains at least one compound selected from a sulfonimide compound, a disulfonyldiazomethane compound or an onium salt compound as an essential component, and generates a radiation-sensitive acid that generates an acid upon exposure. Agent (hereinafter referred to as “acid generator (B)”).
As said sulfonimide compound, the compound represented by following formula (4) can be mentioned, for example.

In the formula (4), R ⁷ represents a divalent group such as an alkylene group, an arylene group, or an alkoxylen group, and R ⁸ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group. Represents a group.

As a specific example of the sulfonimide compound,
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- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10- Camphorsulfonyloxy) succinimide, N- (10-camphors) Phonyloxy) 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- (10-camphorsulfonyloxy) naphthylimide, N-[(5-methyl-5-carboxymethylbicyclo [2.2.1] heptane-2 -Yl) sulfonyloxy] succinimide,

N- (n-octylsulfonyloxy) succinimide, N- (n-octylsulfonyloxy) phthalimide, N- (n-octylsulfonyloxy) diphenylmaleimide, N- (n-octylsulfonyloxy) bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (n-octylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (n-octylsulfonyloxy) naphthylimide, N- (4- Methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4 Methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6- Oxy-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) naphthylimide,

N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoro Methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide N- (2-trifluoromethylphenylsulfonyloxy) naphthylimi N- (4-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-trifluoromethylphenylsulfonyloxy) phthalimide, N- (4-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-tri Fluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide, N- (4-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxy Imido, N- (4-trifluoromethylphenylsulfonyloxy) naphthyl Bromide,

N- (perfluorophenylsulfonyloxy) succinimide, N- (perfluorophenylsulfonyloxy) phthalimide, N- (perfluorophenylsulfonyloxy) diphenylmaleimide, N- (perfluorophenylsulfonyloxy) bicyclo [2.2.1] ] Hept-5-ene-2,3-dicarboximide, N- (perfluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (perfluorophenylsulfonyloxy) naphthylimide, N- (1- Naphthylsulfonyloxy) succinimide, N- (1-naphtho) Rusulfonyloxy) phthalimide, N- (1-naphthylsulfonyloxy) diphenylmaleimide, N- (1-naphthylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N -(1-naphthylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthylsulfonyloxy) bicyclo [2.2.1 ] Heptane-5,6-oxy-2,3-dicarboximide, N- (1-naphthylsulfonyloxy) naphthylimide,

N- (nonafluoro-n-butylsulfonyloxy) succinimide, N- (nonafluoro-n-butylsulfonyloxy) phthalimide, N- (nonafluoro-n-butylsulfonyloxy) diphenylmaleimide, N- (nonafluoro-n-butylsulfonyloxy) ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 Ene-2,3-dicarboximide, N- (nonafluoro-n-butylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (nonafluoro- n-butylsulfonyloxy) naphthylimide, N- (perfluoro-n-octylsulfo) Ruoxy) succinimide, N- (perfluoro-n-octylsulfonyloxy) phthalimide, N- (perfluoro-n-octylsulfonyloxy) diphenylmaleimide, N- (perfluoro-n-octylsulfonyloxy) bicyclo [2.2 .1] Hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (perfluoro-n-octylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (perfluoro-n-octyl) Sulfonyloxy) naphthylimide,

N- (phenylsulfonyloxy) succinimide, N- (phenylsulfonyloxy) phthalimide, N- (phenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (phenylsulfonyloxy) bicyclo [2 2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (phenylsulfonyloxy) naphthylimide and the like.

Among these sulfonimide compounds, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (nonafluoro-n-butylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (phenylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-[(5-methyl-5-carboxymethylbicyclo [2.2.1] heptan-2-yl) Sulfonyloxy] succinimide is preferred.
In this invention, a sulfonimide compound can be used individually or in mixture of 2 or more types.

式（５）において、各Ｒ⁹は相互に独立にアルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を表す。 As said disulfonyl diazomethane compound, the compound represented by following formula (5) can be mentioned, for example.

In the formula (5), each R ⁹ independently represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

Specific examples of the disulfonyldiazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, and bis (2,4-dimethyl). Phenylsulfonyl) diazomethane, bis (4-t-butylphenylsulfonyl) diazomethane, bis (4-t-butylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, (methylsulfonyl) 4-methylphenylsulfonyldiazomethane, (cyclohexyl) Sulfonyl) 4-methylphenylsulfonyldiazomethane, (cyclohexylsulfonyl) 1,1-dimethylethylsulfonyldiazomethane, bis (1,1-dimethyl) Ethylsulfonyl) 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.
Among these disulfonyldiazomethane compounds, bis (cyclohexylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8- Sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] undecan-7-sulfonyl) diazomethane, and bis (4-t-butylsulfonyl) diazomethane are preferred.
In the present invention, the disulfonyldiazomethane compounds can be used alone or in admixture of two or more.

Examples of the onium salt compounds include sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts, and the like.
Specific examples of the onium salt compounds include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium pyrenesulfonate, triphenylsulfonium n-dodecyl. Benzenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfoniumbenzenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium n-octanesulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-tri Fluoromethylbenzenesulfonate, triphenyl Rufonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium perfluorobenzenesulfonate, (4-t-butylphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-t-butylphenyl) diphenylsulfonium nonafluoro-n- Butanesulfonate, (4-t-butylphenyl) diphenylsulfonium perfluoro-n-octanesulfonate, (4-t-butylphenyl) diphenylsulfonium pyrenesulfonate, (4-t-butylphenyl) diphenylsulfonium n-dodecylbenzenesulfonate, (4-t-butylphenyl) diphenylsulfonium p-toluenesulfonate, (4-t-butylphenyl) diphenylsulfate Nitrobenzenesulfonate, (4-tert-butylphenyl) diphenylsulfonium 10-camphorsulfonate, (4-tert-butylphenyl) diphenylsulfonium n-octanesulfonate, (4-tert-butylphenyl) diphenylsulfonium 2-trifluoromethylbenzene Sulfonate, (4-t-butylphenyl) diphenylsulfonium 4-trifluoromethanebenzene sulfonate, (4-t-butylphenyl) diphenylsulfonium perfluorobenzene sulfonate,

(4-t-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium perfluoro-n-octanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium pyrenesulfonate, (4-t-butoxyphenyl) diphenylsulfonium n-dodecylbenzenesulfonate, (4-t-butoxyphenyl) diphenylsulfonium p-toluenesulfonate, (4-t-butoxy Phenyl) diphenylsulfonium benzenesulfonate, (4-t-butoxyphenyl) diphenylsulfonium 10-camphorsulfonate, (4-t-butoxypheny ) Diphenylsulfonium n-octanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium 2-trifluoromethylbenzenesulfonate, (4-t-butoxyphenyl) diphenylsulfonium 4-trifluoromethylbenzenesulfonate, (4-t-butoxy) Phenyl) diphenylsulfonium perfluorobenzenesulfonate, (4-hydroxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-hydroxyphenyl) diphenylsulfonium perfluoro-n- Octanesulfonate, (4-hydroxyphenyl) diphenylsulfonium pyrenesulfonate, (4-hydroxyphene L) Diphenylsulfonium n-dodecylbenzenesulfonate, (4-hydroxyphenyl) diphenylsulfonium p-toluenesulfonate, (4-hydroxyphenyl) diphenylsulfoniumbenzenesulfonate, (4-hydroxyphenyl) diphenylsulfonium 10-camphorsulfonate, (4- Hydroxyphenyl) diphenylsulfonium n-octanesulfonate, (4-hydroxyphenyl) diphenylsulfonium 2-trifluoromethylbenzenesulfonate, (4-hydroxyphenyl) diphenylsulfonium 4-trifluoromethylbenzenesulfonate, (4-hydroxyphenyl) diphenylsulfonium Perfluorobenzenesulfonate,

Tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium nonafluoro-n-butanesulfonate, tris (4-methoxyphenyl) sulfonium perfluoro-n-octanesulfonate, tris (4-methoxyphenyl) ) Sulfonium pyrenesulfonate, tris (4-methoxyphenyl) sulfonium n-dodecylbenzenesulfonate, tris (4-methoxyphenyl) sulfonium p-toluenesulfonate, tris (4-methoxyphenyl) sulfoniumbenzenesulfonate, tris (4-methoxyphenyl) Sulfonium 10-camphorsulfonate, tris (4-methoxyphenyl) sulfonium n-octanesulfonate, tris (4-methoxy) Enyl) sulfonium 2-trifluoromethylbenzenesulfonate, tris (4-methoxyphenyl) sulfonium 4-trifluoromethylbenzenesulfonate, tris (4-methoxyphenyl) sulfonium perfluorobenzenesulfonate, bis (4-methoxyphenyl) p-toluyl Sulfonium trifluoromethanesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium nonafluoro-n-butanesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium perfluoro-n-octanesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium pyrenesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium n-dodecylbenzenesulfonate, bis (4-methoate) Ciphenyl) p-toluylsulfonium p-toluenesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium benzenesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium 10-camphorsulfonate, bis (4-methoxyphenyl) p- Toluylsulfonium n-octanesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium 2-trifluoromethylbenzenesulfonate, bis (4-methoxyphenyl) p-toluylsulfonium 4-trifluoromethylbenzenesulfonate, bis (4-methoxy Phenyl) p-toluylsulfonium perfluorobenzenesulfonate,

(4-fluorophenyl) diphenylsulfonium trifluoromethanesulfonate, (4-fluorophenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) diphenylsulfonium 10-camphor sulfonate, tris (4-fluorophenyl) sulfonium trifluoro Lomethanesulfonate, tris (4-fluorophenyl) sulfonium nonafluoro-n-butanesulfonate, tris (4-fluorophenyl) sulfonium 10-camphor sulfonate, tris (4-fluorophenyl) sulfonium p-toluenesulfonate, 2,4 , 6-Trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfoniu 2,4-difluoro benzenesulfonate, 2,4,6-trimethylphenyl sulfonium p- toluenesulfonate,

Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium n-dodecylbenzenesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodoniumbenzenesulfonate Diphenyliodonium 10-camphorsulfonate, diphenyliodonium n-octanesulfonate, diphenyliodonium 2-trifluoromethylbenzenesulfonate, diphenyliodonium 4-trifluoromethylbenzenesulfonate, diphenyliodonium perfluorobenzenesulfonate, bis (4-me Ruphenyl) iodonium trifluoromethanesulfonate, bis (4-methylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-methylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-methylphenyl) iodonium pyrenesulfonate, Bis (4-methylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-methylphenyl) iodonium p-toluenesulfonate, bis (4-methylphenyl) iodoniumbenzenesulfonate, bis (4-methylphenyl) iodonium 10-camphorsulfonate Bis (4-methylphenyl) iodonium n-octanesulfonate, bis (4-methylphenyl) iodonium 2-trifluoromethylbenzene Sulfonates, bis (4-methylphenyl) iodonium 4-trifluoromethyl benzenesulfonate, bis (4-methylphenyl) iodonium perfluoro sulfonate,

Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-t-butylphenyl) iodonium pyrenesulfonate, bis (4-t-butylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, bis (4-t- Butylphenyl) iodonium benzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium n-octanesulfonate, bis (4-t-butyl) Enyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium perfluorobenzenesulfonate, bis (4-t- Butylphenyl) iodonium 2,4-difluorobenzenesulfonate, bis (3,4-dimethylphenyl) iodonium trifluoromethanesulfonate, bis (3,4-dimethylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (3,4 Dimethylphenyl) iodonium perfluoro-n-octanesulfonate, bis (3,4-dimethylphenyl) iodonium pyrenesulfonate, bis (3,4-dimethylphenyl) iodonium n-do Silbenzene sulfonate, bis (3,4-dimethylphenyl) iodonium p-toluenesulfonate, bis (3,4-dimethylphenyl) iodonium benzenesulfonate, bis (3,4-dimethylphenyl) iodonium 10-camphorsulfonate, bis (3 , 4-Dimethylphenyl) iodonium n-octanesulfonate, bis (3,4-dimethylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (3,4-dimethylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis ( 3,4-dimethylphenyl) iodonium perfluorobenzenesulfonate,

(4-nitrophenyl) phenyliodonium trifluoromethanesulfonate, (4-nitrophenyl) phenyliodonium nonafluoro-n-butanesulfonate, (4-nitrophenyl) phenyliodonium perfluoro-n-octanesulfonate, (4-nitrophenyl) Phenyliodonium pyrenesulfonate, (4-nitrophenyl) phenyliodonium n-dodecylbenzenesulfonate, (4-nitrophenyl) phenyliodonium p-toluenesulfonate, (4-nitrophenyl) phenyliodoniumbenzenesulfonate, (4-nitrophenyl) phenyl Iodonium 10-camphorsulfonate, (4-nitrophenyl) phenyliodonium n-octanesulfonate, (4-nitrophenyl) Phenyliodonium 2-trifluoromethylbenzenesulfonate, (4-nitrophenyl) phenyliodonium 4-trifluoromethylbenzenesulfonate, (4-nitrophenyl) phenyliodonium perfluorobenzenesulfonate, bis (3-nitrophenyl) iodonium trifluoromethanesulfonate Bis (3-nitrophenyl) iodonium nonafluoro-n-butanesulfonate, bis (3-nitrophenyl) iodonium perfluoro-n-octanesulfonate, bis (3-nitrophenyl) iodonium pyrenesulfonate, bis (3-nitrophenyl) ) Iodonium n-dodecylbenzenesulfonate, bis (3-nitrophenyl) iodonium p-toluenesulfonate, bis (3-nitrofe) L) iodonium benzene sulfonate, bis (3-nitrophenyl) iodonium 10-camphor sulfonate, bis (3-nitrophenyl) iodonium n-octane sulfonate, bis (3-nitrophenyl) iodonium 2-trifluoromethylbenzene sulfonate, bis ( 3-nitrophenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (3-nitrophenyl) iodonium perfluorobenzenesulfonate,

(4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, (4-methoxyphenyl) phenyliodonium nonafluoro-n-butanesulfonate, (4-methoxyphenyl) phenyliodonium perfluoro-n-octanesulfonate, (4-methoxyphenyl) Phenyliodonium pyrenesulfonate, (4-methoxyphenyl) phenyliodonium n-dodecylbenzenesulfonate, (4-methoxyphenyl) phenyliodonium p-toluenesulfonate, (4-methoxyphenyl) phenyliodoniumbenzenesulfonate, (4-methoxyphenyl) phenyl Iodonium 10-camphorsulfonate, (4-methoxyphenyl) phenyliodonium n-octanesulfonate, ( -Methoxyphenyl) phenyliodonium 2-trifluoromethylbenzenesulfonate, (4-methoxyphenyl) phenyliodonium 4-trifluoromethylbenzenesulfonate, (4-methoxyphenyl) phenyliodonium perfluorobenzenesulfonate, (4-fluorophenyl) phenyl Iodonium trifluoromethanesulfonate, (4-fluorophenyl) phenyliodonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) phenyliodonium 10-camphorsulfonate,

Bis (4-fluorophenyl) iodonium trifluoromethanesulfonate, bis (4-fluorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-fluorophenyl) iodonium 10-camphorsulfonate, bis (4-chlorophenyl) iodonium trifluoromethane Sulfonate, bis (4-chlorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-chlorophenyl) iodonium perfluoro-n-octanesulfonate, bis (4-chlorophenyl) iodonium pyrenesulfonate, bis (4-chlorophenyl) iodonium n -Dodecylbenzenesulfonate, bis (4-chlorophenyl) iodonium p-toluenesulfonate, bis (4-chlorophenyl) iodo Donium benzene sulfonate, bis (4-chlorophenyl) iodonium 10-camphor sulfonate, bis (4-chlorophenyl) iodonium n-octane sulfonate, bis (4-chlorophenyl) iodonium 2-trifluoromethylbenzene sulfonate, bis (4-chlorophenyl) Iodonium 4-trifluoromethylbenzenesulfonate, bis (4-chlorophenyl) iodonium perfluorobenzenesulfonate,

Bis (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, bis (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-trifluoromethylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-trifluoromethylphenyl) iodonium pyrenesulfonate, bis (4-trifluoromethylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, bis (4-trifluoro Methylphenyl) iodonium benzenesulfonate, bis (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate, bis (4-trifluoromethyl) Ruphenyl) iodonium n-octanesulfonate, bis (4-trifluoromethylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-trifluoromethylphenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (4-trifluoro Methylphenyl) iodonium perfluorobenzenesulfonate, bis (1-naphthyl) iodonium trifluoromethanesulfonate, bis (1-naphthyl) iodonium nonafluoro-n-butanesulfonate, bis (1-naphthyl) iodonium perfluoro-n-octanesulfonate, Bis (1-naphthyl) iodonium pyrenesulfonate, bis (1-naphthyl) iodonium n-dodecylbenzenesulfonate, bis (1-naphthyl) Iodonium p-toluenesulfonate, bis (1-naphthyl) iodoniumbenzenesulfonate, bis (1-naphthyl) iodonium 10-camphorsulfonate, bis (1-naphthyl) iodonium n-octanesulfonate, bis (1-naphthyl) iodonium 2-tri Fluoromethylbenzenesulfonate, bis (1-naphthyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (1-naphthyl) iodonium perfluorobenzenesulfonate, and the like can be given.

  Among these onium salt compounds, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium 10- Camphorsulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-trifluorobenzenesulfonate, triphenylsulfonium 2,4-difluoromethylbenzenesulfonate, tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris ( 4-methoxyphenyl) sulfonium nonafluoro-n-butanesulfone , Tris (4-methoxyphenyl) sulfonium 10-camphorsulfonate,

(4-fluorophenyl) diphenylsulfonium trifluoromethanesulfonate, (4-fluorophenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) diphenylsulfonium 10-camphor sulfonate, tris (4-fluorophenyl) sulfonium trifluoro Lomethanesulfonate, tris (4-fluorophenyl) sulfonium nonafluoro-n-butanesulfonate, tris (4-fluorophenyl) sulfonium 10-camphorsulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 2,4, 6-trimethylphenyldiphenylsulfonium p-toluenesulfonate, 2,4,6-trimethylphenyldiphenyl Sulfonium 2,4-difluoro benzenesulfonate,

Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 10-camphorsulfonate, di (p-toluyl) iodonium trifluoromethanesulfonate, di (p-toluyl) ) Iodonium nonafluoro-n-butanesulfonate, di (p-toluyl) iodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n -Butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t- Tilphenyl) iodonium p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium 10-camphorsulfonate, bis (4-tert-butylphenyl) iodonium 2-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) Iodonium 4-trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium 2,4-difluorobenzenesulfonate,

(4-fluorophenyl) phenyliodonium trifluoromethanesulfonate, (4-fluorophenyl) phenyliodonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) phenyliodonium 10-camphorsulfonate, bis (4-fluorophenyl) iodonium trifluoro Lomethanesulfonate, bis (4-fluorophenyl) iodonium nonafluoro-n-butanesulfonate, and bis (4-fluorophenyl) iodonium 10-camphorsulfonate are preferred.
In this invention, an onium salt compound can be used individually or in mixture of 2 or more types.

In the present invention, as the acid generator (B), a radiation sensitive acid generator other than the sulfonimide compound, the disulfonyldiazomethane compound or the onium salt compound (hereinafter referred to as “other acid generator”) is used in combination. You can also.
Examples of other acid generators include sulfone compounds, sulfonate ester compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, and the like.
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.
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Specific examples of the sulfonate compound include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), pyrogallol tris (nonafluoro-n-butanesulfonate), pyrogallol tris (methanesulfonate), nitrobenzyl-9,10-diethoxyanthracene. -2-sulfonate, α-methylol benzoin tosylate, α-methylol benzoin trifluoromethane sulfonate, α-methylol benzoin n-octane sulfonate, α-methylol benzoin n-dodecane sulfonate, and the like.

式（６）において、各Ｒ¹⁰は相互に独立に直鎖状もしくは分岐状の１価の脂肪族炭化水素基、シクロアルキル基、アリール基、アラルキル基またはヘテロ原子を有する他の１価の有機基を表し、ＶおよびＷは相互に独立に、アリール基、水素原子、直鎖状もしくは分岐状の１価の脂肪族炭化水素基またはヘテロ原子を有する他の１価の有機基を表し、かつＶおよびＷの少なくとも一方がアリール基であるか、あるいはＶとＷが相互に連結して少なくとも１個の不飽和結合を有する炭素単環構造または炭素多環構造を形成しているか、あるいはＶとＷが相互に連結して下記式で表される基を形成している。

ただし、Ｖ'およびＷ'は相互に独立に、かつ複数存在するＶ'およびＷ'はそれぞれ同一でも異なってもよく、水素原子、ハロゲン原子、直鎖状もしくは分岐状のアルキル基、シクロアルキル基、アリール基またはアラルキル基を表すか、あるいは同一のもしくは異なる炭素原子に結合したＶ'とＷ'が相互に連結して炭素単環構造を形成しており、ｒは２〜１０の整数である。 As said disulfonylmethane compound, the compound represented by following formula (6) can be mentioned, for example.

In the formula (6), each R ¹⁰ is independently a linear or branched monovalent aliphatic hydrocarbon group, cycloalkyl group, aryl group, aralkyl group, or other monovalent organic having a hetero atom. V and W each independently represent an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group or other monovalent organic group having a hetero atom, and At least one of V and W is an aryl group, or V and W are connected to each other to form a carbon monocyclic structure or a carbon polycyclic structure having at least one unsaturated bond; W are connected to each other to form a group represented by the following formula.

However, V ′ and W ′ are independent from each other, and a plurality of V ′ and W ′ may be the same or different and each represents a hydrogen atom, a halogen atom, a linear or branched alkyl group, or a cycloalkyl group. Represents 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 r is an integer of 2 to 10. .

式（７−１）および式（７−２）において、各Ｒ¹¹および各Ｒ¹²は相互に独立に１価の有機基を表す。
式（７−１）および式（７−２）において、Ｒ¹¹の好ましい具体例としては、メチル基、エチル基、ｎ―プロピル基、フェニル基、トシル基、トリフルオロメチル基、ペンタフルオロエチル基等を挙げることができ、またＲ¹²の好ましい具体例としては、フェニル基、トシル基、１−ナフチル基等を挙げることができる。 Examples of the oxime sulfonate compound include compounds represented by the following formula (7-1) or formula (7-2).

In Formula (7-1) and Formula (7-2), each R ¹¹ and each R ¹² independently represent a monovalent organic group.
In formula (7-1) and formula (7-2), preferred specific examples of R ¹¹ are methyl group, ethyl group, n-propyl group, phenyl group, tosyl group, trifluoromethyl group, pentafluoroethyl group. In addition, preferred specific examples of R ¹² include a phenyl group, a tosyl group, and a 1-naphthyl group.

  Specific examples of the hydrazine sulfonate compound include bis (phenylsulfonyl) hydrazine, bis (4-methylphenylsulfonyl) hydrazine, bis (trifluoromethylsulfonyl) hydrazine, bis (pentafluoroethylsulfonyl) hydrazine, and bis (n-propyl). Sulfonyl) hydrazine, phenylsulfonylhydrazine, 4-methylphenylsulfonylhydrazine, trifluoromethylsulfonylhydrazine, pentafluoroethylsulfonylhydrazine, n-propylsulfonylhydrazine, (trifluoromethylsulfonyl) 4-methylphenylsulfonylhydrazine, and the like. it can.

In the present invention, the amount of the acid generator (B) used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight per 100 parts by weight of the acid dissociable group-containing resin (A). is there. In this case, if the amount of the acid generator (B) used is less than the predetermined range, the sensitivity and developability tend to be lowered, while if it is more than the predetermined range, the pattern shape, heat resistance and the like tend to be lowered.
Moreover, the usage-amount of another acid generator is 30 weight% or less normally with respect to the whole quantity of an acid generator (B), Preferably it is 10 weight% or less. In this case, if the use ratio of the other acid generator is larger than the predetermined value, the intended effect of the present invention may be impaired.

式（８）において、各Ｒ¹³は相互に独立に水素原子、アルキル基、アリール基またはアラルキル基を表し、これらの各基は置換されてもよい。 The positive-type radiation-sensitive resin composition of the present invention has an effect of controlling the diffusion phenomenon in the resist film of the acid generated from the acid generator (B) by exposure and suppressing undesirable chemical reaction in the non-exposed area. It is preferable to add an acid diffusion control agent.
By using such an acid diffusion control agent, the storage stability of the composition is further improved, the resolution of the resist is improved, and the change in the line width of the resist pattern due to fluctuations in PED can be suppressed. It is extremely excellent in stability.
As the acid diffusion controller, a nitrogen-containing organic compound whose basicity is not changed by exposure or heat treatment in the resist pattern forming step is preferable.
As such a nitrogen-containing organic compound, for example, a compound represented by the following formula (8) (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)”), diamino polymer having 3 or more nitrogen atoms (hereinafter referred to as “nitrogen-containing compound (iii)”), amide group-containing compound, urea compound, nitrogen-containing complex. Examples thereof include a ring compound and a (co) polymer of N, N-dimethylacrylamide.

In the formula (8), each R ¹³ independently represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and each of these groups may be substituted.

  Examples of the nitrogen-containing compound (i) include linear, branched or cyclic monoalkylamines 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, methyl Linear, branched or cyclic dialkylamines such as cyclohexylamine and dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri -N-heptylamine, tri-n-octylamine, tri-n-nonylamine Linear, branched or cyclic trialkylamines such as tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, and tricyclohexylamine; linear, branched or cyclic such as ethanolamine, diethanolamine, and triethanolamine Cyclic alkanolamines; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, 1-naphthylamine, etc. And aromatic amines.

Examples of the nitrogen-containing compound (ii) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, tetramethylenediamine, Hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2′-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- ( 4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene Zen, 1,3-bis can be mentioned [1- (4-aminophenyl) -1-methylethyl] benzene, and the like.
Examples of the nitrogen-containing compound (iii) include polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide (co) polymer, and the like.

Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. 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, tributylthiourea and the like. be able to.
Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, and 2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-methyl Such as pyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, acridine, etc. In addition to pyridines, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, etc. To list It can be.
Examples of the (co) polymer of N, N-dimethylacrylamide include, for example, 4-hydroxystyrene / 4-t-butoxystyrene / N, N-dimethylacrylamide copolymer, 4-hydroxystyrene / 4-t-butoxy. Examples thereof include styrene / styrene / N, N-dimethylacrylamide copolymer.

  Further, as a nitrogen-containing organic compound that acts as an acid diffusion controller, a base precursor having an acid dissociable group such as N- (t-butoxycarbonyl) piperidine, N- (t-butoxycarbonyl) imidazole, N- ( t-butoxycarbonyl) benzimidazole, N- (t-butoxycarbonyl) -2-phenylbenzimidazole, N- (t-butoxycarbonyl) di-n-octylamine, N- (t-butoxycarbonyl) diethanolamine, N- (T-Butoxycarbonyl) dicyclohexylamine, N- (t-butoxycarbonyl) diphenylamine and the like can be used.

Of these nitrogen-containing organic compounds, nitrogen-containing compounds (i), nitrogen-containing heterocyclic compounds, (co) polymers of N, N-dimethylacrylamide, base precursors having acid dissociable groups, and the like are preferable.
The acid diffusion controller can be used alone or in admixture of two or more.
The compounding amount of the acid diffusion controller is usually 15 parts by weight or less, preferably 0.001 to 10 parts by weight, particularly preferably 0.005 to 5 parts by weight per 100 parts by weight of the acid dissociable group-containing resin (A). It is. In this case, when the compounding amount of the acid diffusion controller is larger than a predetermined value, the sensitivity as a resist and the developability of the exposed portion tend to be lowered. In addition, if the compounding quantity of an acid diffusion control agent is less than 0.001 weight part, there exists a possibility that the pattern shape and dimension fidelity as a resist may fall depending on process conditions.

In the positive radiation sensitive resin composition of the present invention, a surfactant exhibiting an effect of improving the coating property and striation of the composition, the developing property as a resist, and the like can be blended.
Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenol ether, polyoxyethylene n-nonylphenol ether, polyethylene glycol dilaurate, polyethylene Glycol distearate and the like can be mentioned, and as commercial products, for example, Ftop EF301, EF303, EF352 (above, manufactured by Tochem Products), Megafax F171, F173 (above) Dainippon Ink & Chemicals, Inc.), Florad FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, C102, the SC103, the SC104, the SC105, the 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.).
These surfactants can be used alone or in admixture of two or more.
The compounding amount of the surfactant is usually 2 parts by weight or less per 100 parts by weight of the acid dissociable group-containing resin (A).

Solvent The positive radiation sensitive resin composition of the present invention is prepared as a composition solution by, for example, being uniformly dissolved in a solvent and then filtered through a filter having a pore diameter of about 200 nm.
The solvent used for the preparation of the composition solution contains an alcohol compound as an essential component, and the alcohol compound is a 1 to 4 valent saturated alcohol compound having a boiling point of 190 ° C. or higher and having 3 to 20 carbon atoms. Here, the boiling point is a value at 760 mmHg (101,325 Pa).
Of the alcohol compounds, 1 to 4 valent saturated alcohols in which the hydrogen atom of the hydroxyl group is not substituted are preferred. This is because the latent heat of evaporation increases due to the association of hydroxyl groups, and the evaporation amount is easily adjusted.
Examples of alcohol compounds that can be used in the present invention include glycerin, diethylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, 1,3-butanediol, 1,4-butanediol, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. Can be mentioned.
The addition amount is usually 0.01 to 20% by weight, preferably 0.05 to 15% by weight, and more preferably 01 to 10% by weight of the resist composition. When the addition amount is small, the effect of the present invention cannot be obtained, and when the addition amount is large, the coating property and the resolution tend to be lowered. These solvents can be used alone or in admixture of two or more.
Moreover, the ratio of the said alcohol compound in all the solvents is 0.1 to 30 weight%, and a composition density | concentration is 2 to 30 weight%.

Examples of other solvents that can be used in combination with the alcohol compound include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, and the like. Alkyl ether acetates; 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-propyl ether, Propylene glycol dialkyl ethers such as pyrene glycol di-n-butyl ether; propylene glycol such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate Monoalkyl ether acetates; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate; n-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate, i-acetate Aliphatic carbo such as propyl, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, i-propyl propionate, n-butyl propionate, i-butyl propionate Acid esters; ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxy Other esters such as butyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; methyl ethyl ketone, 2-pentanone, 2-hexanone, 2-heptanone , 3-heptanone, 4- And ketones such as heptanone and cyclohexanone; amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone.
These solvents can be used alone or in admixture of two or more.

Formation of resist pattern When forming a resist pattern from a radiation-sensitive resin composition, the composition solution prepared as described above is applied by appropriate application means such as spin coating, cast coating, roll coating, etc. For example, it is applied onto a substrate such as a silicon wafer or a wafer coated with aluminum, and in some cases, a heat treatment (hereinafter referred to as “PB”) is performed at a temperature of about 70 ° C. to 160 ° C. to form a resist film. After that, drawing is performed by irradiating radiation, preferably EB. The drawing conditions 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 heat treatment (hereinafter referred to as “PEB”) is performed at a temperature of 50 to 200 ° C., preferably 70 to 160 ° C. for 30 seconds or more after irradiation. ) Is preferable. In this case, when the temperature of the PEB is less than 50 ° C., there is a possibility that the variation in sensitivity depending on the type of the substrate is widened.
Then, a predetermined resist pattern is formed by developing with an alkali developer usually at 10 to 50 ° C. for 10 to 200 seconds, preferably at 15 to 30 ° C. for 15 to 100 seconds.
Examples of the alkali developer include alkali metal hydroxide, aqueous ammonia, mono-, di- or tri-alkylamines, mono-, di- or tri-alkanolamines, heterocyclic amines, and tetraalkyls. Alkaline compounds such as ammonium hydroxides, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene are usually used. An alkaline aqueous solution dissolved so as to have a concentration of 1 to 10% by weight, preferably 1 to 5% by weight, particularly preferably 1 to 3% by weight is used.
In addition, 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 or an antistatic film can be provided on the resist film in order to prevent the influence of basic impurities contained in the environmental atmosphere and the charge in the film.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
Here,% and parts are based on weight unless otherwise specified.
Synthesis Example 1: Synthesis of acid-dissociable group-containing resin (A-1) 101 g of 4-acetoxystyrene, 5 g of styrene, 42 g of 4-t-butoxystyrene, 6 g of azobisisobutyronitrile (AIBN), and 1 g of t-dodecyl mercaptan Was dissolved in 160 g of propylene glycol monomethyl ether and polymerized for 16 hours under a nitrogen atmosphere while maintaining the reaction temperature at 70 ° C. After the polymerization, the reaction solution was dropped into 2,000 g of n-hexane to coagulate and purify the resulting resin. Next, 150 g of propylene glycol monomethyl ether was added to the purified resin, and then 300 g of methanol, 80 g of triethylamine and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting resin was redissolved in acetone so that the solid content concentration was 20% by weight, and then dropped into 2,000 g of water to solidify, thereby forming a white The powder was filtered and dried overnight at 50 ° C. under reduced pressure.
The obtained resin had an Mw of 16,000 and an Mw / Mn of 1.7. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of 4-hydroxystyrene, styrene and 4-t-butoxystyrene was 72: 5: 23. This resin is referred to as “acid-labile group-containing resin (A-1)”.

  Mw and Mn of the resin (A-1) and the resins obtained in the following synthesis examples were measured using a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation. It was measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of 0 ml / min, elution solvent tetrahydrofuran, and column temperature of 40 ° C.

Synthesis Example 2: Synthesis of acid-dissociable group-containing resin (A-2) 4-acetoxystyrene 100 g, tert-butyl acrylate 25 g, styrene 18 g, AIBN 6 g and t-dodecyl mercaptan 1 g were dissolved in 230 g of propylene glycol monomethyl ether. The polymerization was carried out for 16 hours under a nitrogen atmosphere while maintaining the reaction temperature at 70 ° C. After the polymerization, the reaction solution was dropped into 2,000 g of n-hexane to coagulate and purify the resulting resin. Next, 150 g of propylene glycol monomethyl ether was added to the purified resin, and then 300 g of methanol, 80 g of triethylamine and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting resin was redissolved in acetone so that the solid content concentration was 20% by weight, and then dropped into 2,000 g of water to solidify, thereby forming a white The powder was filtered and dried overnight at 50 ° C. under reduced pressure.
The obtained resin has Mw of 11,500 and Mw / Mn of 1.6. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene, t-butyl acrylate and styrene is 61:19:20. This resin is referred to as “acid-labile group-containing resin (A-2)”.

Synthesis Example 3 Synthesis of Acid-Dissociable Group-Containing Resin (A-3) The solvent was refluxed for 6 hours in the presence of sodium metal, and then used after distillation under a nitrogen atmosphere. The monomer was bubbled with dry nitrogen for 1 hour and then distilled before use. 4-7.6-ethoxystyrene 37.6 g, 4-t-butoxystyrene 11.0 g, and styrene 1.4 g are dissolved in cyclohexane 200 g, charged in a dry pressure-resistant glass bottle and packed with neoprene (DuPont brand name) with a perforated crown. And sealed. After cooling this pressure-resistant glass bottle to −20 ° C., n-butyllithium (1.83 mol / l cyclohexane solution) was added in the order of 2.96 ml and N, N, N ′, N′-tetramethylethylenediamine 0.98 g. The mixture was added and reacted for 1 hour while maintaining the temperature at -20 ° C. Thereafter, 1.0 g of methanol was injected to stop the reaction. It was confirmed that the color of the solution changed from red to colorless. After washing with 200 g of 3% by weight oxalic acid solution, 200 g of propylene glycol monomethyl ether and 1.5 g of 4-toluenesulfonic acid were added, and the mixture was stirred at room temperature (23 to 25 ° C.) for 3 hours for hydrolysis. The obtained copolymer solution was dropped into 2,000 g of water to solidify, and the resulting white powder was filtered and dried overnight at 50 ° C. under reduced pressure.
The obtained resin had Mw of 16,000 and Mw / Mn of 1.3. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of 4-hydroxystyrene, styrene and 4-t-butoxystyrene was 72: 5: 23. This resin is referred to as “acid-labile group-containing resin (A-3)”.

Synthesis Example 4: Synthesis of acid-dissociable group-containing resin (A-4) 173 g of 4-acetoxystyrene, 56 g of 4-t-butoxystyrene, 11 g of 2,5-dimethylhexane-2,5-diacrylate, azobisisobuty After 14 g of ronitrile and 11 g of t-dodecyl mercaptan were dissolved in 240 g of propylene glycol monomethyl ether, polymerization was carried out for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. After polymerization, the reaction solution was dropped into 2,000 g of hexane, and the resulting copolymer was coagulated and purified. Further, this coagulated purified product was dried at 50 ° C. under reduced pressure for 3 hours.
Next, 150 g of propylene glycol monomethyl ether was again added to 190 g of this purified polymer, and then 300 g of methanol, 100 g of triethylamine and 15 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting copolymer was dissolved in acetone so that the solid content concentration was 20% by weight, and then dropped into 2,000 g of water to solidify to form. The white powder was filtered and dried overnight at 50 ° C. under reduced pressure.
The obtained resin had Mw of 27,000 and Mw / Mn of 2.6. As a result of ¹³ C-NMR analysis, 4-hydroxystyrene, 4-t-butoxystyrene and 2,5-dimethylhexane-2 were obtained. , 5-diacrylate copolymerization molar ratio was 75: 22: 3. This resin is referred to as “acid-labile group-containing resin (A-4)”.

Synthesis Example 5 Synthesis of Acid-Dissociable Group-Containing Resin (A-5) 24 g of poly (p-hydroxystyrene) having an Mw of 12000 was dissolved in 100 g of dioxane, and then bubbled with nitrogen gas for 30 minutes. Thereafter, 5 g of ethyl vinyl ether and 1 g of p-toluenesulfonic acid pyridinium salt as a catalyst were added to this solution and reacted at room temperature for 12 hours. Next, the reaction solution was dropped into a 1% by mass aqueous ammonia solution to precipitate a polymer, filtered, and dried overnight in a vacuum dryer at 50 ° C.
This polymer has Mw of 15000 and Mw / Mn of 1.7. As a result of ¹³ C-NMR analysis, 35% of the hydrogen atoms in the phenolic hydroxyl group in poly (p-hydroxystyrene) are 1-ethoxyethyl. It had a structure substituted with a group. This polymer is referred to as “resin (A-5)”.

Examples 1-6 and Comparative Examples 1-2
Each component shown in Table 1 (where parts are based on weight standards) was mixed in the amounts shown in Table 1 to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 200 nm to prepare a composition solution. Next, each composition solution was spin-coated on a silicon wafer in a clean track ACT-8 manufactured by Tokyo Electron Co., Ltd., and then PB was performed under the conditions shown in Table 1 to form a resist film having a thickness of 100 nm. .
Subsequently, the resist film was irradiated with an electron beam using a simple electron beam drawing apparatus (manufactured by Hitachi, model “HL800D”, output: 50 KeV, current density: 5.0 ampere / cm ² ). PEB was performed under the conditions shown in Table 1. Thereafter, a 2.38 wt% tetramethylammonium hydroxide aqueous solution was used and developed by the paddle method at 23 ° C. for 1 minute, and then washed with pure water and dried to form a resist pattern. Table 1 shows the evaluation results of each resist.

The material used for each Example and comparative example except the said acid dissociable group containing resin (A) is shown below.
Acid generator (B)
B-1: N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide B-2: 2,4,6 trimethylphenyldiphenylsulfonium 4-tri Fluoromethylbenzenesulfonate B-3: Bis (t-butylsulfonyl) diazomethane B-4: Diphenyliodonium trifluoromethanesulfonate B-5: Triphenylsulfonium trifluoromethanesulfonate solvent (C)
C-1: Glycerin C-2: Diethylene glycol monobutyl ether (C ₄ H ₉ OCH ₂ CH ₂ OCH ₂ CH ₂ OH)
C-3: Diethylene glycol (HOCH ₂ CH ₂ OCH ₂ CH ₂ OH)
Other solvents (D)
D-1: Ethyl lactate D-2: Ethyl 3-ethoxypropionate D-3: Propylene glycol monomethyl ether acetate diffusion control agent (E)
E-1: 2-phenylbenzimidazole E-2: Nt-butoxycarbonyl-2-phenylbenzimidazole E-3: tri-n-octylamine E-4: 4-phenylpyridine

Here, each resist was evaluated in the following manner.
(1) Sensitivity (L / S)
A resist film formed on a silicon wafer is exposed to light, immediately subjected to PEB, then developed with alkali, washed with water, and dried to form a resist pattern. A line-and-space pattern (1L1S) having a line width of 150 nm The exposure amount for forming a line width of 1: 1 was set as the optimum exposure amount, and the sensitivity was evaluated based on the optimum exposure amount.
(2) Resolution (L / S)
For the line-and-space pattern (1L1S), the minimum line width (nm) of the line pattern resolved with the optimum exposure dose was taken as the resolution.
(3) LWR (nano edge roughness characteristics)
A line pattern of a line-and-space pattern (1L1S) having a designed line width of 150 nm was observed with a scanning electron microscope for semiconductor S-9220 Hitachi high-resolution FEB measuring device. FIG. 1 shows a schematic diagram of the pattern (unevenness is exaggerated from the actual). 1A is a plan view, and FIG. 1B is a sectional view of a pattern 2 formed on the silicon wafer 1. For the shape observed in each example, the nano edge roughness was evaluated by measuring the difference ΔCD between the line width and the design line width of 150 nm at the most remarkable unevenness generated along the lateral surface 2a of the line pattern.

The radiation-sensitive resin composition of the present invention contains a high boiling point solvent, has excellent line-and-space pattern resolution at the time of pattern formation of the radiation-sensitive resin composition, and is excellent in nano edge roughness. , EUV, and X-ray fine pattern formation. Therefore, the radiation-sensitive resin composition of the present invention is extremely useful as a chemically amplified resist for manufacturing semiconductor devices, which is expected to be further miniaturized from now on.

It is a schematic diagram of a line pattern for LWR measurement.

Explanation of symbols

1 Substrate 2 Resist pattern

Claims (4)

A composition containing an acid-dissociable group-containing resin (A) that is insoluble in alkali or hardly soluble in alkali and easily soluble in alkali by the action of an acid, and a radiation-sensitive acid generator (B) in a solvent containing an alcohol compound A positive-type radiation-sensitive resin composition dissolved,
The acid-dissociable group-containing resin (A) includes the following repeating unit (i) and repeating unit (ii), and the alcohol compound has 1 to 3 carbon atoms having a boiling point of 190 ° C. or higher at normal pressure of 760 mmHg. A positive-type radiation-sensitive resin composition, which is a tetravalent saturated alcohol compound.
Repeating unit (i); repeating unit represented by the following formula (1)

(In the formula (1), R represents a hydrogen atom or a methyl group, R ¹ represents a monovalent organic group, p is an integer of 0 to 3, q is an integer of 1 to 3, R ¹ may be the same or different from each other.)
Repeating unit (ii): at least one repeating unit selected from repeating units represented by the following formula (2-1), formula (2-2), and formula (2-3)

(In Formula (2-1) to Formula (2-3), R and R ′ each represent a hydrogen atom or a methyl group; in Formula (2-1), R ² represents a monovalent organic group (provided that − represents an excluding group corresponding to OR ^3), R ³ represents a monovalent acid-dissociable group, s is an integer of 0 to 3, t is an integer from 1 to 3, R ² there are a plurality of And a plurality of R ^{3 s} may be the same or different from each other; in the formula (2-2), R ⁴ represents 1-ethylcyclopentyl group, 1-methylcyclopentyl group, t-butyl group or 2-methyl- Represents a 2-adamantyl group; in formula (2-3), R ⁵ represents a divalent acid-dissociable group. The positive radiation-sensitive resin composition according to claim 1, wherein the acid-dissociable group-containing resin (A) contains a repeating unit (iii) represented by the following formula (3).

(In Formula (3), R ⁶ represents a monovalent organic group (excluding the group corresponding to —OR ³ in Formula (2-1)), r is an integer of 0 to 3, and there are a plurality of them. R ⁶ may be the same or different from each other.)   The alcohol compound is at least one selected from glycerin, diethylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, 1,3-butanediol, 1,4-butanediol, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. The positive radiation sensitive resin composition according to claim 1, wherein the positive radiation sensitive resin composition is provided.   The said radiation sensitive acid generator (B) contains at least 1 compound chosen from a sulfonimide compound, a disulfonyl diazomethane compound, or an onium salt compound, The claim 1, 2 or 3 characterized by the above-mentioned. A positive-type radiation-sensitive resin composition.

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