WO2011070718A1 - Low-molecular-weight positive-type radiation-sensitive composition, and resist pattern formation method - Google Patents

Abstract

Disclosed are: a radiation-sensitive composition which enables the formation of a resist pattern having a satisfactory shape and contains a resist material (a compound) that can be produced and quality-controlled readily; and a resist pattern formation method using the radiation-sensitive composition. Specifically disclosed are: a positive-type radiation-sensitive composition comprising (A) a low-molecular-weight compound which has at least one phenolic hydroxy or carboxyl group having an acid labile functional group introduced thereinto in the molecule, is insoluble in an alkaline developing solution but can become soluble in an alkaline developing solution upon receiving the action of an acid, and has a molecular weight of 400 to 3000 and a Mw/Mn ratio ranging from 1.00 to 1.05 inclusive, (B) a low-molecular-weight compound which has at least one phenolic hydroxy or carboxyl group in the molecule, is soluble in an alkaline developing solution, and has a molecular weight of 350 to 2500 and a Mw/Mn ratio ranging from 1.00 to 1.05 inclusive, (C) an acid generating agent, (E) an acid diffusion inhibitor, and a solvent; and a resist pattern formation method using the composition.

Description

Low molecular weight positive radiation sensitive composition and resist pattern forming method

The present invention relates to a useful positive radiation-sensitive composition containing a specific low molecular weight compound and a resist pattern forming method using the same.

Conventional general resist materials have been high molecular weight positive resists. However, high molecular weight positive resist materials (polymers) have a large molecular weight of about 10,000 to 100,000 and a wide molecular weight distribution. Therefore, in lithography using high molecular weight resist, roughness occurs on the surface of fine patterns, and the pattern dimensions are controlled. It becomes difficult to do, and the yield decreases. Therefore, there is a limit to miniaturization in conventional lithography using a polymer resist material. In order to produce a finer pattern, various low molecular weight positive resist materials have been proposed.
Conventional low molecular weight positive resist materials (compounds) are generally obtained by reacting a low molecular weight polyphenol with an acid-dissociable functional group introduction reagent. However, in that case, the resulting resist material is a mixture composed of compounds with different numbers of introduced protective groups, and it is difficult to control the production ratio, and it is difficult to obtain a positive resist with stable quality, which is practical and not necessary. (See Patent Document 1). In addition, a pure substance can be obtained by introducing protective groups into all phenolic hydroxyl groups of low molecular weight polyphenols, but in that case, the sensitivity of a positive resist using the same decreases and is not practical (Patent Document 1). reference). Furthermore, there is a report in which a pure substance is obtained by introducing a carboxyl group into a low molecular weight polyphenol and selectively introducing a protective group only into the carboxyl group (see Patent Document 2). However, in that case, there is a problem that the production of a low molecular weight polyphenol having a carboxyl group introduced therein is complicated and the purity of the resulting low molecular weight positive resist material is low, and improvements have been desired.

JP 2009-173623 A JP 2009-173625 A

An object of the present invention is to provide a positive radiation-sensitive composition that solves the above problems and a resist pattern forming method using the same.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a useful positive-type radiation-sensitive composition containing a specific low molecular weight compound is effective in solving the above-mentioned problems, and has a good resist pattern shape. The present invention has been found.

（式（１Ａ）中、Ｌは、独立して、単結合、炭素数１～２０の直鎖状もしくは分岐状のアルキレン基、炭素数３～２０のシクロアルキレン基、炭素数６～２４のアリーレン基、－Ｏ－、－ＯＣ（＝Ｏ）－、－ＯＣ（＝Ｏ）Ｏ－、－Ｎ（Ｒ^５）－Ｃ（＝Ｏ）－、－Ｎ（Ｒ^５）－Ｃ（＝Ｏ）Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ_２－およびこれらの任意の組み合わせからなる群から選択される二価の基であり、Ｒ^１は、独立して、炭素数１～２０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数６～２０のアリール基、炭素数１～２０のアルコキシル基、シアノ基、ニトロ基、複素環基、ハロゲン原子および炭素数１～２０のアルキルシリル基からなる群から選択される官能基、炭素数２～２０の置換メチル基、炭素数３～２０の１－置換エチル基、炭素数４～２０の１－置換－ｎ－プロピル基、炭素数３～２０の１－分岐アルキル基、炭素数１～２０のシリル基、炭素数２～２０のアシル基、炭素数２～２０の１－置換アルコキシアルキル基、炭素数２～２０の環状エーテル基、炭素数２～２０のアルコキシカルボニル基およびアルコキシカルボニルアルキル基からなる群から選択される酸解離性官能基、または水素原子であり、Ｒ’は、独立して、炭素数２～２０のアルキル基、または下記式

で表わされる基であり、Ｒ^４は、炭素数１～２０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数６～２０のアリール基、炭素数１～２０のアルコキシ基、シアノ基、ニトロ基、複素環基、ハロゲン原子および炭素数１～２０のアルキルシリル基からなる群から選択される官能基、または炭素数２～２０の置換メチル基、炭素数３～２０の１－置換エチル基、炭素数４～２０の１－置換－ｎ－プロピル基、炭素数３～２０の１－分岐アルキル基、炭素数１～２０のシリル基、炭素数２～２０のアシル基、炭素数２～２０の１－置換アルコキシアルキル基、炭素数２～２０の環状エーテル基、炭素数２～２０のアルコキシカルボニル基およびアルコキシカルボニルアルキル基からなる群から選択される酸解離性官能基であり、Ｒ^１またはＲ^４の少なくとも１つは酸解離性官能基であり、Ｒ^５は水素原子または炭素数１～２０のアルキル基であり、ｍは１～４の整数であり、ｐは０～５の整数である。）

（式（１Ｂ）中、Ｌ^Ａは、独立して、単結合、炭素数１～２０の直鎖状もしくは分岐状のアルキレン基、炭素数３～２０のシクロアルキレン基、炭素数６～２４のアリーレン基、－Ｏ－、－ＯＣ（＝Ｏ）－、－ＯＣ（＝Ｏ）Ｏ－、－Ｎ（Ｒ^５Ａ）－Ｃ（＝Ｏ）－、－Ｎ（Ｒ^５Ａ）－Ｃ（＝Ｏ）Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ_２－およびこれらの任意の組み合わせからなる群から選択される二価の基であり、Ｒ^１Ａは、独立して、炭素数１～２０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数６～２０のアリール基、炭素数１～２０のアルコキシル基、シアノ基、ニトロ基、水酸基、複素環基、ハロゲン原子、カルボキシル基、および炭素数１～２０のアルキルシリル基からなる群から選択される官能基、または水素原子であり、Ｒ”は、独立して、炭素数２～２０のアルキル基、または下記式

で表わされる基であり、Ｒ^４Ａは、炭素数１～２０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数６～２０のアリール基、炭素数１～２０のアルコキシ基、シアノ基、ニトロ基、複素環基、水酸基、ハロゲン原子、カルボキシル基および炭素数１～２０のアルキルシリル基からなる群から選択される官能基、または炭素数２～２０の置換メチル基、炭素数３～２０の１－置換エチル基、炭素数４～２０の１－置換－ｎ－プロピル基、炭素数３～２０の１－分岐アルキル基、炭素数１～２０のシリル基、炭素数２～２０のアシル基、炭素数２～２０の１－置換アルコキシアルキル基、炭素数２～２０の環状エーテル基、炭素数２～２０のアルコキシカルボニル基およびアルコキシカルボニルアルキル基からなる群から選択される酸解離性官能基であり、Ｒ^１ＡまたはＲ^４Ａの少なくとも１つはフェノール性水酸基またはカルボキシル基であり、Ｒ^５Aは水素原子または炭素数１～２０のアルキル基であり、ｍ^Ａは１～４の整数であり、ｐ^Ａは０～５の整数である。）
５．　第１項～第４項のいずれかに記載の感放射線性組成物を用いて、基板上にレジスト膜を形成する工程、該レジスト膜を露光する工程、および該レジスト膜を現像してレジストパターンを形成する工程を含むレジストパターン形成方法。 That is, the present invention is as follows.
1. Compound (A) satisfying all the conditions a) to e) below, Compound (B) satisfying all the conditions f) to i) below, visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV) A positive electrode containing an acid generator (C), an acid diffusion controller (E), and a solvent that generate acid directly or indirectly by irradiation with any radiation selected from the group consisting of X-rays, and ion beams Type radiation-sensitive composition, wherein the composition comprises 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, and the sum of the weight of the compound (A) and the weight of the compound (B) is A positive-type radiation-sensitive composition that is 50 to 99% by weight of the total weight of solid components.
a) Molecular weight: 400 to 3000
b) Insoluble in alkali developer (tetramethylammonium hydroxide (TMAH) 2.38 wt%) c) Soluble in alkali developer (TMAH 2.38 wt%) by the action of acid d) At least one in the molecule E) 1.00 ≦ Mw / Mn ≦ 1.05 (Mw: number average molecular weight, Mw: weight average molecular weight)
f) Molecular weight: 350-2500
g) Soluble in alkali developer (TMAH 2.38 wt%) h) At least one phenolic hydroxyl group or carboxyl group in the molecule i) 1.00 ≦ Mw / Mn ≦ 1.05
2. The positive radiation sensitive composition according to claim 1, wherein the compound (A) is a compound (Aa) in which an acid-dissociable functional group is introduced into all phenolic hydroxyl groups and carboxyl groups of the compound (B).
3. The positive radiation sensitive composition according to claim 1, wherein the compound (B) is a compound (Bb) in which no acid-dissociable functional group is introduced into all phenolic hydroxyl groups and carboxyl groups.
4). The compound (A) is the compound (Aa), a cyclic compound (A1) represented by the following formula (1A), and the compound (B) is the compound (Bb), The positive radiation-sensitive composition according to item 1, which is a cyclic compound (B1) represented by the formula (1B).

(In the formula (1A), L is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene having 6 to 24 carbon atoms. Group, —O—, —OC (═O) —, —OC (═O) O—, —N (R ⁵ ) —C (═O) —, —N (R ⁵ ) —C (═O) O A divalent group selected from the group consisting of —, —S—, —SO—, —SO ₂ — and any combination thereof, and R ¹ is independently an alkyl group having 1 to 20 carbon atoms. Cycloalkyl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxyl group having 1 to 20 carbon atoms, cyano group, nitro group, heterocyclic group, halogen atom and alkylsilyl having 1 to 20 carbon atoms A functional group selected from the group consisting of a group, a substituted methyl group having 2 to 20 carbon atoms, and 1- Substituted ethyl group, 1-substituted n-propyl group having 4 to 20 carbon atoms, 1-branched alkyl group having 3 to 20 carbon atoms, silyl group having 1 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms, carbon An acid-dissociable functional group selected from the group consisting of a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms and an alkoxycarbonylalkyl group, or A hydrogen atom, and R ′ is independently an alkyl group having 2 to 20 carbon atoms, or a group represented by the following formula:

R ⁴ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cyano group. , A nitro group, a heterocyclic group, a functional group selected from the group consisting of a halogen atom and an alkylsilyl group having 1 to 20 carbon atoms, a substituted methyl group having 2 to 20 carbon atoms, or a 1-substitution having 3 to 20 carbon atoms Ethyl group, 1-substituted n-propyl group having 4 to 20 carbon atoms, 1-branched alkyl group having 3 to 20 carbon atoms, silyl group having 1 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms, carbon number An acid-dissociable functional group selected from the group consisting of 2 to 20 1-substituted alkoxyalkyl groups, cyclic ether groups having 2 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms and alkoxycarbonylalkyl groups; R ¹ Others are at least one acid-dissociable functional groups R ^4, R ⁵ is a hydrogen atom or an alkyl group having a carbon number of 1 ~ 20, m is an integer of 1 ~ 4, p is from 0 to 5 It is an integer. )

(In the formula (1B), ^{L A} is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, C3-C20 cycloalkylene group, the number of 6 to 24 carbon atoms Arylene group, —O—, —OC (═O) —, —OC (═O) O—, —N (R ^5A ) —C (═O) —, —N (R ^5A ) —C (═O) A divalent group selected from the group consisting of O—, —S—, —SO—, —SO ₂ — and any combination thereof, and R ^1A is independently alkyl having 1 to 20 carbon atoms. Group, cycloalkyl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxyl group having 1 to 20 carbon atoms, cyano group, nitro group, hydroxyl group, heterocyclic group, halogen atom, carboxyl group, and carbon A functional group selected from the group consisting of a number 1 to 20 alkylsilyl group, or a hydrogen atom Yes, R "is independently an alkyl group having 2-20 carbon atoms or the following formula,

R ^4A is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cyano group. , A functional group selected from the group consisting of a nitro group, a heterocyclic group, a hydroxyl group, a halogen atom, a carboxyl group and an alkylsilyl group having 1 to 20 carbon atoms, or a substituted methyl group having 2 to 20 carbon atoms, and 3 to 3 carbon atoms 20 1-substituted ethyl groups, 1-substituted n-propyl groups having 4 to 20 carbon atoms, 1-branched alkyl groups having 3 to 20 carbon atoms, silyl groups having 1 to 20 carbon atoms, 2 to 20 carbon atoms An acid selected from the group consisting of an acyl group, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group A dissociative functional ^group, at least one of ^{R 1A} and ^{R 4A} is a phenolic hydroxyl group or carboxyl group, ^{R 5A} is an hydrogen atom or an alkyl group of a carbon number of 1 ~ 20, ^{m A} is 1-4 It is an integer, and p ^A is an integer of 0 to 5. )
5. A step of forming a resist film on a substrate, a step of exposing the resist film using the radiation-sensitive composition according to any one of Items 1 to 4, and developing the resist film to develop a resist pattern A resist pattern forming method including a step of forming a film.

According to the present invention, it is possible to provide a positive radiation-sensitive composition that solves the above problems, and a resist pattern forming method using the composition. The present invention facilitates the production of a resist compound useful for a positive radiation-sensitive composition and can increase the purity of the resist compound, thereby facilitating quality control. A positive radiation sensitive composition containing the resist compound gives a good resist pattern.

Hereinafter, the present invention will be described in detail.
[Positive radiation sensitive composition]
The present invention
Compound (A) satisfying all the following conditions a) to e):
Compound (B) satisfying all the following conditions f) to i):
An acid generator that generates an acid directly or indirectly upon irradiation with radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam ( C), a positive radiation sensitive composition comprising an acid diffusion controller (E), and a solvent,
The composition comprises 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent,
The present invention relates to a positive radiation-sensitive composition in which the sum of the weight of the compound (A) and the weight of the compound (B) is 50 to 99% by weight of the total weight of the solid component.
a) Molecular weight: 400-5000
b) Insoluble in alkali developer (TMAH 2.38 wt%) c) Soluble in alkali developer (TMAH 2.38 wt%) by the action of acid d) At least one acid-dissociable functional group is introduced into the molecule E) having a phenolic hydroxyl group or carboxyl group e) 1.00 ≦ Mw / Mn ≦ 1.05
f) Molecular weight: 350-4000
g) Soluble in alkali developer (TMAH 2.38 wt%) h) At least one phenolic hydroxyl group or carboxyl group in the molecule i) 1.00 ≦ Mw / Mn ≦ 1.05

Here, being soluble in an alkaline developer means that the dissolution rate of an amorphous film prepared by spin coating using a solution in which the compound is dissolved in a solvent described later is 10 Å / sec or more. The term “insoluble in an alkaline developer” means that the dissolution rate of an amorphous film prepared by spin coating using a solution obtained by dissolving the compound in a solvent described later is 5% / sec or less.

Mw / Mn represents polydispersity, Mn is the number average molecular weight, Mw is the weight average molecular weight, and can be determined by GPC analysis or the like. Mw / Mn is 1.00 ≦ Mw / Mn ≦ 1.05, preferably 1.00 ≦ Mw / Mn ≦ 1.03, more preferably 1.00 ≦ Mw / Mn ≦ 1.01, Mw / Mn Mn = 1.00 is composed of a single component, and is particularly preferable because the roughness of the resulting resist pattern is reduced.

An acid-dissociable functional group is a group that can be introduced into a phenolic hydroxyl group and / or carboxyl group and dissociates by the action of an acid to produce the original phenolic hydroxyl group and / or carboxyl group. It can be appropriately selected from those proposed for hydroxystyrene-based resins, (meth) acrylic acid-based resins and the like used in the amplified radiation-sensitive composition. For example, a substituted methyl group, 1-substituted ethyl group, 1-substituted n-propyl group, 1-branched alkyl group, silyl group, acyl group, 1-substituted alkoxymethyl group, cyclic ether group, alkoxycarbonyl group, etc. Preferably mentioned. The acid dissociable functional group preferably has no crosslinkable functional group.

As the compound (A), it is preferable to use a compound (Aa) in which an acid-dissociable functional group is introduced into all the phenolic hydroxyl groups and carboxyl groups of the compound (B) from the viewpoint of production and quality control. It is easier to introduce an acid dissociable functional group into all phenolic hydroxyl groups and carboxyl groups of the compound (B) than to introduce an acid dissociable functional group into some phenolic hydroxyl groups and carboxyl groups. Thus, a high-purity compound advantageous for quality control can be obtained.

As the compound (B), it is preferable to use a compound (Bb) having no acid-dissociable functional group introduced into all phenolic hydroxyl groups and carboxyl groups from the viewpoint of production and quality control. The compound (B) having an acid dissociable functional group that is soluble in an alkali developer can be obtained by introducing an acid dissociable functional group into some phenolic hydroxyl groups and carboxyl groups. Control of the reaction and quality control are more difficult than the compound (Bb) in which no acid-dissociable functional group is introduced into all phenolic hydroxyl groups and carboxyl groups.

It is more preferable to use the compound (Aa) and the compound (Bb) in combination from the viewpoint of production and ease of quality control. The ratio is appropriately determined depending on the dissolution rate of the solid component in the 2.38 mass% TMAH aqueous solution at 23 ° C., but usually compound (Aa): compound (Bb) = 10 to 90:10 to 90 (% by weight) More preferably, compound (Aa): compound (Bb) = 12.5-50: 50-87.5 (% by weight), more preferably compound (Aa): compound (Bb) = 15-30: 70 To 85 (% by weight). With the above blending ratio, high sensitivity and high resolution can be obtained, and the line edge roughness becomes small.

In the present invention, the compound (A) is the compound (Aa), a cyclic compound (A1) represented by the following formula (1A), and the compound (B) is the compound (Bb) The cyclic compound (B1) represented by the following formula (1B) is preferable.

（式（１Ａ）中、Ｌは、独立して、単結合、炭素数１～２０の直鎖状もしくは分岐状のアルキレン基、炭素数３～２０のシクロアルキレン基、炭素数６～２４のアリーレン基、－Ｏ－、－ＯＣ（＝Ｏ）－、－ＯＣ（＝Ｏ）Ｏ－、－Ｎ（Ｒ^５）－Ｃ（＝Ｏ）－、－Ｎ（Ｒ^５）－Ｃ（＝Ｏ）Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ_２－およびこれらの任意の組み合わせからなる群から選択される二価の基であり、Ｒ^１は独立して、炭素数１～２０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数６～２０のアリール基、炭素数１～２０のアルコキシル基、シアノ基、ニトロ基、複素環基、ハロゲン原子、炭素数１～２０のアルキルシリル基、これらの誘導体からなる群から選択される官能基、炭素数２～２０の置換メチル基、炭素数３～２０の１－置換エチル基、炭素数４～２０の１－置換－ｎ－プロピル基、炭素数３～２０の１－分岐アルキル基、炭素数１～２０のシリル基、炭素数２～２０のアシル基、炭素数２～２０の１－置換アルコキシアルキル基、炭素数２～２０の環状エーテル基、炭素数２～２０のアルコキシカルボニル基およびアルコキシカルボニルアルキル基からなる群から選択される酸解離性官能基、または水素原子であり、Ｒ’は独立して、炭素数２～２０のアルキル基、または下記式

で表わされる基またはこれらの誘導体であり、Ｒ^４は炭素数１～２０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数６～２０のアリール基、炭素数１～２０のアルコキシ基、シアノ基、ニトロ基、複素環基、ハロゲン原子、炭素数１～２０のアルキルシリル基、およびこれらの誘導体からなる群から選択される官能基、または炭素数２～２０の置換メチル基、炭素数３～２０の１－置換エチル基、炭素数４～２０の１－置換－ｎ－プロピル基、炭素数３～２０の１－分岐アルキル基、炭素数１～２０のシリル基、炭素数２～２０のアシル基、炭素数２～２０の１－置換アルコキシアルキル基、炭素数２～２０の環状エーテル基、炭素数２～２０のアルコキシカルボニル基およびアルコキシカルボニルアルキル基からなる群から選択される酸解離性官能基であり、Ｒ^１またはＲ^４の少なくとも１つは酸解離性官能基であり、Ｒ^５は水素原子または炭素数１～２０のアルキル基であり、ｍは１～４の整数であり、ｐは０～５の整数である。）

(In the formula (1A), L is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene having 6 to 24 carbon atoms. Group, —O—, —OC (═O) —, —OC (═O) O—, —N (R ⁵ ) —C (═O) —, —N (R ⁵ ) —C (═O) O A divalent group selected from the group consisting of —, —S—, —SO—, —SO ₂ — and any combination thereof, wherein R ¹ is independently an alkyl group having 1 to 20 carbon atoms, A cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cyano group, a nitro group, a heterocyclic group, a halogen atom, and an alkylsilyl group having 1 to 20 carbon atoms. , A functional group selected from the group consisting of these derivatives, a substituted methyl group having 2 to 20 carbon atoms, and 3 to 3 carbon atoms 20 1-substituted ethyl groups, 1-substituted n-propyl groups having 4 to 20 carbon atoms, 1-branched alkyl groups having 3 to 20 carbon atoms, silyl groups having 1 to 20 carbon atoms, 2 to 20 carbon atoms Acid dissociation selected from the group consisting of acyl groups, 1-substituted alkoxyalkyl groups having 2 to 20 carbon atoms, cyclic ether groups having 2 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms and alkoxycarbonylalkyl groups A functional group or a hydrogen atom, and R ′ is independently an alkyl group having 2 to 20 carbon atoms, or a group represented by the following formula:

Or a derivative thereof, wherein R ⁴ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. , A cyano group, a nitro group, a heterocyclic group, a halogen atom, an alkylsilyl group having 1 to 20 carbon atoms, and a functional group selected from the group consisting of these derivatives, or a substituted methyl group having 2 to 20 carbon atoms, carbon 1-substituted ethyl group having 3 to 20 carbon atoms, 1-substituted n-propyl group having 4 to 20 carbon atoms, 1-branched alkyl group having 3 to 20 carbon atoms, silyl group having 1 to 20 carbon atoms, 2 carbon atoms Selected from the group consisting of an acyl group having ˜20, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms and an alkoxycarbonylalkyl group. Wherein R ¹ or R ⁴ is an acid dissociable functional group, R ⁵ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and m is 1 to 4 is an integer, and p is an integer of 0 to 5. )

（式（１Ｂ）中、Ｌ^Ａは、独立して、単結合、炭素数１～２０の直鎖状もしくは分岐状のアルキレン基、炭素数３～２０のシクロアルキレン基、炭素数６～２４のアリーレン基、－Ｏ－、－ＯＣ（＝Ｏ）－、－ＯＣ（＝Ｏ）Ｏ－、－Ｎ（Ｒ^５Ａ）－Ｃ（＝Ｏ）－、－Ｎ（Ｒ^５Ａ）－Ｃ（＝Ｏ）Ｏ－、－Ｓ－、－ＳＯ－、－ＳＯ_２－およびこれらの任意の組み合わせからなる群から選択される二価の基であり、Ｒ^１Ａは独立して、炭素数１～２０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数６～２０のアリール基、炭素数１～２０のアルコキシル基、シアノ基、ニトロ基、水酸基、複素環基、ハロゲン原子、カルボキシル基、炭素数１～２０のアルキルシリル基、これらの誘導体からなる群から選択される官能基、または水素原子であり、Ｒ”は独立して、炭素数２～２０のアルキル基、または下記式

で表わされる基またはこれらの誘導体であり、Ｒ^４Ａは炭素数１～２０のアルキル基、炭素数３～２０のシクロアルキル基、炭素数６～２０のアリール基、炭素数１～２０のアルコキシ基、シアノ基、ニトロ基、複素環基、水酸基、ハロゲン原子、カルボキシル基、炭素数１～２０のアルキルシリル基、およびこれらの誘導体からなる群から選択される官能基、または炭素数２～２０の置換メチル基、炭素数３～２０の１－置換エチル基、炭素数４～２０の１－置換－ｎ－プロピル基、炭素数３～２０の１－分岐アルキル基、炭素数１～２０のシリル基、炭素数２～２０のアシル基、炭素数２～２０の１－置換アルコキシアルキル基、炭素数２～２０の環状エーテル基、炭素数２～２０のアルコキシカルボニル基およびアルコキシカルボニルアルキル基からなる群から選択される酸解離性官能基であり、Ｒ^１ＡまたはＲ^４Ａの少なくとも１つはフェノール性水酸基またはカルボキシル基であり、Ｒ^５Ａは水素原子または炭素数１～２０のアルキル基であり、ｍ^Ａは１～４の整数であり、ｐ^Ａは０～５の整数である。）

(In the formula (1B), ^{L A} is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, C3-C20 cycloalkylene group, the number of 6 to 24 carbon atoms Arylene group, —O—, —OC (═O) —, —OC (═O) O—, —N (R ^5A ) —C (═O) —, —N (R ^5A ) —C (═O) A divalent group selected from the group consisting of O—, —S—, —SO—, —SO ₂ — and any combination thereof, and R ^1A is independently an alkyl group having 1 to 20 carbon atoms. Cycloalkyl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxyl group having 1 to 20 carbon atoms, cyano group, nitro group, hydroxyl group, heterocyclic group, halogen atom, carboxyl group, carbon number 1 Up to 20 alkylsilyl groups, functional groups selected from the group consisting of these derivatives, or An atom, R "is independently an alkyl group having 2-20 carbon atoms or the following formula,

R ^4A is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. , A cyano group, a nitro group, a heterocyclic group, a hydroxyl group, a halogen atom, a carboxyl group, an alkylsilyl group having 1 to 20 carbon atoms, and a functional group selected from the group consisting of these derivatives, or a group having 2 to 20 carbon atoms Substituted methyl group, 1-substituted ethyl group having 3 to 20 carbon atoms, 1-substituted n-propyl group having 4 to 20 carbon atoms, 1-branched alkyl group having 3 to 20 carbon atoms, silyl group having 1 to 20 carbon atoms Group, acyl group having 2 to 20 carbon atoms, 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, cyclic ether group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, and alkoxycarbonyl An acid dissociable functional group selected from the group consisting of alkyl groups, wherein at least one of R ^1A or R ^4A is a phenolic hydroxyl group or a carboxyl group, and R ^5A is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ^{M A} is an integer of 1 to 4, and p ^A is an integer of 0 to 5. )

The acid dissociable functional group may be appropriately selected and used from those proposed in hydroxystyrene-based resins, (meth) acrylic acid-based resins and the like used in chemically amplified resist compositions for KrF and ArF. it can. For example, a substituted methyl group, 1-substituted ethyl group, 1-substituted n-propyl group, 1-branched alkyl group, silyl group, acyl group, 1-substituted alkoxymethyl group, cyclic ether group, alkoxycarbonyl group, etc. Preferably mentioned. The acid dissociable functional group preferably has no crosslinkable functional group.

The substituted methyl group is usually a substituted methyl group having 2 to 20 carbon atoms, preferably a substituted methyl group having 4 to 18 carbon atoms, and more preferably a substituted methyl group having 6 to 16 carbon atoms. For example, methoxymethyl group, methylthiomethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, t-butoxymethyl group, 2-methylpropoxymethyl group, ethylthiomethyl group, methoxy Ethoxymethyl group, phenyloxymethyl group, 1-cyclopentyloxymethyl group, 1-cyclohexyloxymethyl group, benzylthiomethyl group, phenacyl group, 4-bromophenacyl group, 4-methoxyphenacyl group, piperonyl group, and the following formula ( The substituent etc. which are shown by 7) can be mentioned.

（式（７）中、Ｒ^２は、炭素数１～４のアルキル基である。炭素数１～４のアルキル基としては、メチル基、エチル基、イソプロピル基、ｎ－プロピル基、ｔ－ブチル基、ｎ－ブチル基等が挙げられる。）

(In the formula (7), R ² is an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, isopropyl, n-propyl, and t-butyl. Group, n-butyl group and the like.)

The 1-substituted ethyl group is usually a 1-substituted ethyl group having 3 to 20 carbon atoms, preferably a 1-substituted ethyl group having 5 to 18 carbon atoms, and more preferably a substituted ethyl group having 7 to 16 carbon atoms. . For example, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group, n-propoxyethyl group, Isopropoxyethyl group, n-butoxyethyl group, t-butoxyethyl group, 2-methylpropoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-cyclopentyloxy Examples thereof include an ethyl group, a 1-cyclohexyloxyethyl group, a 1-phenylethyl group, a 1,1-diphenylethyl group, and a substituent represented by the following formula (8).

（式（８）中、Ｒ^２は、前記と同様である。）

(In Formula (8), R ² is the same as described above.)

The 1-substituted-n-propyl group is usually a 1-substituted-n-propyl group having 4 to 20 carbon atoms, preferably a 1-substituted-n-propyl group having 6 to 18 carbon atoms, and having 8 carbon atoms. More preferred are 1 to 16 1-substituted-n-propyl groups. Examples thereof include a 1-methoxy-n-propyl group and a 1-ethoxy-n-propyl group.
The 1-branched alkyl group is usually a 1-branched alkyl group having 3 to 20 carbon atoms, preferably a 1-branched alkyl group having 5 to 18 carbon atoms, and more preferably a branched alkyl group having 7 to 16 carbon atoms. . For example, isopropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, 2-methyladamantyl group, 2-ethyladamantyl group, etc. Can be mentioned.

The silyl group is usually a silyl group having 1 to 20 carbon atoms, preferably a silyl group having 3 to 18 carbon atoms, and more preferably a silyl group having 5 to 16 carbon atoms. For example, trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, tert-butyldiphenylsilyl group, tri-tert-butylsilyl group and triphenylsilyl Groups and the like.
The acyl group is usually an acyl group having 2 to 20 carbon atoms, preferably an acyl group having 4 to 18 carbon atoms, and more preferably an acyl group having 6 to 16 carbon atoms. Examples include acetyl group, phenoxyacetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, adamantylcarbonyl group, benzoyl group and naphthoyl group.

The 1-substituted alkoxymethyl group is usually a 1-substituted alkoxymethyl group having 2 to 20 carbon atoms, preferably a 1-substituted alkoxymethyl group having 4 to 18 carbon atoms, and a 1-substituted alkoxy group having 6 to 16 carbon atoms. More preferred are alkoxymethyl groups. Examples thereof include 1-cyclopentylmethoxymethyl group, 1-cyclopentylethoxymethyl group, 1-cyclohexylmethoxymethyl group, 1-cyclohexylethoxymethyl group, 1-cyclooctylmethoxymethyl group, 1-adamantylmethoxymethyl group, and the like. .
The cyclic ether group is usually a cyclic ether group having 2 to 20 carbon atoms, preferably a cyclic ether group having 4 to 18 carbon atoms, and more preferably a cyclic ether group having 6 to 16 carbon atoms. Examples thereof include a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 4-methoxytetrahydropyranyl group, and a 4-methoxytetrahydrothiopyranyl group.

The alkoxycarbonyl group is usually an alkoxycarbonyl group having 2 to 20 carbon atoms, preferably an alkoxycarbonyl group having 4 to 18 carbon atoms, and more preferably an alkoxycarbonyl group having 6 to 16 carbon atoms. For example, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a tert-butoxycarbonyl group, or an acid dissociable functional group represented by n = 0 in the following formula (9) Etc.

The alkoxycarbonylalkyl group is usually an alkoxycarbonylalkyl group having 2 to 20 carbon atoms, preferably an alkoxycarbonylalkyl group having 4 to 18 carbon atoms, and more preferably an alkoxycarbonylalkyl group having 6 to 16 carbon atoms. For example, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, an n-propoxycarbonylmethyl group, an isopropoxycarbonylmethyl group, an n-butoxycarbonylmethyl group, or an acid dissociative function represented by n = 1 to 4 in the following formula (9) Groups and the like.

（式（９）中、Ｒ^２は水素または炭素数１～４の直鎖あるいは分岐アルキル基であり、ｎは０～４の整数である。）

(In the formula (9), R ² is hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 4)

Of these acid dissociable functional groups, a substituted methyl group, a 1-substituted ethyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, and an alkoxycarbonylalkyl group are preferred, and a substituted methyl group, 1-substituted An ethyl group, an alkoxycarbonyl group and an alkoxycarbonylalkyl group are more preferred because of their high sensitivity, and further, an acid dissociation property having a structure selected from a cycloalkane having 3 to 12 carbon atoms, a lactone and an aromatic ring having 6 to 16 carbon atoms. A functional group is more preferable. The cycloalkane having 3 to 12 carbon atoms may be monocyclic or polycyclic, but is preferably polycyclic. Specific examples include monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane and the like. More specifically, monocycloalkane such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornane, Examples include polycycloalkanes such as isobornane, tricyclodecane, and tetracyclodecane. Among these, adamantane, tricyclodecane, and tetracyclodecane are preferable, and adamantane and tricyclodecane are particularly preferable. The cycloalkane having 3 to 12 carbon atoms may have a substituent. Examples of the lactone include butyrolactone or a cycloalkane group having 3 to 12 carbon atoms having a lactone group. Examples of the aromatic ring having 6 to 16 carbon atoms include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a pyrene ring, and a benzene ring and a naphthalene ring are preferable, and a naphthalene ring is particularly preferable.
In particular, an acid dissociable functional group selected from the group consisting of groups represented by the following formula (10) is preferable because of its high resolution.

(In the formula (10), R ^6A is a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R ⁶ is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, cyano A group, a nitro group, a heterocyclic group, a halogen atom, or a carboxyl group, n ₁ is an integer of 0 to 4, n ₂ is an integer of 1 to 5, and n ₀ is an integer of 0 to 4.)
The acid dissociable functional group R ¹ is a repeating unit represented by the following formula (11) and the following formula (12) or R ¹ (R ¹ is the same as above) as long as the effects of the present invention are not impaired. It may be a substituent consisting of the terminal group shown.

In the formula (11) and / or (12), R ¹ is the same as described above. L is as defined above, and preferably a single bond, a methylene group, an ethylene group or a carbonyl group. A plurality of Q may be the same or different. n ₅ is an integer of 0 to 4, n ₆ is an integer of 1 to 3, and x is an integer of 0 to 3, which satisfies 1 ≦ n ₅ + n ₆ ≦ 5. A plurality of n ₅ , n ₆ and x may be the same or different. R ³ is a halogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, alkenyl group, acyl group, alkoxycarbonyl group, alkyloyloxy group, aryloyloxy group, cyano group, And a substituent selected from the group consisting of nitro groups. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom; examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples thereof include alkyl groups having 1 to 4 carbon atoms such as butyl group; examples of cycloalkyl groups include cyclohexyl group, norbornyl group and adamantyl group; examples of aryl groups include phenyl group, tolyl group, xylyl group, and naphthyl group. Aralkyl groups include benzyl group, hydroxybenzyl group, dihydroxybenzyl group, etc .; alkoxy groups include methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, isopropoxy group, n -Butoxy group, isobutoxy group, sec-butoxy group an alkoxy group having 1 to 4 carbon atoms such as a tert-butoxy group; an oxy group such as a phenoxy group as an aryloxy group; a carbon atom such as a vinyl group, a propenyl group, an allyl group, or a butenyl group as an alkenyl group; Examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, an isovaleryl group, a pivaloyl group and the like, and an aliphatic acyl group having 1 to 6 carbon atoms, and Aromatic acyl groups such as benzoyl group and toluoyl group are exemplified; as alkoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec- Butoxycarbonyl group, tert-butoxycar An alkoxycarbonyl group having 2 to 5 carbon atoms such as an nyl group; the alkyloyloxy group includes an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, and a pivaloyloxy group. An aryloyloxy group includes a benzoyloxy group and the like. A plurality of R ³ may be the same or different.

In the present invention, the acid dissociable functional group means a characteristic group that is cleaved in the presence of an acid to generate an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a hexafluoroisopropanol group. A phenolic hydroxyl group and a carboxyl group are preferable, and a phenolic hydroxyl group is particularly preferable. The acid-dissociable functional group preferably has a property of causing a chain-breaking reaction in the presence of an acid in order to enable pattern formation with higher sensitivity and higher resolution.

The compound (A) represented by the above formula (1) is subjected to a condensation reaction of at least one selected from the group consisting of the aromatic carbonyl compound (A11) and a phenol (A12), and then introduced with an acid-dissociable functional group. Obtained by reacting reagents.

The aromatic carbonyl compound (A11) is benzaldehyde and derivatives thereof, such as benzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, ethylmethylbenzaldehyde, isopropylmethylbenzaldehyde, diethylbenzaldehyde, anisaldehyde, naphthoaldehyde. Aldehyde, anthraldehyde, cyclopropylbenzaldehyde, cyclobutanebenzaldehyde, cyclopentanebenzaldehyde, cyclohexanebenzaldehyde, phenylbenzaldehyde, naphthylbenzaldehyde, adamantylbenzaldehyde, norbornylbenzaldehyde, lactylbenzaldehyde, isopropylbenzaldehyde , Normal propyl benzaldehyde, bromobenzaldehyde, dimethylaminobenzaldehyde, cyclopropylbenzaldehyde, cyclobutanebenzaldehyde, cyclopentanebenzaldehyde, cyclohexanebenzaldehyde, phenylbenzaldehyde, naphthylbenzaldehyde, adamantylbenzaldehyde, norbornylbenzaldehyde, lactylbenzaldehyde, hydroxybenzaldehyde and dihydroxybenzaldehyde Propyl benzaldehyde, butyl benzaldehyde, hydroxy benzaldehyde, cyclohexyl benzaldehyde, and phenyl benzaldehyde are preferable, and propyl benzaldehyde, butyl benzaldehyde, cyclohexyl benzaldehyde and More preferably nil benzaldehyde, more preferably propyl benzaldehyde and cyclohexyl benzaldehyde. The aromatic carbonyl compound (A11) may have a linear or branched alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a halogen atom, or the like as long as the effects of the present invention are not impaired. The aromatic carbonyl compound (A11) may be used alone or in combination of two or more.

Examples of the phenols (A12) include phenol, catechol, resorcinol, hydroquinone, pyrogallol and the like, which may have a substituent described later, 4-substituted phenol, resorcinol, pyrogallol are preferable, and resorcinol, pyrogallol are more preferable. Resorcinol is more preferred. The phenols (A12) are linear or branched alkyl groups having 1 to 20 carbon atoms, cyclic alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, cyano groups, and the like within a range not impairing the effects of the present invention. It may have a hydroxyl group, a halogen atom or the like. The phenols (A12) may be used alone or in combination of two or more.

The compound represented by the above formula (1B) can be produced by a known method. For example, in an organic solvent such as methanol or ethanol, 0.1 to 10 moles of phenols (A12) per 1 mole of aromatic carbonyl compound (A11), acid catalyst (hydrochloric acid, sulfuric acid, paratoluenesulfonic acid, etc.) The reaction mixture is reacted at 60 to 150 ° C. for about 0.5 to 20 hours, filtered, washed with an alcohol such as methanol, washed with water, filtered, separated and dried. Instead of the acid catalyst, a basic catalyst (such as sodium hydroxide, barium hydroxide or 1,8-diazabicyclo [5.4.0] undecene-7) may be used and reacted in the same manner. Further, the compound represented by the formula (1B) is produced by converting the aromatic carbonyl compound (A11) into a dihalide with hydrogen halide or halogen gas, and reacting the isolated dihalide with a phenol (A12). You can also.

Compound (A) can be obtained by introducing an acid dissociable functional group into at least one phenolic hydroxyl group or carboxyl group of compound (B). A method for introducing an acid-dissociable functional group into at least one phenolic hydroxyl group or carboxyl group of the compound (B) is known. For example, an acid dissociable functional group can be introduced into at least one phenolic hydroxyl group or carboxyl group of the compound (B) as follows. A compound for introducing an acid-dissociable functional group (acid-dissociable functional group-introducing reagent) can be synthesized or easily obtained by a known method. For example, an active carboxylic acid derivative such as acid chloride, acid anhydride, dicarbonate, etc. Compounds, alkyl halides, vinyl alkyl ethers, dihydropyrans, halocarboxylic acid alkyl esters and the like can be mentioned but are not particularly limited.

For example, the compound (B) is dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like. Subsequently, vinyl alkyl ether such as ethyl vinyl ether or dihydropyran is added, and the reaction is carried out at 20 to 60 ° C. for 6 to 72 hours at atmospheric pressure in the presence of an acid catalyst such as pyridinium-p-toluenesulfonate. The reaction solution is neutralized with an alkali compound and added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain compound (A).

Also, the compound (B) is dissolved or suspended in an aprotic solvent such as acetone, THF, propylene glycol monomethyl ether acetate or the like. Subsequently, an alkyl halide such as ethyl chloromethyl ether or a halocarboxylic acid alkyl ester such as methyl adamantyl bromoacetate is added and reacted in the presence of an alkali catalyst such as potassium carbonate at 20 to 110 ° C. for 6 to 72 hours. . The reaction solution is neutralized with an acid such as hydrochloric acid and added to distilled water to precipitate a white solid, and then the separated white solid is washed with distilled water and dried to obtain compound (A).

More preferably, two or more aromatic carbonyl compounds (A11) are used. By using two or more aromatic carbonyl compounds (A11), the solubility of the resulting cyclic compound in a semiconductor safety solvent is improved.

The molecular weight of the compound represented by the above formula (1A) is 990 to 2900, preferably 1040 to 2650, more preferably 1080 to 2400, and further preferably 1150 to 2200. The molecular weight of the compound represented by the formula (1B) is 790 to 2000, preferably 840 to 1750, more preferably 880 to 1500, and further preferably 950 to 1300. Within the above range, it is possible to have heat resistance while maintaining the film forming property required for the resist material.

（式（２Ａ）において、Ｘは水素原子またはハロゲン原子であり、ｍ_１は１～４の整数であり、ｍ_２は０～３の整数であり、ｍ_１＋ｍ_２＝４であり、Ｒ^１またはＲ^４の少なくとも１つは酸解離性官能基であり、Ｒ^１、Ｒ^４、ｐは前記と同様である。） The compound (A) represented by the above formula (1A) is preferably a compound represented by the following formula (2A).

(In the formula (2A), X is a hydrogen atom or a halogen atom, m ₁ is an integer of 1 to 4, m ₂ is an integer of 0 to 3, m ₁ + m ₂ = 4, and R ¹ Or at least one of R ⁴ is an acid-dissociable functional group, and R ¹ , R ⁴ , and p are the same as above.)

（式（３Ａ）において、Ｒ^２は、炭素数２～２０の置換メチル基、炭素数３～２０の１－置換エチル基、炭素数４～２０の１－置換－ｎ－プロピル基、炭素数３～２０の１－分岐アルキル基、炭素数１～２０のシリル基、炭素数２～２０のアシル基、炭素数２～２０の１－置換アルコキシアルキル基、炭素数２～２０の環状エーテル基、炭素数２～２０のアルコキシカルボニル基およびアルコキシカルボニルアルキル基からなる群から選択される酸解離性官能基であり、Ｘ、ｍ_１、ｍ_２、Ｒ^４、ｐは前記と同様である。） As the compound (A) represented by the above formula (1A), a compound represented by the following formula (3A) is more preferable.

(In the formula (3A), R ² represents a substituted methyl group having 2 to 20 carbon atoms, a 1-substituted ethyl group having 3 to 20 carbon atoms, a 1-substituted n-propyl group having 4 to 20 carbon atoms, 1-20 branched alkyl group having 3-20 carbon atoms, silyl group having 1-20 carbon atoms, acyl group having 2-20 carbon atoms, 1-substituted alkoxyalkyl group having 2-20 carbon atoms, cyclic ether group having 2-20 carbon atoms And an acid dissociable functional group selected from the group consisting of an alkoxycarbonyl group having 2 to 20 carbon atoms and an alkoxycarbonylalkyl group, and X, m ₁ , m ₂ , R ⁴ and p are as defined above.

（式（４Ａ）において、Ｒ^２、Ｒ^４、ｐは前記と同様である。） The compound (A) represented by the above formula (1A) is more preferably a compound represented by the following formula (4A).

(In the formula (4A), R ² , R ⁴ and p are the same as above.)

（式（５Ａ）において、Ｒ^２は前記と同様である。） As the compound (A) represented by the above formula (1A), a compound represented by the following formula (5A) is particularly preferable.

(In Formula (5A), R ² is the same as described above.)

（式（２Ｂ）において、Ｘは水素原子またはハロゲン原子であり、ｍ_１は１～４の整数であり、ｍ_２は０～３の整数であり、ｍ_１＋ｍ_２＝４であり、Ｒ^４、ｐは前記と同様である。） The compound (B) represented by the above formula (1B) is preferably a compound represented by the following formula (2B).

(In the formula (2B), X is a hydrogen atom or a halogen atom, m ₁ is an integer of 1 to 4, m ₂ is an integer of 0 to 3, m ₁ + m ₂ = 4, and R ⁴ , P is the same as above.)

（式（３Ｂ）において、ｍ_１、Ｒ^４、ｐは前記と同様である。） As the compound (B) represented by the above formula (1B), a compound represented by the following formula (3B) is more preferable.

(In Formula (3B), m ₁ , R ⁴ and p are the same as above.)

（式（４Ｂ）において、Ｒ^４、ｐは前記と同様である。） The compound (B) represented by the above formula (1B) is more preferably a compound represented by the following formula (4B).

(In the formula (4B), R ⁴ and p are as defined above.)

As the compound (B) represented by the above formula (1B), a compound represented by the following formula (5B) is particularly preferable.

The compound (A) has high heat resistance and is amorphous so that it is excellent in film-forming properties, does not have sublimation properties, is excellent in alkali developer dissolution deterrence, etching resistance, and the like. It is suitably used as a component (base material).
Also, in terms of production, various aldehydes including industrially produced aromatic aldehydes and phenols such as resorcinol and pyrogallol are used as raw materials to undergo a dehydration condensation reaction with a nonmetallic catalyst such as hydrochloric acid, and then industrial Since the acid-dissociable functional group-introducing reagent that has been produced in general is reacted with a nonmetallic catalyst such as hydrochloric acid or amines, it can be produced in a high yield, so that it is extremely excellent in practicality.

The compound (B) has high heat resistance and is amorphous so that it has excellent film-forming properties, no sublimation, excellent alkali developer solubility, etching resistance, and the like. It is suitably used as (base material).
Also, in terms of production, various aldehydes including industrially produced aromatic aldehydes and phenols such as resorcinol and pyrogallol are used as raw materials to cause a dehydration condensation reaction with a nonmetallic catalyst such as hydrochloric acid. Since it can be produced in a yield, it is extremely excellent in practicality.

In order to reduce the amount of residual metal in compound (A) or compound (B), purification may be performed as necessary. Further, when the acid catalyst remains, generally the storage stability of the positive radiation sensitive composition is lowered, or when the basic catalyst remains, generally the sensitivity of the positive radiation sensitive composition is lowered. Purification for the purpose may be performed. The purification can be performed by a known method as long as the compound (A) or the compound (B) is not denatured, and is not particularly limited. For example, the method is washed with water, washed with an acidic aqueous solution, washed with a basic aqueous solution. A method of treating with an ion exchange resin, a method of treating with silica gel column chromatography, and the like. These purification methods are more preferably performed in combination of two or more. Acidic aqueous solution, basic aqueous solution, ion exchange resin, and silica gel column chromatography are optimal depending on the metal to be removed, the amount and type of acidic compound and / or basic compound, the type of dissolution inhibitor to be purified, etc. Can be selected as appropriate. For example, hydrochloric acid, nitric acid, acetic acid aqueous solution having a concentration of 0.01 to 10 mol / L as acidic aqueous solution, aqueous ammonia solution having a concentration of 0.01 to 10 mol / L as basic aqueous solution, cation exchange resin as ion exchange resin, For example, Amberlyst 15J-HG Dry made by Organo can be mentioned. You may dry after refinement | purification. Drying can be performed by a known method, and is not particularly limited, and examples thereof include a method of vacuum drying and hot air drying under conditions where the compound (A) or the compound (B) is not denatured.

The compound (A) and compound (B) in the present invention can take a cis isomer and a trans isomer, but may have any structure or mixture. When used as a resist component of a radiation-sensitive composition, it is preferable to have only a cis- or trans-structure because it is a pure substance compound and the uniformity of the components in the resist film is high. A method for obtaining a cyclic compound having only a cis- or trans-structure is performed by a known method such as separation by column chromatography or preparative liquid chromatography or optimization of a reaction solvent and reaction temperature during production. Can do.

The glass transition temperature of the compound (A) and the compound (B) in the present invention is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. When the glass transition temperature is within the above range, the semiconductor lithography process has heat resistance capable of maintaining the pattern shape and can provide performance such as high resolution.
In the present invention, the calorific value of crystallization determined by differential scanning calorimetry of the glass transition temperatures of the compound (A) and the compound (B) in the present invention is preferably less than 20 J / g. Further, (crystallization temperature) − (glass transition temperature) is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher. When the crystallization exotherm is less than 20 J / g, or (crystallization temperature) − (glass transition temperature) is within the above range, an amorphous film can be easily formed by spin coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.

In the present invention, the crystallization calorific value, the crystallization temperature, and the glass transition temperature can be determined by measurement and differential scanning calorimetry as follows using DSC / TA-50WS manufactured by Shimadzu Corporation. About 10 mg of a sample is put in an aluminum non-sealed container and heated to a melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (50 ml / min). After the rapid cooling, the temperature is again raised to the melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (30 ml / min). After further rapid cooling, the temperature is raised again to 400 ° C. at a rate of temperature increase of 20 ° C./min in a nitrogen gas stream (30 ml / min). The temperature at the midpoint where the discontinuity appears in the baseline (where the specific heat has changed to half) is the glass transition temperature (Tg), and the temperature of the exothermic peak that appears thereafter is the crystallization temperature. The calorific value is obtained from the area of the region surrounded by the exothermic peak and the baseline, and is defined as the crystallization calorific value.

Compound (A) and Compound (B) have low sublimation properties under normal pressure at 100 ° C. or lower, preferably 120 ° C. or lower, more preferably 130 ° C. or lower, further preferably 140 ° C. or lower, particularly preferably 150 ° C. or lower. It is preferable. The low sublimation property means that, in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10%, preferably 5%, more preferably 3%, still more preferably 1%, particularly preferably 0.1. % Or less is preferable. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. Moreover, a favorable pattern shape can be given with low LER.

Compound (A) and Compound (B) are preferably F <3.0 (F represents the total number of atoms / (total number of carbon atoms−total number of oxygen atoms)), more preferably F <2.5. Fulfill. By satisfying the above conditions, the dry etching resistance is excellent.

Compound (A) and Compound (B) are propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone, anisole, butyl acetate, propion A solvent selected from ethyl acid and ethyl lactate and having the highest solubility in compound (A) and compound (B) at 23 ° C., preferably 1% by weight or more, more preferably 5% by weight Or more, more preferably 10% by weight or more, particularly preferably a solvent selected from PGMEA, PGME, and CHN and having the highest solubility in the compound (A) and the compound (B) at 23 ° C., Dissolves 20% by weight or more. By satisfying the above conditions, use in a semiconductor manufacturing process in actual production is possible, and storage stability is also improved.

A non-acid-dissociable functional group may be introduced into at least one phenolic hydroxyl group and / or carboxyl group of the compound (B) as long as the effects of the present invention are not impaired. The non-acid-dissociable functional group refers to a characteristic group that does not cleave in the presence of an acid and does not generate an alkali-soluble group. For example, C1-20 alkyl group, C3-20 cycloalkyl group, C6-20 aryl group, C1-20 alkoxyl group, cyano group, nitro group, hydroxyl group, Examples thereof include a cyclic group, a halogen atom, a carboxyl group, a C1-20 alkylsilyl group, and a functional group selected from the group consisting of these derivatives.

The above compound (A) and compound (B) can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process.

The positive radiation sensitive composition of the present invention can form an amorphous film by spin coating. The dissolution rate of the amorphous film formed by spin-coating the positive radiation-sensitive composition of the present invention in a 2.38 mass% TMAH aqueous solution at 23 ° C. is preferably 5 Å / sec or less, and preferably 0.05 to 5 Å / sec. More preferably, 0.0005 to 5 K / sec is even more preferable. When the dissolution rate is 5 Å / sec or less, it is insoluble in an alkali developer and can be used as a resist. In addition, when the amorphous film has a dissolution rate of 0.0005 K / sec or more, resolution may be improved. This is presumed to be due to the increase in the contrast of the interface between the unexposed portion dissolved in the alkali developer and the exposed portion not dissolved in the alkali developer due to the change in solubility of the cyclic compound before and after exposure. Further, there is an effect of reducing LER and reducing defects.

2.38 mass at 23 ° C. of a portion exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray of an amorphous film formed by spin-coating the solid component of the positive radiation-sensitive composition of the present invention. The dissolution rate in the% TMAH aqueous solution is preferably 10 Å / sec or more, more preferably 10 to 10000 Å / sec, and still more preferably 100 to 1000 Å / sec. When the dissolution rate is 10 Å / sec or more, it can be dissolved in an alkali developer to form a resist. In addition, when the exposed portion has a dissolution rate of 10000 kg / sec or less, resolution may be improved. This is presumed to be because the micro surface portion of the cyclic compound is dissolved and LER is reduced. There is also an effect of reducing defects.

The positive radiation-sensitive composition of the present invention comprises 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent. The solid components are preferably 1 to 50% by weight and the solvent 50 to 99% by weight, more preferably 2 to 40% by weight of the solid component and the solvent 60 to 98% by weight, and particularly preferably 2 to 10% by weight of the solid component and the solvent 90%. ~ 98% by weight.
The sum of the weight of the compound (A) and the weight of the compound (B) is 50 to 99% by weight, preferably 65 to 80% by weight, more preferably 60 to 70% by weight based on the total weight of the solid component. . When the blending ratio is as described above, high resolution is obtained and the line edge roughness is reduced.

（式（７－１）中、Ｒ^１３は、同一でも異なっていても良く、それぞれ独立に、水素原子、直鎖状、分枝状もしくは環状アルキル基、直鎖状、分枝状もしくは環状アルコキシ基、ヒドロキシル基またはハロゲン原子であり；Ｘ^-は、アルキル基、アリール基、ハロゲン置換アルキル基もしくはハロゲン置換アリール基を有するスルホン酸イオンまたはハロゲン化物イオンである。） The acid generator (C) is preferably at least one selected from the group consisting of compounds represented by the following formulas (7-1) to (7-8).

(In formula (7-1), R ¹³ may be the same or different, and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. A group, a hydroxyl group or a halogen atom; X ⁻ is a sulfonate ion or a halide ion having an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.

The compound represented by the formula (7-1) includes triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, diphenyltolylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n- Octane sulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, di-2,4,6-trimethylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-t-butoxyphenyl Sulfonium nonafluoro-n-butanesulfonate, diphenyl-4-hydroxyphenylsulfonium trifluoromethane Sulfonate, bis (4-fluorophenyl) -4-hydroxyphenylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium nonafluoro-n-butanesulfonate, bis (4-hydroxyphenyl) -phenylsulfonium trifluoromethanesulfonate, tri ( 4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tri (4-fluorophenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium benzenesulfonate, diphenyl-2,4,6-trimethylphenyl-p-toluene Sulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2-trifluoromethyl Benzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-4-trifluoromethylbenzenesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-2,4-difluorobenzenesulfonate, diphenyl-2,4,6 Trimethylphenylsulfonium hexafluorobenzenesulfonate, diphenylnaphthylsulfonium trifluoromethanesulfonate, diphenyl-4-hydroxyphenylsulfonium-p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, diphenyl-4-hydroxyphenylsulfonium 10-camphorsulfonate and cyclo (1,3-perfluoropropanedisulfone) at least selected from the group consisting of imidates It is preferably one.

（式（７－２）中、Ｒ^１４は、同一でも異なっていても良く、それぞれ独立に、水素原子、直鎖状、分枝状もしくは環状アルキル基、直鎖状、分枝状もしくは環状アルコキシ基、ヒドロキシル基またはハロゲン原子を表す。Ｘ^-は前記と同様である。）

(In formula (7-2), R ^{14 s} may be the same or different and each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group. A group, a hydroxyl group or a halogen atom, X ⁻ is the same as defined above.)

The compound represented by the formula (7-2) includes bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t -Butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-tert-butylphenyl) iodonium, p-toluenesulfonate, bis (4-tert-butylphenyl) iodoniumbenzenesulfonate, bis (4-tert-butylphenyl) Iodonium-2-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium-4-trifluoromethylbenzenesulfonate, bis (4-tert-butylphenyl) iodonium-2,4-difluorobenzenesulfonate, bis ( 4 t-butylphenyl) iodonium hexafluorobenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octane Sulfonate, diphenyliodonium, p-toluenesulfonate, diphenyliodoniumbenzenesulfonate, diphenyliodonium10-camphorsulfonate, diphenyliodonium-2-trifluoromethylbenzenesulfonate, diphenyliodonium-4-trifluoromethylbenzenesulfonate, diphenyliodonium-2,4- Difluorobenzenesulfonate, diphe Ruiodonium hexafluorobenzenesulfonate, di (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, di (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, di (4-trifluoromethylphenyl) iodonium Perfluoro-n-octanesulfonate, di (4-trifluoromethylphenyl) iodonium, p-toluenesulfonate, di (4-trifluoromethylphenyl) iodoniumbenzenesulfonate and di (4-trifluoromethylphenyl) iodonium 10-camphorsulfonate It is preferably at least one selected from the group consisting of

（式（７－３）中、Ｑはアルキレン基、アリーレン基またはアルコキシレン基であり、Ｒ^１５はアルキル基、アリール基、ハロゲン置換アルキル基またはハロゲン置換アリール基である。）

(In the formula (7-3), Q is an alkylene group, an arylene group or an alkoxylene group, and R ¹⁵ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.)

The compound represented by the formula (7-3) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- ( Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-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) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) ) Naphthylimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- ( 2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- ( 4-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Siimide, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) Naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept Is preferably a 5-En 2,3-dicarboximide and N- at least one selected from the group consisting of (perfluoro--n- octane sulfonyloxy) naphthylimide.

（式（７－４）中、Ｒ^１６は、同一でも異なっていても良く、それぞれ独立に、任意に置換された直鎖、分枝もしくは環状アルキル基、任意に置換されたアリール基、任意に置換されたヘテロアリール基または任意に置換されたアラルキル基である。）

(In the formula (7-4), R ¹⁶ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, optionally A substituted heteroaryl group or an optionally substituted aralkyl group.)

The compound represented by the formula (7-4) is diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone. , Di (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-trifluoromethylphenyl) disulfone It is preferable.

（式（７－５）中、Ｒ^１７は、同一でも異なっていても良く、それぞれ独立に、任意に置換された直鎖、分枝もしくは環状アルキル基、任意に置換されたアリール基、任意に置換されたヘテロアリール基または任意に置換されたアラルキル基である。）

(In the formula (7-5), R ¹⁷ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, optionally A substituted heteroaryl group or an optionally substituted aralkyl group.)

The compound represented by the formula (7-5) is α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino). -Phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile And at least one selected from the group consisting of α- (methylsulfonyloxyimino) -4-bromophenylacetonitrile.

式（７－６）中、Ｒ^１８は、同一でも異なっていても良く、それぞれ独立に、１以上の塩素原子および１以上の臭素原子を有するハロゲン化アルキル基である。ハロゲン化アルキル基の炭素原子数は１～５が好ましい。

In formula (7-6), R ¹⁸ may be the same or different and each independently represents a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The halogenated alkyl group preferably has 1 to 5 carbon atoms.

In the formulas (7-7) and (7-8), R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or cyclopentyl. Group, cycloalkyl group such as cyclohexyl group, alkoxyl group having 1 to 3 carbon atoms such as methoxy group, ethoxy group, propoxy group, or aryl group such as phenyl group, toluyl group, naphthyl group, preferably 6 carbon atoms ~ 10 aryl groups. L ¹⁹ and L ²⁰ are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- Preferred examples include 1,2-quinonediazidosulfonyl groups such as a 6-sulfonyl group. In particular, 1,2-naphthoquinonediazido-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable. p is an integer of 1 to 3, q is an integer of 0 to 4, and 1 ≦ p + q ≦ 5. J ¹⁹ is a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (7-7-1), a carbonyl group, an ester group, an amide group or an ether group. Y ¹⁹ represents a hydrogen atom, an alkyl group or an aryl group, and X ²⁰ each independently represents a group represented by the following formula (7-8-1).

（式（７－８－１）中、Ｚ^２２はそれぞれ独立に、アルキル基、シクロアルキル基またはアリール基であり、Ｒ^２２はアルキル基、シクロアルキル基またはアルコキシル基であり、ｒは０～３の整数である。）

(In the formula (7-8-1), Z ²² each independently represents an alkyl group, a cycloalkyl group or an aryl group, R ²² represents an alkyl group, a cycloalkyl group or an alkoxyl group, and r represents 0-3. Integer.)

Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, 1,3-bis (cyclohexylsulfonylazomethylsulfonyl) propane, 1, 4 -Bis (phenylsulfonylazomethylsulfonyl) butane, 1,6-bis (phenylsulfonylazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyl) Bissulfonyldiazomethanes such as zomethylsulfonyl) decane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4 Halogen-containing triazines such as 6- (bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) isocyanurate Derivatives and the like.

Of the acid generators, acid generators having an aromatic ring are preferable, and acid generators represented by formula (7-1) or (7-2) are more preferable. X in formula (7-1) or (7-2) ^- is an acid generator having a sulfonic acid ion is more preferably an aryl group or a halogen-substituted aryl group, an acid generator having a sulfonate ion having an aryl group Are particularly preferable, and diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluoromethanesulfonate are particularly preferable. LER can be reduced by using the acid generator.
The acid generator (C) can be used alone or in combination of two or more.

In the present invention, an acid diffusion control agent (E) having an action of controlling undesired chemical reaction in an unexposed region by controlling diffusion of an acid generated from an acid generator by irradiation in a resist film. You may mix | blend with a radiation sensitive composition. By using such an acid diffusion controller (E), the storage stability of the radiation-sensitive composition is improved. In addition, the resolution is improved, and a change in the line width of the resist pattern due to fluctuations in the holding time before electron beam irradiation and the holding time after electron beam irradiation can be suppressed, and the process stability is extremely excellent. Examples of such an acid diffusion controller (E) include electron beam radiation decomposable basic compounds such as a nitrogen atom-containing basic compound, a basic sulfonium compound, and a basic iodonium compound. The acid diffusion controller can be used alone or in combination of two or more.
Examples of the acid diffusion controller include nitrogen-containing organic compounds and basic compounds that decompose upon exposure. Examples of the nitrogen-containing organic compound include the following general formula (10):

で表される化合物（以下、「含窒素化合物（Ｉ）」という。）、同一分子内に窒素原子を２個有するジアミノ化合物（以下、「含窒素化合物（ＩＩ）」という。）、窒素原子を３個以上有するポリアミノ化合物や重合体（以下、「含窒素化合物（ＩＩＩ）」という。）、アミド基含有化合物、ウレア化合物、および含窒素複素環式化合物等を挙げることができる。尚、上記酸拡散制御剤は、１種単独で用いてもよく、２種以上を併用してもよい。

(Hereinafter referred to as “nitrogen-containing compound (I)”), a diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (II)”), and a nitrogen atom. Examples thereof include polyamino compounds and polymers having three or more (hereinafter referred to as “nitrogen-containing compound (III)”), amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. In addition, the said acid diffusion control agent may be used individually by 1 type, and may use 2 or more types together.

In the general formula (10), R ⁶¹ , R ⁶² and R ⁶³ each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, or an aralkyl group. The alkyl group, aryl group, or aralkyl group may be unsubstituted or substituted with another functional group such as a hydroxyl group. Here, examples of the linear, branched or cyclic alkyl group include those having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, and specifically include methyl groups, ethyl groups, and n- Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group N-ethylhexyl group, n-nonyl group, n-decyl group and the like. Examples of the aryl group include those having 6 to 12 carbon atoms, and specific examples include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group. Furthermore, examples of the aralkyl group include those having 7 to 19 carbon atoms, preferably 7 to 13 carbon atoms, and specific examples include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.

Specific examples of the nitrogen-containing compound (I) include mono (cyclohexanamine) such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-dodecylamine, cyclohexylamine and the like. ) Alkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine , Methyl-n-dodecylamine, di-n-dodecylmethyl, cyclohexylmethylamine, dicyclohexylamine and other di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n- Pentylamine, tri-n-hexylamine, tri-n-heptylamine, Tri (cyclo) alkylamines such as ri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, dimethyl-n-dodecylamine, di-n-dodecylmethylamine, dicyclohexylmethylamine, tricyclohexylamine Alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, Aromatic amines such as diphenylamine, triphenylamine and 1-naphthylamine can be exemplified.

Specific 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-aminopheny ) -1-methylethyl] benzene, and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like.

Specific examples of the nitrogen-containing compound (III) include polyethyleneimine, polyallylamine, N- (2-dimethylaminoethyl) acrylamide polymer, and the like.
Specific examples of the amide group-containing compound include, for example, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- And methylpyrrolidone.

Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri- Examples thereof include n-butylthiourea.

Specific 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-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline And pyridines such as acridine; and pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2. ] Octane It can be mentioned.

で表されるスルホニウム化合物、および下記一般式（１１－２）： Examples of the basic compound that decomposes upon exposure include the following general formula (11-1):

A sulfonium compound represented by the general formula (11-2):

で表されるヨードニウム化合物等を挙げることができる。

The iodonium compound etc. which are represented by these can be mentioned.

In the general formulas (11-1) and (11-2), R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ and R ⁷⁵ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom. Represents an alkoxyl group, a hydroxyl group or a halogen atom of ˜6. Z ⁻ represents HO ⁻ , R—COO ⁻ (wherein R represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 1 to 6 carbon atoms, or an alkaryl group having 1 to 6 carbon atoms) or the following general formula (11-3):

で表されるアニオンを示す。

An anion represented by

Specific examples of the basic compound that decomposes upon exposure include, for example, triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, diphenyl-4-hydroxyphenyl. Sulfonium acetate, diphenyl-4-hydroxyphenylsulfonium salicylate, bis (4-tert-butylphenyl) iodonium hydroxide, bis (4-tert-butylphenyl) iodonium acetate, bis (4-tert-butylphenyl) iodonium hydro Oxide, bis (4-tert-butylphenyl) iodonium acetate, bis (4-tert-butylphenyl) iodonium salicylate, 4-tert-butyl Eniru 4-hydroxyphenyl iodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyl iodonium acetate, include 4-t-butylphenyl-4-hydroxyphenyl iodonium salicylate and the like.

The blending amount of the acid diffusion controller (E) is preferably 0.001 to 50% by weight, more preferably 0.001 to 10% by weight, still more preferably 0.001 to 5% by weight, based on the total weight of the solid component. 0.001 to 3% by weight is particularly preferred. Within the above range, it is possible to prevent degradation in resolution, pattern shape, dimensional fidelity, and the like. Furthermore, even if the holding time from electron beam irradiation to heating after radiation irradiation becomes longer, the shape of the pattern upper layer portion does not deteriorate. Further, when the blending amount is 10% by weight or less, it is possible to prevent a decrease in sensitivity, developability of an unexposed portion, and the like. Further, by using such an acid diffusion control agent, the storage stability of the radiation-sensitive composition is improved, the resolution is improved, and the holding time before irradiation and the holding time after irradiation are reduced. Changes in the line width of the resist pattern due to fluctuations can be suppressed, and the process stability is extremely excellent.

The positive radiation-sensitive composition of the present invention has, as necessary, other components (F) as a solubility promoter, a dissolution control agent, a sensitizer, and a surface activity as long as the object of the present invention is not impaired. One kind or two or more kinds of additives such as an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be added.

[1] Dissolution Accelerator A low molecular weight dissolution accelerator increases the solubility of a cyclic compound during development when the solubility of a resist base material in an alkali or other developer is too low, and moderately increases the dissolution rate of a cyclic compound during development. It is a component which has the effect | action to make it use in the range which does not impair the effect of this invention. Examples of the dissolution accelerator include low molecular weight phenolic compounds such as bisphenols and tris (hydroxyphenyl) methane. These dissolution promoters can be used alone or in admixture of two or more. The blending amount of the dissolution accelerator is appropriately adjusted depending on the type of resist base material to be used, but resist base material (compound (A) and compound (B), hereinafter referred to as resist base material (R)) 100. The amount per part by weight is preferably 0 to 100 parts by weight, preferably 0 to 30 parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.

[2] Solubility control agent A solubilization control agent is a component having an action of controlling the solubility of the resist base material when the resist base material is too high in alkali or the like to moderately reduce the dissolution rate during development. It is. As such a dissolution control agent, those that do not chemically change in steps such as baking of resist film, irradiation with radiation, and development are preferable. Examples of the dissolution control agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Can be mentioned. These dissolution control agents can be used alone or in combination of two or more.
The blending amount of the dissolution control agent is appropriately adjusted according to the type of the resist base material (R) to be used, but is preferably 0 to 100 parts by weight, preferably 0 to 100 parts by weight per 100 parts by weight of the resist base material (R). 30 parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.

[3] Sensitizer The sensitizer absorbs the energy of the irradiated radiation and transmits the energy to the acid generator (C), thereby increasing the amount of acid generated. It is a component that improves the apparent sensitivity. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes.
These sensitizers can be used alone or in combination of two or more. The blending amount of the sensitizer is appropriately adjusted according to the type of the resist base material (R) to be used, and is preferably 0 to 100 parts by weight, preferably 0 to 100 parts by weight per 100 parts by weight of the resist base material (R). 30 parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.

[4] Surfactant The surfactant is a component having an action of improving the coating property and striation of the positive radiation-sensitive composition of the present invention, the developability of the resist, and the like. Such a surfactant may be anionic, cationic, nonionic or amphoteric. A preferred surfactant is a nonionic surfactant. Nonionic surfactants have better affinity with the solvent used in the production of the radiation-sensitive composition and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers and higher fatty acid diesters of polyethylene glycol, but are not particularly limited. Commercially available products have the following trade names: F-top (manufactured by Gemco), Mega-Fac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass), Examples include Pepol (manufactured by Toho Chemical Industry Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.)
The compounding amount of the surfactant is appropriately adjusted according to the type of the resist base material (R) to be used, but is preferably 0 to 100 parts by weight, preferably 0 to 100 parts by weight per 100 parts by weight of the resist base material (R). 30 parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.

[5] Organic carboxylic acid or phosphorous oxo acid or derivative thereof For the purpose of preventing sensitivity deterioration or improving resist pattern shape, retention stability, etc., organic carboxylic acid or phosphorous oxo acid or derivative thereof as an optional component Can be contained. In addition, it can be used in combination with an acid diffusion controller, or may be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and the like, and derivatives such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di- phosphonic acids such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester or derivatives thereof, phosphinic acid such as phosphinic acid, phenylphosphinic acid and derivatives such as esters thereof. Of these, phosphonic acid is particularly preferred.
The organic carboxylic acid or phosphorus oxo acid or derivative thereof may be used alone or in combination of two or more. The amount of the organic carboxylic acid or phosphorus oxo acid or derivative thereof is appropriately adjusted according to the type of the resist base (R) to be used, but is 0 to 100 weights per 100 parts by weight of the resist base (R). Parts, preferably 0 to 30 parts by weight, more preferably 0 to 10 parts by weight, still more preferably 0 to 2 parts by weight.

[6] The above-mentioned dissolution control agent, sensitizer, surfactant, and other additives other than organic carboxylic acid or phosphorus oxo acid or derivatives thereof. One or more additives other than the above-mentioned dissolution control agent, sensitizer, and surfactant can be blended as necessary within a range not inhibiting the purpose. Examples of such additives include dyes, pigments, and adhesion aids. For example, it is preferable to add a dye or a pigment because the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced. In addition, it is preferable to add an adhesion assistant because the adhesion to the substrate can be improved. Furthermore, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone.

The composition of the positive radiation sensitive composition of the present invention (compound (A) / compound (B) / acid generator (C) / acid diffusion controller (E) / other components (F)) is based on solid matter. % By weight, preferably 10 to 49.989 / 50 to 89.989 / 0.001 to 39.99 / 0.01 to 39.999 / 0 to 39.989,
More preferably, 10 to 49.989 / 50 to 89.989 / 0.001 to 39.99 / 0.01 to 39.999 / 0 to 15,
More preferably, 12 to 35/60 to 70/10 to 25 / 0.01 to 3/0 to 1
Particularly preferred is 12.5 to 17.5 / 60 to 70/10 to 25 / 0.01 to 3/0. When the above composition is used, the performance such as sensitivity, resolution and alkali developability is excellent.

The positive radiation sensitive composition of the present invention is usually obtained by dissolving each component in a solvent at the time of use to obtain a uniform solution, and then filtering with a filter having a pore size of about 0.2 μm, for example, if necessary. Prepared.

Examples of the solvent used in the preparation of the positive radiation-sensitive composition of the present invention include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono- ethylene glycol monoalkyl ether acetates such as n-butyl ether acetate; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl 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 Propylene glycol monoalkyl ether acetates such as propylene glycol; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate Lactic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate, and the like; 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-meth Other esters such as sibutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; aromatics such as toluene and xylene Hydrocarbons; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone, cyclohexanone; N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. Amides; lactones such as γ-lactone and the like can be mentioned, but there is no particular limitation. These solvents can be used alone or in combination of two or more.

The positive radiation-sensitive composition of the present invention can contain a resin that is soluble in an alkaline aqueous solution as long as the object of the present invention is not impaired. Resins that are soluble in an alkaline aqueous solution include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and heavy polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units. A combination, or a derivative thereof may be used. The amount of the resin soluble in the alkaline aqueous solution is appropriately adjusted according to the kind of the cyclic compound to be used, but is preferably 0 to 30 parts by weight, more preferably 0 to 10 parts per 100 parts by weight of the cyclic compound. Parts by weight, more preferably 0 to 5 parts by weight, particularly preferably 0 parts by weight.

[Method of forming resist pattern]
The present invention uses the positive radiation sensitive composition of the present invention to form a resist film on a substrate, to expose the resist film, and to develop the resist film to form a resist pattern. The present invention relates to a resist pattern forming method including a process. The resist pattern obtained by the present invention can also be formed as an upper layer resist in a multilayer resist process.
In order to form a resist pattern, a resist film is formed by applying the radiation-sensitive composition of the present invention on a conventionally known substrate by a coating means such as spin coating, cast coating or roll coating. The conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. Examples of the wiring pattern material include copper, aluminum, nickel, and gold. If necessary, an inorganic and / or organic film may be provided on the substrate. An inorganic antireflection film (inorganic BARC) is an example of the inorganic film. Examples of the organic film include an organic antireflection film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.
Next, the coated substrate is heated as necessary. The heating conditions vary depending on the composition of the radiation sensitive composition, but are preferably 20 to 250 ° C., more preferably 20 to 150 ° C. Heating may improve the adhesion of the resist to the substrate, which is preferable. Next, the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam. The exposure conditions and the like are appropriately selected according to the composition of the radiation sensitive composition. In the present invention, in order to stably form a high-precision fine pattern in exposure, heating is preferably performed after irradiation with radiation. The heating conditions vary depending on the composition of the radiation sensitive composition, but are preferably 20 to 250 ° C., more preferably 20 to 150 ° C.

Next, the exposed resist film is developed with an alkaline developer to form a predetermined resist pattern. Examples of the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and choline. An alkaline aqueous solution in which one or more compounds are dissolved in a concentration of preferably 1 to 10% by mass, more preferably 1 to 5% by mass is used. When the concentration of the alkaline aqueous solution is 10% by mass or less, it is preferable because the exposed portion can be prevented from being dissolved in the developer.
In addition, an appropriate amount of alcohols such as methanol, ethanol, isopropyl alcohol, and the surfactant can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by mass of isopropyl alcohol. This is preferable since the wettability of the developer with respect to the resist can be improved. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans with water after image development.

After forming the resist pattern, the pattern wiring board is obtained by etching. The etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.
Plating can be performed after forming the resist pattern. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.
The residual resist pattern after etching can be peeled off with an organic solvent or a stronger alkaline aqueous solution than the alkaline aqueous solution used for development. Examples of the organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), etc. Examples of the strong alkaline aqueous solution include 1 to 20% by mass sodium hydroxide aqueous solution, A 1 to 20% by mass aqueous potassium hydroxide solution can be mentioned. Examples of the peeling method include a dipping method and a spray method. In addition, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.
The wiring board obtained by the present invention can also be formed by a method of depositing a metal in vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following synthesis examples, the structure of the compound was confirmed by ¹ H-NMR measurement.

<Synthesis Example> Synthesis and Synthesis Example 1 of Compound (B)
Synthesis of CR-1B A well-dried, nitrogen-substituted dropping funnel, Jim Roth condenser, thermometer, and four-necked flask (1000 ml) equipped with a stirring blade were placed under a nitrogen stream under resorcinol (manufactured by Kanto Chemical Co., Ltd.) 22 g, 0.2 mol), 4-isopropylbenzaldehyde (29.6 g, 0.2 mol), and dehydrated ethanol (200 ml) were added to prepare an ethanol solution. This solution was heated to 85 ° C. with a mantle heater while stirring. Next, 75 ml of concentrated hydrochloric acid (35%) was added dropwise over 30 minutes using a dropping funnel, and then stirred at 85 ° C. for 3 hours. After the completion of the reaction, the mixture was allowed to cool and allowed to reach room temperature, and then cooled in an ice bath. After standing for 1 hour, pale yellow target crude crystals were produced, which were filtered off. The crude crystals were washed twice with 500 ml of methanol, filtered and dried under vacuum to obtain the desired product (hereinafter referred to as CR-1B) (45.6 g, yield 95%).
The structure of this compound was analyzed by LC-MS. As a result, f) the molecular weight of the target product was 960. The chemical shift value (δppm, TMS standard) of ¹ H-NMR in a heavy dimethyl sulfoxide solvent is 1.1 to 1.2 (m, 24H), 2.6 to 2.7 (m, 4H), 5 0.5 (s, 4H), 6.0 to 6.8 (m, 24H), 8.4, 8.5 (d, 8H).
Further, g) soluble in an alkali developer (TMAH 2.38 wt%), h) a phenolic hydroxyl group in the molecule, and e) Mw / Mn = 1.00.

Synthesis of CR-2B Synthesis was performed in the same manner as CR-1 except that 4-isopropylbenzaldehyde in the synthesis example of CR-1B was replaced with 4-cyclohexylaldehyde. As a result, CR-2B (50 g, yield 91%) was obtained.
The structure of this compound was analyzed by LC-MS. As a result, f) the molecular weight of the target product was 1121. The chemical shift value (δppm, TMS standard) of ¹ H-NMR in deuterated chloroform solvent is 0.8 to 1.9 (m, 44H), 5.5, 5.6 (d, 4H), 6. It was 0 to 6.8 (m, 24H), 8.4, 8.5 (m, 8H).
Further, g) soluble in an alkali developer (TMAH 2.38 wt%), h) a phenolic hydroxyl group in the molecule, and e) Mw / Mn = 1.00.

Synthesis of CR-1A-EE100 A well-dried, nitrogen-substituted dropping funnel, Jim Roth condenser, thermometer, and four-necked flask (1000 ml) equipped with a stirring blade were placed under a nitrogen stream under CR-1B 9 5.8 g (80 mmol) of ethyl vinyl ether was added dropwise to a solution consisting of .6 g (10 mmol), 2.5 g of pyridinium p-toluenesulfonate, and 400 ml of acetone. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed, and the resulting solid was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 1/3. As a result, 12.2 g of CR-1A-EE100 in which 100 mol% of the hydrogen atoms of the phenolic hydroxyl group were substituted with an ethoxyethyl group was obtained.
As a result of analyzing the structure of this compound by LC-MS, a) the molecular weight of the target compound was 1537. The chemical shift value (δppm, TMS standard) of ¹ H-NMR in the heavy dimethyl sulfoxide solvent of the obtained product is 0.9 to 1.0 (m, 24H), 1.1 to 1.2 (m , 24H), 1.3-1.4 (m, 24H), 2.6-2.7 (m, 4H), 3.3-3.4 (m, 16H), 5.1 (m, 8H) ), 5.5 (s, 4H), 6.0 to 6.8 (m, 24H).
And b) insoluble in an alkali developer (TMAH 2.38 wt%), c) soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) an acid-dissociable reactive group in the molecule. It had a certain ethoxyethyl group, and e) Mw / Mn = 1.00.

Synthesis of CR-1A-CE100 In a four-necked flask (1000 ml) equipped with a sufficiently dry, nitrogen-substituted dropping funnel, Jim Roth condenser, thermometer, and stirring blade in a nitrogen stream under Synthesis Example 1 To a solution consisting of 9.6 g (10 mmol) of the synthesized CR-1B, 2.5 g of pyridinium p-toluenesulfonate, and 400 ml of 1,3-dioxolane, 10.0 g (80 mmol) of cyclohexyl vinyl ether was added dropwise. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed, and the resulting solid was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 1/3. As a result, 12.2 g of CR-1A-CE100 in which 100 mol% of the hydrogen atoms of the phenolic hydroxyl group were substituted with a cyclohexyloxyethyl group was obtained.
As a result of analyzing the structure of this compound by LC-MS, a) the molecular weight of the target compound was 1969. The chemical shift value (δppm, TMS standard) of ¹ H-NMR in the heavy dimethyl sulfoxide solvent of the obtained product is 1.0 to 3.5 (m, 148H), 5.5 (s, 4H), 6.0 to 6.8 (m, 24H).
And b) insoluble in an alkali developer (TMAH 2.38 wt%), c) soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) an acid-dissociable reactive group in the molecule. It had a certain cyclohexyloxyethyl group, and e) Mw / Mn = 1.00.

Synthesis of CR-2A-EE100 In a four-necked flask (1000 ml) equipped with a sufficiently dry, nitrogen-substituted dropping funnel, Jim Roth condenser, thermometer, and stirring blade in a nitrogen stream under Synthesis Example 2A To a solution consisting of 11.2 g (10 mmol) of the synthesized CR-1B, 2.5 g of pyridinium p-toluenesulfonate, and 400 ml of acetone, 5.8 g (80 mmol) of ethyl vinyl ether was added dropwise. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed, and the resulting solid was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 1/3. 12.5 g of CR-2A-EE100 in which 100 mol% of the hydrogen atoms of the phenolic hydroxyl group were substituted with ethoxyethyl groups was obtained.
The structure of this compound was analyzed by LC-MS. As a result, a) the molecular weight of the target compound was 1697. The chemical shift value (δppm, TMS standard) of ¹ H-NMR in the heavy dimethyl sulfoxide solvent of the obtained product is 0.8 to 1.9 (m, 92H), 3.5 (m, 16H), 5.5, 5.6 (d, 12H), 6.0 to 6.8 (m, 24H).
And b) insoluble in an alkali developer (TMAH 2.38 wt%), c) soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) an acid-dissociable reactive group in the molecule. It had a certain ethoxyethyl group, and e) Mw / Mn = 1.00.

Synthesis of CR-2A-CE100 A four-necked flask (1000 ml) equipped with a well-dried dropping funnel purged with nitrogen, Jim Roth condenser, thermometer, and stirring blade was placed in Synthesis Example 2 under a nitrogen stream. To a solution consisting of 11.2 g (10 mmol) of the synthesized CR-2B, 2.5 g of pyridinium p-toluenesulfonate and 400 ml of 1,3-dioxolane, 10.0 g (80 mmol) of cyclohexyl vinyl ether was added dropwise. The reaction was stirred at room temperature for 24 hours. After completion of the reaction, the solvent was removed, and the resulting solid was purified by column chromatography using a mixed solvent of hexane / ethyl acetate = 1/3. There was obtained 13.2 g of CR-2A-CE100 in which 100 mol% of the hydrogen atoms of the phenolic hydroxyl group were substituted with a cyclohexyloxyethyl group.
The structure of this compound was analyzed by LC-MS. As a result, a) the molecular weight of the target compound was 2129. The chemical shift value (δ ppm, TMS standard) of ¹ H-NMR in the heavy dimethyl sulfoxide solvent of the obtained product is 0.8 to 1.9 (m, 148H), 3.5 (m, 8H), 5.5, 5.6 (d, 12H), 6.0 to 6.8 (m, 24H).
And b) insoluble in an alkali developer (TMAH 2.38 wt%), c) soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) an acid-dissociable reactive group in the molecule. It had a certain cyclohexyloxyethyl group, and e) Mw / Mn = 1.00.

Synthesis of CR-1A-EE50 Synthesis was performed in the same manner as CR-1A-EE100 except that the amount of ethyl vinyl ether in the synthesis example of CR-1A-EE100 was changed to half, and 50 mol% of the hydrogen atoms of the phenolic hydroxyl group were ethoxylated. CR-1A-EE50 (mixture) substituted with an ethyl group was obtained.
The obtained compound is b) insoluble in an alkali developer (TMAH 2.38 wt%), c) becomes soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) within the molecule. It has an ethoxyethyl group which is an acid dissociable reactive group.

Synthesis of CR-1A-CE50 Synthesis was performed in the same manner as CR-1A-CE100 except that the amount of ethyl vinyl ether in the synthesis example of CR-1A-CE100 was changed to half, and 50 mol% of the hydrogen atoms of the phenolic hydroxyl group were ethoxylated. CR-1A-CE50 (mixture) substituted with an ethyl group was obtained.
The obtained compound is b) insoluble in an alkali developer (TMAH 2.38 wt%), c) becomes soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) within the molecule. It has a cyclohexyloxyethyl group which is an acid dissociable reactive group.

Synthesis of CR-2A-EE50 Synthesis was performed in the same manner as CR-2A-EE100 except that the amount of ethyl vinyl ether used in the synthesis example of CR-2A-EE100 was changed to half, and 50 mol% of the hydrogen atoms of the phenolic hydroxyl group was cyclohexane. CR-2A-EE50 (mixture) substituted with a siloxyethyl group was obtained.
The obtained compound is b) insoluble in an alkali developer (TMAH 2.38 wt%), c) becomes soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) within the molecule. It has an ethoxyethyl group which is an acid dissociable reactive group.

Synthesis of CR-2A-CE50 Synthesis was performed in the same manner as CR-2A-CE100, except that the amount of ethyl vinyl ether in the synthesis example of CR-2A-CE100 was changed to half, and 50 mol% of the hydrogen atoms of the phenolic hydroxyl group was cyclohexyl. CR-2A-CE50 (mixture) substituted with a siloxyethyl group was obtained.
The obtained compound is b) insoluble in an alkali developer (TMAH 2.38 wt%), c) becomes soluble in an alkali developer (TMAH 2.38 wt%) by the action of an acid, and d) within the molecule. It has a cyclohexyloxyethyl group which is an acid dissociable reactive group.

(Examples 1 to 4 and Comparative Examples 1 to 8)
Patterning test The ingredients listed in Table 1 were mixed to form a uniform solution, and then filtered through a Teflon (registered trademark) membrane filter having a pore size of 0.1 μm to prepare a radiation-sensitive composition. Went. The results are shown in Table 3.
(1) Evaluation of sensitivity After a resist was spin-coated on a clean silicon wafer, pre-exposure baking (PB) was performed in an oven to form a resist film having a thickness of 60 nm. The resist film was irradiated with an electron beam with a line and space setting of 1: 1 at intervals of 100 nm using an electron beam drawing apparatus (ELS-7500, manufactured by Elionix Co., Ltd.). After irradiation, each was heated at a predetermined temperature for 90 seconds and developed in a 2.38 wt% TMAH aqueous solution for 60 seconds. Thereafter, it was washed with water for 30 seconds and dried to form a positive resist pattern. The obtained line and space was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation). The dose amount (μC / cm ² ) at that time was defined as sensitivity.
A: Dose amount ≦ 50 μC / cm ² (excellent sensitivity)
B: 50 μC / cm ² <dose amount ≦ 120 μC / cm ² (good sensitivity)
C: 120 μC / cm ² <dose amount (sensitivity failure)

(2) Evaluation of Line Edge Roughness (LER) Hitachi Semiconductor's SEM Terminal PC V5 offline length measurement software at (300 points in the length direction (0.75 μm) of 1: 1 line and space at 100 nm intervals (( Using Hitachi Science Systems Co., Ltd.), the distance between the edge and the reference line was measured. The standard deviation (3σ) was calculated from the measurement result.
A: LER (3σ) ≦ 3.5 nm (good LER)
C: 3.5 nm <LER (3σ) (not good LER)

From the results of the patterning test, the radiation-sensitive composition using the specific compound (A) and the compound (B) of the present invention is more than the radiation-sensitive composition using the compound (A) composed of the mixture of the comparative example. Sensitivity and LER were found to be good.

In addition, the specific compound (A) and compound (B) of the present invention can be easily manufactured with a purity of 100%, and can be prepared by simply mixing them, so that quality control is easy. On the other hand, the compound (A) composed of the mixture of the comparative example was a mixture, and the composition thereof varied from production to production, making quality control difficult.

(C) Acid generator P-1: Triphenylbenzenesulfonium trifluoromethanesulfonate (Midori Chemical Co., Ltd.)
(E) Acid diffusion controller Q-1 Trioctylamine (Tokyo Chemical Industry Co., Ltd.)
Solvent S-1 Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)

ＰＥＢ：電子線照射後に加熱する際の温度

PEB: Temperature when heating after electron beam irradiation

(Comparative Example 9)
In Example 4, 100 mol% of a cyclohexyloxyethyl group was introduced into polyhydroxystyrene (PHS) (Mw = 8,000; manufactured by Aldrich), which is a polymer, instead of CR-2A-CE100 of compound (A) by a conventional method. A patterning test was performed in the same manner except that PHS-CE100 was used. As a result, LER was determined to be C.

(Comparative Example 10)
A patterning test was conducted in the same manner as in Example 4, except that polyhydroxystyrene (PHS) (Mw = 8,000; manufactured by Aldrich), which is a polymer, was used instead of CR-2B of the compound (B). As a result, LER was determined to be C.

(Comparative Example 11)
In Example 4, PHS-CE100 was used instead of CR-2A-CE100 of compound (A), and polyhydroxystyrene (PHS) (Mw = 8,000), which is a polymer, was used instead of CR-2B of compound (B). A patterning test was conducted in the same manner except that Aldrich was used. As a result, a pattern was not obtained with a dose of 120 μC / cm ² or less.

In each of Comparative Examples 9 to 11, unevenness considered to be due to poor phase solubility was observed in the film obtained by spin coating.
Furthermore, it was suggested that polyhydroxystyrene which is a polymer or polyhydroxystyrene having an acid-dissociable functional group introduced has a molecular weight distribution, which is not preferable from the viewpoint of quality control.

The present invention is preferably used for an acid amplification type low molecular weight positive radiation sensitive composition and a resist pattern forming method using the composition.

Claims (5)

Compound (A) satisfying all the conditions a) to e) below, Compound (B) satisfying all the conditions f) to i) below, visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV) A positive electrode containing an acid generator (C), an acid diffusion controller (E), and a solvent that generate acid directly or indirectly by irradiation with any radiation selected from the group consisting of X-rays, and ion beams Type radiation-sensitive composition, wherein the composition comprises 1 to 80% by weight of a solid component and 20 to 99% by weight of a solvent, and the sum of the weight of the compound (A) and the weight of the compound (B) is A positive-type radiation-sensitive composition that is 50 to 99% by weight of the total weight of solid components.
a) Molecular weight: 400 to 3000
b) Insoluble in alkali developer (tetramethylammonium hydroxide (TMAH) 2.38 wt%) c) Soluble in alkali developer (TMAH 2.38 wt%) by the action of acid d) At least one in the molecule E) 1.00 ≦ Mw / Mn ≦ 1.05 (Mw: number average molecular weight, Mw: weight average molecular weight)
f) Molecular weight: 350-2500
g) Soluble in alkali developer (TMAH 2.38 wt%) h) At least one phenolic hydroxyl group or carboxyl group in the molecule i) 1.00 ≦ Mw / Mn ≦ 1.05 The positive radiation-sensitive composition according to claim 1, wherein the compound (A) is a compound (Aa) in which an acid-dissociable functional group is introduced into all the phenolic hydroxyl groups and carboxyl groups of the compound (B). The positive radiation sensitive composition according to claim 1, wherein the compound (B) is a compound (Bb) in which no acid-dissociable functional group is introduced into all phenolic hydroxyl groups and carboxyl groups. The compound (A) is the compound (Aa), a cyclic compound (A1) represented by the following formula (1A), and the compound (B) is the compound (Bb), The positive radiation-sensitive composition according to claim 1, which is a cyclic compound (B1) represented by the formula (1B).

(In the formula (1A), L is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or an arylene having 6 to 24 carbon atoms. Group, —O—, —OC (═O) —, —OC (═O) O—, —N (R ⁵ ) —C (═O) —, —N (R ⁵ ) —C (═O) O A divalent group selected from the group consisting of —, —S—, —SO—, —SO ₂ — and any combination thereof, and R ¹ is independently an alkyl group having 1 to 20 carbon atoms. Cycloalkyl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxyl group having 1 to 20 carbon atoms, cyano group, nitro group, heterocyclic group, halogen atom and alkylsilyl having 1 to 20 carbon atoms A functional group selected from the group consisting of a group, a substituted methyl group having 2 to 20 carbon atoms, and 1- Substituted ethyl group, 1-substituted n-propyl group having 4 to 20 carbon atoms, 1-branched alkyl group having 3 to 20 carbon atoms, silyl group having 1 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms, carbon An acid-dissociable functional group selected from the group consisting of a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms and an alkoxycarbonylalkyl group, or A hydrogen atom, and R ′ is independently an alkyl group having 2 to 20 carbon atoms, or a group represented by the following formula:

R ⁴ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cyano group. , A nitro group, a heterocyclic group, a functional group selected from the group consisting of a halogen atom and an alkylsilyl group having 1 to 20 carbon atoms, a substituted methyl group having 2 to 20 carbon atoms, or a 1-substitution having 3 to 20 carbon atoms Ethyl group, 1-substituted n-propyl group having 4 to 20 carbon atoms, 1-branched alkyl group having 3 to 20 carbon atoms, silyl group having 1 to 20 carbon atoms, acyl group having 2 to 20 carbon atoms, carbon number An acid-dissociable functional group selected from the group consisting of 2 to 20 1-substituted alkoxyalkyl groups, cyclic ether groups having 2 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms and alkoxycarbonylalkyl groups; R ¹ Others are at least one acid-dissociable functional groups R ^4, R ⁵ is a hydrogen atom or an alkyl group having a carbon number of 1 ~ 20, m is an integer of 1 ~ 4, p is from 0 to 5 It is an integer. )

(In the formula (1B), ^{L A} is independently a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, C3-C20 cycloalkylene group, the number of 6 to 24 carbon atoms Arylene group, —O—, —OC (═O) —, —OC (═O) O—, —N (R ^5A ) —C (═O) —, —N (R ^5A ) —C (═O) A divalent group selected from the group consisting of O—, —S—, —SO—, —SO ₂ — and any combination thereof, and R ^1A is independently alkyl having 1 to 20 carbon atoms. Group, cycloalkyl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxyl group having 1 to 20 carbon atoms, cyano group, nitro group, hydroxyl group, heterocyclic group, halogen atom, carboxyl group, and carbon A functional group selected from the group consisting of alkylsilyl groups of 1 to 20 or a hydrogen atom Ri, R "is independently an alkyl group having 2-20 carbon atoms or the following formula,

R ^4A is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cyano group. , A functional group selected from the group consisting of a nitro group, a heterocyclic group, a hydroxyl group, a halogen atom, a carboxyl group and an alkylsilyl group having 1 to 20 carbon atoms, or a substituted methyl group having 2 to 20 carbon atoms, and 3 to 3 carbon atoms 20 1-substituted ethyl groups, 1-substituted n-propyl groups having 4 to 20 carbon atoms, 1-branched alkyl groups having 3 to 20 carbon atoms, silyl groups having 1 to 20 carbon atoms, 2 to 20 carbon atoms An acid selected from the group consisting of an acyl group, a 1-substituted alkoxyalkyl group having 2 to 20 carbon atoms, a cyclic ether group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, and an alkoxycarbonylalkyl group A dissociative functional ^group, at least one of ^{R 1A} and ^{R 4A} is a phenolic hydroxyl group or carboxyl ^{group, R 5A} is an hydrogen atom or an alkyl group of a carbon number of 1 ~ 20, ^{m A} is 1-4 It is an integer, and p ^A is an integer of 0 to 5. ) A step of forming a resist film on a substrate, a step of exposing the resist film, and developing the resist film to form a resist pattern using the radiation-sensitive composition according to any one of claims 1 to 4. A resist pattern forming method including the step of: