JP2012037774A - Radiation sensitive resin composition and polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition capable of forming a chemically amplified resist film which effectively responds to electron beams or extreme ultraviolet rays and has excellent nano edge roughness, sensitivity, and resolution to stably produce a fine pattern with a high degree of accuracy, and to provide a polymer used therefor.SOLUTION: A radiation sensitive resin composition contains a polymer which comprises at least one of the repeating units represented by the following formulas (I) and (II) and a (meth)acrylate unit having an acid-dissociable alicyclic group in a side chain.

Description

The present invention relates to a radiation sensitive resin composition and a polymer. More specifically, the present invention relates to various kinds of radiation such as KrF excimer laser, ArF excimer laser, F ₂ excimer laser, EUV (extreme) far ultraviolet rays, synchrotron radiation, etc., X-rays, electron beam, etc. The present invention relates to a radiation-sensitive resin composition used as a chemically amplified resist suitable for microfabrication by the method and a polymer used therefor.

  Conventionally, in a manufacturing process of a semiconductor device such as an IC or LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, there is a tendency to shorten the exposure wavelength from g-line to i-line, KrF excimer laser light, and further ArF excimer laser light. Further, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light is also being developed.

  Lithography using an electron beam or EUV light is positioned as a next-generation or next-generation pattern forming technology, and a resist with high sensitivity and high resolution is desired. In particular, high sensitivity is a very important issue for shortening the wafer processing time. However, with regard to resists for electron beams and EUV, if high sensitivity is pursued, not only the resolution is lowered but also the nano edge roughness deteriorates. Therefore, it is strongly desired to develop a resist that simultaneously satisfies these characteristics. It is rare. Nano edge roughness is designed when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. This refers to the deviation that occurs between the dimensions and the actual pattern dimensions. Since the deviation from the design dimension is transferred by an etching process using a resist as a mask and the electrical characteristics are deteriorated, the yield is lowered. In particular, in the ultrafine region of 0.25 μm or less, nano edge roughness is an extremely important improvement issue. High sensitivity, high resolution, good pattern shape and good nanoedge roughness are in a trade-off relationship, and it is very important how to satisfy this simultaneously.

Furthermore, in lithography using KrF excimer laser light, it is also important to satisfy high sensitivity, high resolution, good pattern shape, and good nano edge roughness at the same time. is necessary.
As a resist suitable for a lithography process using KrF excimer laser light, electron beam, or EUV light, a chemically amplified resist using an acid-catalyzed reaction is mainly used from the viewpoint of high sensitivity. , A phenolic polymer (hereinafter referred to as “phenolic acid-decomposable polymer”), which is insoluble or hardly soluble in an aqueous alkali solution and becomes soluble in an aqueous alkaline solution by the action of an acid, and an acid A chemically amplified resist composition comprising a generator is effectively used.

  For these positive resists, compounds that generate sulfonic acid upon irradiation with actinic rays or radiation using a phenolic acid-decomposable polymer copolymerized with an acid-decomposable acrylate monomer (hereinafter referred to as “sulfonic acid generator”) There are some known resist compositions containing For example, positive resist compositions disclosed in Patent Documents 1 to 5 can be exemplified.

US Pat. No. 5,561,194 JP 2001-166474 A JP 2001-166478 A JP 2003-107708 A JP 2001-194792 A

  However, in any combination of the above positive resist compositions etc., high sensitivity, high resolution, good pattern shape, and good nano edge roughness (low roughness) are not satisfied at the same time in the ultrafine region. Is the current situation.

  The present invention has been made in view of the above circumstances, and is effectively sensitive to X-rays such as (extreme) far ultraviolet rays such as KrF excimer laser, ArF excimer laser, EUV, synchrotron radiation, electron beams, etc. A radiation-sensitive resin composition capable of forming a chemically amplified positive resist film that has excellent edge roughness, sensitivity, and resolution, and that can form a fine pattern with high accuracy and stability, and a polymer used therefor are provided. The purpose is to do.

〔一般式（Ｉ）及び（ＩＩ）において、Ｒ_１〜Ｒ_３は、各々独立に、ヒドロキシ基、ハロゲン原子、置換基を有していてもよいアルキル基、シクロアルキル基、アルコキシ基、−Ｓ−Ｒ_６基（Ｒ_６は置換基を有していてもよいアルキル基、又はアリール基を示す。）、又は、ヘテロ原子を２つ以上有する基を示す。ｌは０〜５の整数を示す。ｍは０〜５の整数を示す。ｎは０〜５の整数を示す。Ｒ_７及びＲ_１１は、各々独立に、水素原子、ハロゲン原子、シアノ基、又は置換基を有していてもよいアルキル基を示す。Ｒ_８〜Ｒ_１０は、各々独立に、水素原子、ヒドロキシ基、ハロゲン原子、ニトロ基、カルボキシル基、置換基を有していてもよいアルキル基、アラルキル基、又はアルコキシ基を示す。Ａは、−Ｏ−基、−ＮＲ_１２−基（Ｒ_１２は、水素原子、置換基を有していてもよいアルキル基、又はアリール基を示す。）を示す。Ｅは、置換基を有していてもよいメチレン基、アルキレン基、又はアリーレン基を示す。〕

〔一般式（１）において、Ｒ_１５は水素原子、メチル基、フッ素原子、又はトリフルオロメチル基を示す。Ｒ_１６は置換基を有していてもよい炭素数６〜２２のアリール基を示す。ＸはＹとともに脂環式炭化水素基を形成するのに必要な原子団であり、且つＹは炭素原子である。〕
［２］前記重合体が、更に、下記一般式（２）〜（６）で表される繰り返し単位のうちの少なくとも１種を含有する前記［１］に記載の感放射線性樹脂組成物。

〔一般式（２）〜（６）において、Ｒ_３１は水素原子、ハロゲン原子、シアノ基又は置換基を有していてもよいアルキル基を示す。Ｒ_３２及びＲ_３３は、それぞれ独立に、水素原子又はヒドロキシル基を示す。Ｘは酸不安定基を示す。Ｚはラクトン構造を有する置換基を示す。Ｊは水素原子、炭素数１〜１５のフルオロアルキル基、又は炭素数１〜１５のフルオロアルコール構造を含有する置換基を示す。〕
［３］前記重合体が、更に、下記一般式（７）〜（１０）で表される繰り返し単位のうちの少なくとも１種を含有する前記［１］又は［２］に記載の感放射線性樹脂組成物。

〔一般式（７）〜（１０）において、Ｒ_３１は水素原子、ハロゲン原子、シアノ基又は置換基を有していてもよいアルキル基を示す。Ｘは酸不安定基を示す。Ｇは酸素原子又はカルボニルオキシ基（−Ｃ（＝Ｏ）Ｏ−）を示す。〕
［４］下記一般式（Ｉ）で表される繰り返し単位、及び下記一般式（ＩＩ）で表される繰り返し単位のうちの少なくとも一方を有する重合体（ｐ１）と、
下記一般式（１）で表される繰り返し単位を有する重合体（ｐ２）と、を含有することを特徴とする感放射線性樹脂組成物。

〔一般式（Ｉ）及び（ＩＩ）において、Ｒ_１〜Ｒ_３は、各々独立に、ヒドロキシ基、ハロゲン原子、置換基を有していてもよいアルキル基、シクロアルキル基、アルコキシ基、−Ｓ−Ｒ_６基（Ｒ_６は置換基を有していてもよいアルキル基、又はアリール基を示す。）、又は、ヘテロ原子を２つ以上有する基を示す。ｌは０〜５の整数を示す。ｍは０〜５の整数を示す。ｎは０〜５の整数を示す。Ｒ_７及びＲ_１１は、各々独立に、水素原子、ハロゲン原子、シアノ基、又は置換基を有していてもよいアルキル基を示す。Ｒ_８〜Ｒ_１０は、各々独立に、水素原子、ヒドロキシ基、ハロゲン原子、ニトロ基、カルボキシル基、置換基を有していてもよいアルキル基、アラルキル基、又はアルコキシ基を示す。Ａは、−Ｏ−基、−ＮＲ_１２−基（Ｒ_１２は、水素原子、置換基を有していてもよいアルキル基、又はアリール基を示す。）を示す。Ｅは、置換基を有していてもよいメチレン基、アルキレン基、又はアリーレン基を示す。〕

〔一般式（１）において、Ｒ_１５は水素原子、メチル基、フッ素原子、又はトリフルオロメチル基を示す。Ｒ_１６は置換基を有していてもよい炭素数６〜２２のアリール基を示す。ＸはＹとともに脂環式炭化水素基を形成するのに必要な原子団であり、且つＹは炭素原子である。〕
［５］下記一般式（Ｉ）で表される繰り返し単位、及び下記一般式（ＩＩ）で表される繰り返し単位のうちの少なくとも一方と、
下記一般式（１）で表される繰り返し単位と、を有することを特徴とする重合体。

〔一般式（Ｉ）及び（ＩＩ）において、Ｒ_１〜Ｒ_３は、各々独立に、ヒドロキシ基、ハロゲン原子、置換基を有していてもよいアルキル基、シクロアルキル基、アルコキシ基、−Ｓ−Ｒ_６基（Ｒ_６は置換基を有していてもよいアルキル基、又はアリール基を示す。）、又は、ヘテロ原子を２つ以上有する基を示す。ｌは０〜５の整数を示す。ｍは０〜５の整数を示す。ｎは０〜５の整数を示す。Ｒ_７及びＲ_１１は、各々独立に、水素原子、ハロゲン原子、シアノ基、又は置換基を有していてもよいアルキル基を示す。Ｒ_８〜Ｒ_１０は、各々独立に、水素原子、ヒドロキシ基、ハロゲン原子、ニトロ基、カルボキシル基、置換基を有していてもよいアルキル基、アラルキル基、又はアルコキシ基を示す。Ａは、−Ｏ−基、−ＮＲ_１２−基（Ｒ_１２は、水素原子、置換基を有していてもよいアルキル基、又はアリール基を示す。）を示す。Ｅは、置換基を有していてもよいメチレン基、アルキレン基、又はアリーレン基を示す。〕

〔一般式（１）において、Ｒ_１５は水素原子、メチル基、フッ素原子、又はトリフルオロメチル基を示す。Ｒ_１６は置換基を有していてもよい炭素数６〜２２のアリール基を示す。ＸはＹとともに脂環式炭化水素基を形成するのに必要な原子団であり、且つＹは炭素原子である。〕 The present invention is as follows.
[1] At least one of a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II);
A radiation-sensitive resin composition comprising a polymer having a repeating unit represented by the following general formula (1).

[In General Formulas (I) and (II), R _{1 to} R ₃ each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, —S -R ₆ group (R ₆ represents an optionally substituted alkyl group, or an aryl group.), or a group having a hetero atom or two or more. l represents an integer of 0 to 5. m shows the integer of 0-5. n shows the integer of 0-5. R ₇ and R ₁₁ each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R _{8 to} R ₁₀ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group that may have a substituent, an aralkyl group, or an alkoxy group. A represents an —O— group or an —NR ₁₂ — group (R ₁₂ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group). E shows the methylene group, alkylene group, or arylene group which may have a substituent. ]

[In General Formula (1), R ₁₅ represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group. R ₁₆ represents an aryl group having 6 to 22 carbon atoms which may have a substituent. X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y, and Y is a carbon atom. ]
[2] The radiation sensitive resin composition according to [1], wherein the polymer further contains at least one of repeating units represented by the following general formulas (2) to (6).

[In General Formulas (2) to (6), R ₃₁ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R ₃₂ and R ₃₃ each independently represent a hydrogen atom or a hydroxyl group. X represents an acid labile group. Z represents a substituent having a lactone structure. J represents a hydrogen atom, a fluoroalkyl group having 1 to 15 carbon atoms, or a substituent containing a fluoroalcohol structure having 1 to 15 carbon atoms. ]
[3] The radiation sensitive resin according to [1] or [2], wherein the polymer further contains at least one of repeating units represented by the following general formulas (7) to (10). Composition.

[In General Formulas (7) to (10), R ₃₁ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. X represents an acid labile group. G represents an oxygen atom or a carbonyloxy group (—C (═O) O—). ]
[4] A polymer (p1) having at least one of a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II):
A radiation-sensitive resin composition comprising a polymer (p2) having a repeating unit represented by the following general formula (1).

[In General Formulas (I) and (II), R _{1 to} R ₃ each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, —S -R ₆ group (R ₆ represents an optionally substituted alkyl group, or an aryl group.), or a group having a hetero atom or two or more. l represents an integer of 0 to 5. m shows the integer of 0-5. n shows the integer of 0-5. R ₇ and R ₁₁ each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R _{8 to} R ₁₀ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group that may have a substituent, an aralkyl group, or an alkoxy group. A represents an —O— group or an —NR ₁₂ — group (R ₁₂ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group). E shows the methylene group, alkylene group, or arylene group which may have a substituent. ]

[In General Formula (1), R ₁₅ represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group. R ₁₆ represents an aryl group having 6 to 22 carbon atoms which may have a substituent. X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y, and Y is a carbon atom. ]
[5] At least one of a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II);
And a repeating unit represented by the following general formula (1).

[In General Formulas (I) and (II), R _{1 to} R ₃ each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, —S -R ₆ group (R ₆ represents an optionally substituted alkyl group, or an aryl group.), or a group having a hetero atom or two or more. l represents an integer of 0 to 5. m shows the integer of 0-5. n shows the integer of 0-5. R ₇ and R ₁₁ each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R _{8 to} R ₁₀ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group that may have a substituent, an aralkyl group, or an alkoxy group. A represents an —O— group or an —NR ₁₂ — group (R ₁₂ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group). E shows the methylene group, alkylene group, or arylene group which may have a substituent. ]

[In General Formula (1), R ₁₅ represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group. R ₁₆ represents an aryl group having 6 to 22 carbon atoms which may have a substituent. X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y, and Y is a carbon atom. ]

According to the radiation sensitive resin composition of the present invention, KrF excimer laser, ArF excimer laser, EUV and other (extreme) deep ultraviolet rays, synchrotron radiation and other X-rays and electron beams are effectively sensitive to nano edge roughness, A chemically amplified resist film having excellent sensitivity and resolution and capable of forming a fine pattern with high accuracy and stability can be formed.
The polymer of the present invention is sensitive to X-rays such as (extreme) deep ultraviolet rays such as KrF excimer laser, ArF excimer laser, EUV, synchrotron radiation, and electron beam, and is excellent in nano edge roughness, sensitivity and resolution, It can be suitably used as a polymer component in a radiation sensitive resin composition for forming a chemically amplified resist film capable of forming a fine pattern with high accuracy and stability.

It is a typical top view at the time of seeing a line pattern from the upper part. It is typical sectional drawing of a line pattern shape.

Hereinafter, the present invention will be described in detail.
[1] Radiation sensitive resin composition (i)
The radiation sensitive resin composition (i) of the present invention is characterized by containing a specific polymer.

[1-1] Polymer (A)
The polymer contained in the radiation-sensitive resin composition (i) of the present invention (hereinafter also referred to as “polymer (A)”) is an alkali-insoluble or hardly alkali-soluble polymer, It is a polymer that is easily soluble in alkali. The term “alkali insoluble or hardly soluble in alkali” as used herein refers to alkali development conditions employed when forming a resist pattern from a resist film formed from a radiation-sensitive resin composition containing the polymer (A). Below, when a 100 nm-thick film using only the polymer (A) is developed instead of the resist film, it means that 50% or more of the initial film thickness of the film remains after development.

  The polymer (A) contains at least one of a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II).

〔一般式（Ｉ）及び（ＩＩ）において、Ｒ_１〜Ｒ_３は、各々独立に、ヒドロキシ基、ハロゲン原子、置換基を有していてもよいアルキル基、シクロアルキル基、アルコキシ基、−Ｓ−Ｒ_６基（Ｒ_６は置換基を有していてもよいアルキル基、又はアリール基を示す。）、又は、ヘテロ原子を２つ以上有する基を示す。ｌは０〜５の整数を示す。ｍは０〜５の整数を示す。ｎは０〜５の整数を示す。Ｒ_７及びＲ_１１は、各々独立に、水素原子、ハロゲン原子、シアノ基、又は置換基を有していてもよいアルキル基を示す。Ｒ_８〜Ｒ_１０は、各々独立に、水素原子、ヒドロキシ基、ハロゲン原子、ニトロ基、カルボキシル基、置換基を有していてもよいアルキル基、アラルキル基、又はアルコキシ基を示す。Ａは、−Ｏ−基、−ＮＲ_１２−基（Ｒ_１２は、水素原子、置換基を有していてもよいアルキル基、又はアリール基を示す。）を示す。Ｅは、置換基を有していてもよいメチレン基、アルキレン基、又はアリーレン基を示す。〕

[In General Formulas (I) and (II), R _{1 to} R ₃ each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, —S -R ₆ group (R ₆ represents an optionally substituted alkyl group, or an aryl group.), or a group having a hetero atom or two or more. l represents an integer of 0 to 5. m shows the integer of 0-5. n shows the integer of 0-5. R ₇ and R ₁₁ each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R _{8 to} R ₁₀ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group that may have a substituent, an aralkyl group, or an alkoxy group. A represents an —O— group or an —NR ₁₂ — group (R ₁₂ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group). E shows the methylene group, alkylene group, or arylene group which may have a substituent. ]

As a halogen atom in R < ₁ > -R < ₃ > of general formula (I) and (II), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.
Examples of the alkyl group in R _{1 to} R ₃ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a t-butyl group. Groups and the like. Among these, those having 1 to 4 carbon atoms are preferable.
Examples of the cycloalkyl group in R _{1 to} R ₃ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Among these, those having 5 to 6 carbon atoms are preferable.
Examples of the alkoxy group in R _{1 to} R ₃ include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, and t-butoxy. Groups and the like. Among these, those having 1 to 4 carbon atoms are preferable.
One or more hydrogen atoms in each of the alkyl group, cycloalkyl group and alkoxy group may be substituted. Specific examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), phenyl group, acetoxy group, alkyl group, alkoxy group and the like.

Examples of the alkyl group of R ₆ in the —S—R ₆ group of R _{1 to} R ₃ include, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a 2-methylpropyl group. , 1-methylpropyl group, t-butyl group and the like.
Examples of the aryl group for R ₆ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, and a 1-phenanthryl group. Among these, those having 6 to 12 carbon atoms are preferable.
In addition, one or more hydrogen atoms in each of the alkyl group and aryl group of R ₆ may be substituted with the above-described substituent.

Furthermore, the group having two or more heteroatoms in R _{1 to} R ₃ is not particularly limited, but —OSO ₂ —Rx and —SO ₂ —Rx (Rx each independently has a substituent. An alkyl group, a cycloalkyl group, an alkoxy group, or an aryl group, which may be present, is preferable. The substituent in Rx is preferably a halogen atom.
Specific examples of the group having two or more heteroatoms include groups having structures represented by the following formulas (h1) to (h8). Among these, groups represented by (h1) and (h2) are preferable.

L in general formula (I) and (II) shows the integer of 0-5, Preferably it is an integer of 0-2.
Moreover, m shows the integer of 0-5, Preferably it is an integer of 0-2.
Furthermore, n shows the integer of 0-5, Preferably it is an integer of 0-2.

  In the present invention, each of the general formulas (I) and (II) may have at least one group having two or more heteroatoms. In this case, it is preferable that the total (l + m + n) of l, m and n is 1 to 2.

As a halogen atom in R < ₇ > -R < ₁₁ > of general formula (I) and (II), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.
Examples of the alkyl group in R _{7 to} R ₁₁ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and t-butyl. Groups and the like. Among these, those having 1 to 4 carbon atoms are preferable. One or more hydrogen atoms in the alkyl group may be substituted with the above-described substituent.

Examples of the aralkyl group in R _{8 to} R ₁₀ include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. Among these, those having 6 to 12 carbon atoms are preferable.
Examples of the alkoxy group in R _{8 to} R ₁₀ include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, and t-butoxy. Groups and the like. Among these, those having 1 to 4 carbon atoms are preferable.
In addition, one or more hydrogen atoms in each of the aralkyl group and the alkoxy group in R _{8 to} R ₁₀ may be substituted with the above-described substituent.

Examples of the alkyl group of R ₁₂ in the —NR ₁₂ — group of A in the general formula (II) include, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like. Among these, those having 1 to 6 carbon atoms are preferable.
Examples of the aryl group for R ₁₂ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, and a 1-phenanthryl group. Among these, those having 6 to 12 carbon atoms are preferable.
One or more hydrogen atoms in each of the alkyl group and aryl group in A may be substituted with the above-described substituent.

Examples of the alkylene group in E of the general formula (II) include ethylene group; propylene group such as 1,3-propylene group and 1,2-propylene group; tetramethylene group, pentamethylene group, hexamethylene group, 1- Methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4- And a butylene group. Among these, those having 2 to 6 carbon atoms are preferable.
Examples of the arylene group of E include a phenylene group, a naphthylene group, methylphenylene, ethylphenylene, chlorophenylene group, bromophenylene group, and fluorophenylene group. Among these, those having 6 to 12 carbon atoms are preferable.
In addition, one or more hydrogen atoms in each of the methylene group, the alkylene group, and the arylene group in E may be substituted with the above-described substituent.

  The repeating units (I) and (II) can be obtained by using, for example, compounds represented by the following general formulas (Im) and (II-m) as monomers, respectively.

〔一般式（Ｉ−ｍ）及び（ＩＩ−ｍ）において、Ｒ_１〜Ｒ_３は、各々独立に、ヒドロキシ基、ハロゲン原子、置換基を有していてもよいアルキル基、シクロアルキル基、アルコキシ基、−Ｓ−Ｒ_６基（Ｒ_６は置換基を有していてもよいアルキル基、又はアリール基を示す。）、又は、ヘテロ原子を２つ以上有する基を示す。ｌは０〜５の整数を示す。ｍは０〜５の整数を示す。ｎは０〜５の整数を示す。Ｒ_７及びＲ_１１は、各々独立に、水素原子、ハロゲン原子、シアノ基、又は置換基を有していてもよいアルキル基を示す。Ｒ_８〜Ｒ_１０は、各々独立に、水素原子、ヒドロキシ基、ハロゲン原子、ニトロ基、カルボキシル基、置換基を有していてもよいアルキル基、アラルキル基、又はアルコキシ基を示す。Ａは、−Ｏ−基、−ＮＲ_１２−基（Ｒ_１２は、水素原子、置換基を有していてもよいアルキル基、又はアリール基を示す。）を示す。Ｅは、置換基を有していてもよいメチレン基、アルキレン基、又はアリーレン基を示す。〕

[In General Formulas (Im) and (II-m), R _{1 to} R ₃ each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, or an alkoxy group. A group, —S—R ₆ group (R ₆ represents an optionally substituted alkyl group or aryl group), or a group having two or more heteroatoms; l represents an integer of 0 to 5. m shows the integer of 0-5. n shows the integer of 0-5. R ₇ and R ₁₁ each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R _{8 to} R ₁₀ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group that may have a substituent, an aralkyl group, or an alkoxy group. A represents an —O— group or an —NR ₁₂ — group (R ₁₂ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group). E shows the methylene group, alkylene group, or arylene group which may have a substituent. ]

In the general formulas (Im) and (II-m), R _{1 to} R ₃ , R _{7 to} R ₁₁ , 1, m, n, A, and E are the same as those in the general formulas (I) and (II). _{R 1 ~R 3, R 7 ~R} 11, l, m, n, the same meanings as a and E.

  Specific examples of the monomers represented by the formulas (Im) and (II-m) include, for example, compounds represented by the formulas (I-1) to (I-8), and the formula (II- Examples thereof include compounds represented by 1) to (II-23).

The monomer represented by the general formula (Im) includes, for example, a compound represented by the general formula (Y) and a compound represented by the general formula (YY) as represented by the following reaction formula: Can be produced in a methylene chloride / water mixed solvent.
Moreover, the monomer represented by the general formula (II-m) is represented by the compound represented by the general formula (X) and the general formula (XX) as represented by the following reaction formula, for example. It can be produced by reacting a compound with a methylene chloride / water mixed solvent.

In the general formulas (Y), (YY), (Im), (X), (XX) and (II-m), R _{1 to} R ₃ , R _{7 to} R ₁₁ , l, m, n, A and E have the same meanings as R _{1 to} R ₃ , R _{7 to} R ₁₁ , l, m, n, A, and E in the general formulas (I) and (II).

  In the polymer (A), each of the repeating units (I) and (II) may be contained alone or in combination of two or more.

  The polymer (A) contains a repeating unit represented by the following general formula (1).

〔一般式（１）において、Ｒ_１５は水素原子、メチル基、フッ素原子、又はトリフルオロメチル基を示す。Ｒ_１６は置換基を有していてもよい炭素数６〜２２のアリール基を示す。ＸはＹとともに脂環式炭化水素基を形成するのに必要な原子団であり、且つＹは炭素原子である。〕

[In General Formula (1), R ₁₅ represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group. R ₁₆ represents an aryl group having 6 to 22 carbon atoms which may have a substituent. X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y, and Y is a carbon atom. ]

  In the general formula (1), the number of carbon atoms of the alicyclic hydrocarbon group formed by X and Y is not particularly limited, but is preferably 5 to 25, more preferably 5 to 20, and still more preferably 5 to 5. 15.

  The alicyclic hydrocarbon group may be monocyclic or polycyclic. Specific examples of the structure of the alicyclic moiety include the following structures (a-1) to (a-50).

  In particular, the alicyclic hydrocarbon group formed by X in the general formula (1) together with Y is preferably a group having a monocyclo, bicyclo, tricyclo, or tetracyclo structure.

Specific examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, and cyclododecanyl group; adamantyl group, noradamantyl group Group, decalin residue (decalinyl group), tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group and the like.
Among these, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group; an adamantyl group, a decalin residue, a norbornyl group, and the like are preferable. In particular, a cycloalkyl group having 5 to 15 carbon atoms is preferable.

  The alicyclic hydrocarbon group may be substituted or unsubstituted. Specific examples of the substituent include, for example, hydroxy group, carboxyl group, halogen atom (fluorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl group, etc. Can be mentioned.

Examples of the aryl group having 6 to 22 carbon atoms of R ₁₆ include groups derived from structures such as the following (x-1) to (x-3). When R ₁₆ is a group derived from the following (x-2) (namely, naphthyl group), the bonding position bonded to Y in the general formula (1) is either the 1-position or the 2-position. May be. When R ₁₆ is a group derived from the following (x-3) (ie, anthryl group), the bonding positions bonded to Y in the general formula (1) are the 1-position, 2-position and 9-position. Either may be sufficient.
One or more hydrogen atoms in the aryl group may be substituted. Specific examples of the substituent include, for example, methyl group, ethyl group, hydroxy group, carboxyl group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group) Etc.), alkyloxycarbonyl groups and the like.

  In the polymer (A) of the present invention, the repeating unit (1) is a repeating unit represented by the following general formula (1-1) [hereinafter referred to as “repeating unit (1-1)”. ].

〔一般式（１−１）において、Ｒ_１５は水素原子、メチル基、フッ素原子、又はトリフルオロメチル基を示す。ＸはＹとともに脂環式炭化水素基を形成するのに必要な原子団であり、且つＹは炭素原子である。〕

[In General Formula (1-1), R ₁₅ represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group. X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y, and Y is a carbon atom. ]

  Regarding the “alicyclic hydrocarbon group which X forms with Y” in the general formula (1-1), the explanation of “the alicyclic hydrocarbon group which X forms with Y” in the general formula (1) described above It can be applied as it is.

  Moreover, the said repeating unit (1) can be obtained by using the compound represented by the following general formula (m-1) as a monomer, for example.

〔一般式（ｍ−１）において、Ｒ_１５は水素原子、メチル基、フッ素原子、又はトリフルオロメチル基を示す。Ｒ_１６は置換基を有していてもよい炭素数６〜２２のアリール基を示す。ＸはＹとともに脂環式炭化水素基を形成するのに必要な原子団であり、且つＹは炭素原子である。〕

[In General Formula (m-1), R ₁₅ represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group. R ₁₆ represents an aryl group having 6 to 22 carbon atoms which may have a substituent. X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y, and Y is a carbon atom. ]

In addition, R <_15> , R <_16> , X and Y in General formula (m-1) are synonymous with R <_15> , R < ₁₆ >, X and Y in the said General formula (1).

  The monomer represented by the general formula (m-1) can be produced, for example, by a reaction between a tertiary alcohol compound having a 1-phenylcyclohexanol residue and methacrylic acid chloride.

  In the polymer (A), only one type of repeating unit (1) may be included, or two or more types of repeating units (1) may be included.

  In addition, the polymer (A) in the present invention is represented by the following general formulas (2) to (6) in addition to at least one of the repeating unit (I) and the repeating unit (II) and the repeating unit (1). Repeating units represented [hereinafter referred to as “repeat units (2) to (6)”. ] May be further included.

〔一般式（２）〜（６）において、Ｒ_３１は水素原子、ハロゲン原子、シアノ基又は置換基を有していてもよいアルキル基を示す。Ｒ_３２及びＲ_３３は、それぞれ独立に、水素原子又はヒドロキシル基を示す。Ｘは酸不安定基を示す。Ｚはラクトン構造を有する置換基を示す。Ｊは水素原子、炭素数１〜１５のフルオロアルキル基、又は炭素数１〜１５のフルオロアルコール構造を含有する置換基を示す。〕

[In General Formulas (2) to (6), R ₃₁ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R ₃₂ and R ₃₃ each independently represent a hydrogen atom or a hydroxyl group. X represents an acid labile group. Z represents a substituent having a lactone structure. J represents a hydrogen atom, a fluoroalkyl group having 1 to 15 carbon atoms, or a substituent containing a fluoroalcohol structure having 1 to 15 carbon atoms. ]

When the said polymer (A) contains a repeating unit (2), it decomposes | disassembles by the effect | action of an acid, generate | occur | produces carboxylic acid, and becomes a polymer which becomes alkali-soluble.
Although the acid labile group of X in General formula (2) is not specifically limited, Specifically, the group shown by the following general formula (L1)-(L4), C4-C20 (preferably 4-15) A tertiary alkyl group, a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, and the like.

Here, a broken line shows a bond (hereinafter the same).
In General Formula (L1), R ^L01 and R ^L02 each independently represent a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 18 (preferably 1 to 10) carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, norbornyl group , Tricyclodecanyl group, tetracyclododecanyl group, adamantyl group and the like.
R ^L03 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms (preferably 1 to 10 carbon atoms). For example, linear, branched or cyclic alkyl groups, and those in which some of the hydrogen atoms in these alkyl groups are substituted with hydroxyl groups, alkoxy groups, oxo groups, amino groups, alkylamino groups, etc. Can do. Specific examples include the following substituted alkyl groups.

In the general formula (L1), R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 may be bonded to each other to form a ring together with the carbon atom or oxygen atom to which they are bonded, When forming a ring, R ^L01 , R ^L02 and R ^L03 each represent a methylene group or a linear or branched alkylene group having 2 to 18 carbon atoms (preferably 2 to 10 carbon atoms).

In the general formula (L2), R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms (preferably 4 to 15), each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, and 4 to 20 carbon atoms. An oxoalkyl group or a group represented by the above general formula (L1) is shown.
As the tertiary alkyl group, specifically, a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, a 2-cyclopentylpropan-2-yl group, a 2-cyclohexylpropan-2-yl group, 2- (bicyclo [2.2.1] heptan-2-yl) propan-2-yl group, 2- (adamantan-1-yl) propan-2-yl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl Group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group Examples include groups.
Specific examples of the trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group.
Specific examples of the oxoalkyl group include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, and a 5-methyl-2-oxooxolan-5-yl group.
Moreover, y is an integer of 0-6.

In General Formula (L3), R ^L05 represents a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms that may be substituted, or an aryl group that has 6 to 20 carbon atoms that may be substituted. Show.
Specific examples of the alkyl group which may be substituted include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n- A linear, branched or cyclic alkyl group such as a pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, or a part of hydrogen atoms in these alkyl groups is a hydroxyl group, an alkoxy group, a carboxy group, an alkoxy group. Examples include those substituted with a carbonyl group, an oxo group, an amino group, an alkylamino group, a cyano group, a mercapto group, an alkylthio group, a sulfo group, and the like.
Specific examples of the aryl group which may be substituted include a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a pyrenyl group.
Further, m is 0 or 1, n is an integer of 0 to 3, and satisfies 2 ≦ 2m + n ≦ 3.

In General Formula (L4), R ^L06 represents an ^optionally substituted linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. Show. Specifically, the same thing as ^RL05 can be illustrated.
R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, n-octyl group Group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, etc. A cyclic alkyl group, or a part of hydrogen atoms in these alkyl groups is a hydroxyl group, alkoxy group, carboxy group, alkoxycarbonyl group, oxo group, amino group, alkylamino group, cyano group, mercapto group, alkylthio group, The thing substituted by the sulfo group etc. can be illustrated.
R ^{L07 to} R ^L16 may be bonded to each other to form a ring together with the carbon atom to which they are bonded (for example, R ^L07 and R ^L08 , R ^L07 and R ^L09 , R ^L08 and R ^L10). , R ^L09 and R ^L10 , R ^L11 and R ^L12 , R ^L13 and R ^L14, etc.), in this case, those involved in the bond represent a divalent hydrocarbon group having 1 to 15 carbon atoms, specifically Can be exemplified by those obtained by removing one hydrogen atom from those exemplified for the monovalent hydrocarbon group. R ^{L07 to} R ^L16 may be bonded to each other adjacent to each other to form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and R ^L15 , R ^L13 and R ^L15 etc.).

  Here, specific examples of the linear or branched group among the acid labile groups represented by the general formula (L1) include the following groups.

  Specific examples of the acid labile group represented by the general formula (L1) include cyclic tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, and tetrahydropyran-2-yl group. And 2-methyltetrahydropyran-2-yl group.

  Specific examples of the acid labile group represented by the general formula (L2) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1 1,1-diethylpropyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1 Examples include -ethyl-2-cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

  Specific examples of the acid labile group represented by the general formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec-butylcyclopentyl, 1-cyclohexylcyclopentyl, 1- (4-methoxy-n-butyl) cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl Examples include -1-cyclopenten-3-yl, 3-methyl-1-cyclohexen-3-yl, and 3-ethyl-1-cyclohexen-3-yl.

  As the acid labile group represented by the general formula (L4), groups represented by the following formulas (L4-1) to (L4-4) are particularly preferable.

The broken lines in the general formulas (L4-1) to (L4-4) indicate the coupling position and the coupling direction.
R ^L41 each independently represents a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, A cyclohexyl group etc. can be illustrated.

  In the general formulas (L4-1) to (L4-4), enantiomers and diastereomers may exist, but the general formulas (L4-1) to (L4-4) may exist. ) Represents all of these stereoisomers. These stereoisomers may be used alone or as a mixture.

  For example, the general formula (L4-3) represents one or a mixture of two selected from the groups represented by the following general formulas (L4-3-1) and (L4-3-2). To do.

  The general formula (L4-4) represents one or a mixture of two or more selected from groups represented by the following general formulas (L4-4-1) to (L4-4-4). And

  The above general formulas (L4-1) to (L4-4), (L4-3-1), (L4-3-2) and (L4-4-1) to (L4-4-4) Enantioisomers and enantioisomer mixtures are also shown representatively.

  The bonding directions of (L4-1) to (L4-4), (L4-3-1), (L4-3-2) and (L4-4-1) to (L4-4-4) are respectively By being on the exo side with respect to the bicyclo [2.2.1] heptane ring, high reactivity in the acid-catalyzed elimination reaction is realized (see JP 2000-336121 A). In the production of a monomer having a tertiary exo-alkyl group having a bicyclo [2.2.1] heptane skeleton as a substituent, the following general formulas (L4-1-endo) to (L4-4-endo) are used. In some cases, a monomer substituted with the indicated endo-alkyl group may be included, but in order to achieve good reactivity, the exo ratio is preferably 50 mol% or more, and the exo ratio is 80 mol% or more. More preferably.

  Specific examples of the acid labile group represented by the formula (L4) include the following groups.

Moreover, the tertiary alkyl group having 4 to 20 carbon atoms of the acid labile group in X of the general formula (2), each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, and oxoalkyl having 4 to 20 carbon atoms. Specific examples of the group include the same groups as those described above for R ^L04 .

  Here, the following can be illustrated as a specific repeating unit represented by the said General formula (2).

  Moreover, as a specific repeating unit represented by the said General formula (3), the following can be illustrated.

  Moreover, as a specific repeating unit represented by the said General formula (4), the following can be illustrated.

  Moreover, as a specific repeating unit represented by the said General formula (5), the following can be illustrated.

  Moreover, as a specific repeating unit represented by the said General formula (6), the following can be illustrated.

  Moreover, the polymer (A) in the present invention is represented by the following general formulas (7) to (10) in addition to at least one of the repeating unit (I) and the repeating unit (II) and the repeating unit (1). Repeating units represented [hereinafter referred to as “repeat units (7) to (10)”. ] May be further included. In addition, when the polymer (A) contains at least one of the repeating units (7) to (10), the polymer (A) is one of the repeating units (2) to (6). At least one kind may be further included.

〔一般式（７）〜（１０）において、Ｒ_３１は水素原子、ハロゲン原子、シアノ基又は置換基を有していてもよいアルキル基を示す。Ｘは酸不安定基を示す。Ｇは酸素原子又はカルボニルオキシ基（−Ｃ（＝Ｏ）Ｏ−）を示す。〕

[In General Formulas (7) to (10), R ₃₁ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. X represents an acid labile group. G represents an oxygen atom or a carbonyloxy group (—C (═O) O—). ]

  When the polymer (A) contains the repeating unit (7), it decomposes by the action of an acid to generate a phenolic hydroxyl group and / or a carboxylic acid, thereby giving a polymer that is alkali-soluble. The acid labile group X can be used in various ways. Specifically, the groups represented by the above general formulas (L1) to (L4), a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms. , Each alkyl group may be a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, or the like.

  Specific examples of the repeating unit represented by the general formula (7) include the following.

  The position of substitution of hydroxynaphthalene in the repeating unit (10) and the position of substitution of hydroxyl group in hydroxynaphthalene are arbitrary, but this repeating unit (10) is composed of 6-hydroxy-2-vinylnaphthalene, 4-hydroxy It is preferably derived from -1-vinylnaphthalene or the like. In particular, those derived from 6-hydroxy-2-vinylnaphthalene are preferred.

The polymer (A) in the present invention includes a repeating unit obtained from a monomer containing a carbon-carbon double bond other than those described above, for example, methyl methacrylate, methyl crotonic acid, dimethyl maleate, itaconic acid. Substituted acrylic esters such as dimethyl, unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid, norbornene, norbornene derivatives, tetracyclo [6.2.1.1 ^3,6 . ^0,7 ] dodecene derivatives, cyclic olefins such as norbornadiene, unsaturated acid anhydrides such as itaconic anhydride, acenaphthylene, vinylnaphthalene and other repeating units obtained from other monomers may be contained.

The total content of the repeating units (I) and (II) in the polymer (A) of the present invention is 1 mol% or more when the total of all the repeating units in the polymer (A) is 100 mol%. More preferably, it is 1-20 mol%, More preferably, it is 2-15 mol%. This content is preferably 1 mol% or more from the viewpoint of obtaining good sensitivity.
The content of the repeating unit (1) is preferably 5 mol% or more, more preferably 5 to 50 mol%, when the total of all repeating units in the polymer (A) is 100 mol%. More preferably, it is 10-45 mol%. When this content is 5 mol% or more, the nano edge roughness can be excellent.
The total content of the repeating units (2) to (6) is preferably 5 to 95 mol%, more preferably when the total of all repeating units in the polymer (A) is 100 mol%. Is 10 to 90 mol%, more preferably 10 to 80 mol%. When this content is 5 mol% or more, the nano edge roughness can be excellent.
The total content of the repeating units (7) to (10) is preferably from 5 to 95 mol%, more preferably when the total of all repeating units in the polymer (A) is 100 mol%. Is 10 to 90 mol%, more preferably 10 to 80 mol%. When this content is 5 mol% or more, the nano edge roughness can be excellent.

  Although the synthesis method of the polymer (A) in this invention is not specifically limited, For example, it can obtain by well-known radical polymerization or anionic polymerization. Further, the side chain hydroxystyrene unit in other repeating units can be obtained by subjecting the obtained polymer (A) to hydrolysis of an acetoxy group or the like in the presence of a base or acid in an organic solvent.

  In the radical polymerization, for example, necessary monomers such as the compounds (Im) and (II-m) are stirred in a suitable organic solvent in a nitrogen atmosphere in the presence of a radical polymerization initiator. It can be carried out by heating.

Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), and 2,2′-azobis- (4-methoxy). -2,4-dimethylvaleronitrile) 2,2'-azobismethylbutyronitrile, 2,2'-azobiscyclohexanecarbonitrile, cyanomethylethylazoformamide, 2,2'-azobis (2,4-dimethyl) Azo compounds such as methyl propionate) and 2,2'-azobiscyanovaleric acid; benzoyl peroxide, lauroyl peroxide, 1,1'-bis- (t-butylperoxy) cyclohexane, 3,5,5-trimethyl Examples thereof include organic peroxides such as hexanoyl peroxide and t-butylperoxy-2-ethylhexanoate, and hydrogen peroxide.
In this polymerization, a polymerization aid such as 2,2,6,6-tetramethyl-1-piperidinyloxy, iodine, mercaptan, styrene dimer may be added as necessary.

The reaction temperature in the radical polymerization is not particularly limited, and is appropriately selected depending on the type of initiator and the like (for example, 50 to 200 ° C.). In particular, when an azo initiator or a peroxide initiator is used, a temperature at which the half life of the initiator is about 10 minutes to about 30 hours is preferable, and more preferably, the half life of the initiator is about 30 minutes to about 10 hours. Temperature.
The reaction time varies depending on the type of initiator and the reaction temperature, but the reaction time during which 50% or more of the initiator is consumed is desirable, and in many cases is about 0.5 to 24 hours.

  The anionic polymerization is carried out by, for example, removing necessary monomers such as the compounds (Im) and (II-m) in a suitable organic solvent in a nitrogen atmosphere in the presence of an anionic polymerization initiator. It can be carried out by stirring and maintaining at a predetermined temperature.

  Examples of the anionic polymerization initiator include n-butyl lithium, s-butyl lithium, t-butyl lithium, ethyl lithium, ethyl sodium, 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium. Organic alkali metals such as

The reaction temperature in the anionic polymerization is not particularly limited, and is appropriately selected depending on the kind of the initiator. In particular, when alkyl lithium is used as an initiator, the temperature is preferably −100 to 50 ° C., more preferably −78 to 30 ° C.
The reaction time varies depending on the type of initiator and the reaction temperature, but the reaction time during which 50% or more of the initiator is consumed is desirable, and in many cases is about 0.5 to 24 hours.

  In addition, in the synthesis | combination of the said polymer (A), it is also possible to perform a polymerization reaction by heating and to perform cationic polymerization, without using a polymerization initiator.

Moreover, when introducing a hydroxystyrene unit by hydrolyzing the side chain of the polymer (A), examples of the acid used for the hydrolysis reaction include p-toluenesulfonic acid and its hydrate, methane Organic acids such as sulfonic acid, trifluoromethanesulfonic acid, malonic acid, succinic acid, 1,1,1-fluoroacetic acid; inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, hydrobromic acid; or pyridinium p-toluenesulfonate, ammonium Examples thereof include salts such as p-toluenesulfonate and 4-methylpyridinium p-toluenesulfonate.
Furthermore, examples of the base include inorganic bases such as potassium hydroxide, sodium hydroxide, sodium carbonate, and potassium carbonate; organic bases such as triethylamine, N-methyl-2-pyrrolidone, piperidine, and tetramethylammonium hydroxide.

Examples of the organic solvent used for the polymerization and hydrolysis include ketones such as acetone, methyl ethyl ketone, and methyl amyl ketone; ethers such as diethyl ether and tetrahydrofuran (THF); methanol, ethanol, propanol, and the like. Alcohols; aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated alkyls such as chloroform, bromoform, methylene chloride, methylene bromide, and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cellosolves; dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, etc. Protic polar solvents, and the like.
Among these, acetone, methyl amyl ketone, methyl ethyl ketone, tetrahydrofuran, methanol, ethanol, propanol, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable.

The polymer (A) has a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC), preferably 2000 to 100,000, more preferably 2000 to 40000. More preferably, it is 2000-25000.
Further, the ratio (Mw / Mn) of Mw of the polymer (A) to polystyrene-reduced number average molecular weight (hereinafter also referred to as “Mn”) measured by GPC is usually 1 to 5, more preferably 1 To 3, more preferably 1 to 2.5.

  Since the radiation sensitive resin composition (i) of this invention contains the said polymer (A), it is excellent in a sensitivity. From this point of view, this radiation-sensitive resin composition is effectively sensitive to X-rays such as KrF excimer laser, ArF excimer laser, EUV and the like, and X-rays such as synchrotron radiation and electron beams in the lithography process. In addition, it is possible to form a chemically amplified positive resist film having low roughness, excellent sensitivity and resolution, and capable of forming a fine pattern with high accuracy and stability.

[1-2] Acid Diffusion Control Agent The radiation-sensitive resin composition (i) of the present invention is also referred to as an acid diffusion control agent (hereinafter referred to as “acid diffusion control agent (B)” in addition to the polymer (A). ) Is further preferably contained.
The acid diffusion control agent (B) is a component having an action of controlling a diffusion phenomenon in the resist film (resist film) of an acid generated from the polymer (A) by exposure and suppressing an undesirable chemical reaction in a non-exposed region. It is.
In the radiation sensitive resin composition of the present invention, by adding this acid diffusion controller (B), the storage stability of the resulting radiation sensitive resin composition is improved, and the resist film formed is The resolution can be sufficiently improved. Furthermore, a radiation-sensitive resin composition that can suppress a change in the line width of the resist pattern due to fluctuations in the holding time (PED) from the exposure to the heat treatment after the exposure, and has excellent process stability. can get.

As the acid diffusion controller (B), for example, a nitrogen-containing organic compound or a photosensitive basic compound (photo-degradable basic compound) is preferably used. Of these, it is preferable to use a photosensitive basic compound.
Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (i) (hereinafter referred to as “nitrogen-containing compound (i)”), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as “ Nitrogen-containing compound (ii) ”), polyamino compounds and polymers having three or more nitrogen atoms (hereinafter collectively referred to as“ nitrogen-containing compound (iii) ”), amide group-containing compounds, urea compounds, nitrogen-containing compounds Examples include heterocyclic compounds.

〔一般式（ｉ）において、各Ｒ^１７は、相互に独立に、水素原子、直鎖状、分岐状若しくは環状の置換されていてもよいアルキル基、置換されていてもよいアリール基、又は置換されていてもよいアラルキル基を表す。〕

[In General Formula (i), each R ¹⁷ is independently a hydrogen atom, a linear, branched or cyclic alkyl group which may be substituted, an aryl group which may be substituted, or a substituent. Represents an aralkyl group which may be substituted. ]

  Examples of the nitrogen-containing compound (i) include mono- (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; -Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. Of di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octyl Amine, tri-n-nonylamine, tri-n-decylamine, cyclohexane Tri (cyclo) alkylamines such as sildimethylamine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3 -Methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylaniline Aromatic amines such as

  Examples of the nitrogen-containing compound (ii) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diamino. Diphenyl 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-amino Phenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methyl Ethyl] benzene, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) -2-imidazolidinone, 2-quinoxalinol, N, N, N ′ , N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine and the like are preferable.

  As the nitrogen-containing compound (iii), for example, polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer and the like are preferable.

  Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, and Nt. -Butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, (S)- (-)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxy Piperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbo Rupiperazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′- Diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N′N′-tetra-t-butoxycarbonylhexamethylenediamine, N, N′-di-t-butoxycarbonyl-1 , 7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl-1,9-diaminononane, N, N′-di- t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N N'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenyl In addition to Nt-butoxycarbonyl group-containing amino compounds such as benzimidazole, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, Pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, isocyanuric acid tris (2-hydroxyethyl) and the like are preferable.

  Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, and tri-n-butyl. Thiourea and the like are preferable.

  Examples of the nitrogen-containing heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2. -Imidazoles such as methyl-1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenyl Pyridines such as pyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, 2,2 ′: 6 ′, 2 ″ -terpyridine; piperazine, 1- (2- Piperazines such as (hydroxyethyl) piperazine Pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3- (N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane and the like are preferable.

  The photosensitive basic compound (photo-degradable basic compound) is a component that decomposes in the exposed region and loses basicity, and remains in the unexposed portion without being decomposed. Since such a photosensitive basic compound can effectively use an acid generated in an exposed portion (that is, an exposed region) as compared with a non-photosensitive basic compound, the nano edge roughness and resolution can be reduced. Can be improved.

  The kind of the said photosensitive basic compound is not specifically limited as long as it has the said property. Specifically, for example, compounds represented by the following general formulas (B1) and (B2) can be suitably used. In particular, the compound represented by the following general formula (B1) is preferable.

〔一般式（Ｂ１）及び（Ｂ２）において、Ｒ_１３及びＲ_１４は、それぞれ、１価の有機基である。Ｚ⁻は、Ｒ_１５Ｏ⁻又はＲ_１５ＣＯＯ⁻であり、Ｒ_１５は１価の有機基である。〕

[In General Formulas (B1) and (B2), R ₁₃ and R ₁₄ are each a monovalent organic group. Z ^- _{is, R 15} O ^-, or _R 15 COO ^- and _{is, R 15} is a monovalent organic group. ]

Examples of the monovalent organic group in R ₁₃ and R ₁₄ in the general formulas (B1) and (B2) include a hydrogen atom, a halogen atom, and a C 1-10 alkyl group which may have a substituent, Or the alicyclic hydrocarbon group etc. which may have a substituent are mentioned.

As a C1-C10 alkyl group which may have the said substituent, a methyl group, an ethyl group, n-butyl group, a tert- butyl group, a trifluoromethyl group etc. are mentioned, for example. This alkyl group includes a hydroxy group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc.), alkyloxycarbonyl group. It may be substituted with a substituent such as (t-butoxycarbonylmethyloxy group and the like).
Moreover, as an alicyclic hydrocarbon group which may have the said substituent, the structure of the said general formula (a-1)-(a-50) etc. are mentioned. The alicyclic hydrocarbon group includes a hydroxy group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc.), It may be substituted with a substituent such as an alkyloxycarbonyl group (such as t-butoxycarbonylmethyloxy group).
Furthermore, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among these, it is preferable that said R <_13> and R < ₁₄ > are a hydrogen atom and a tert- butyl group.
In the above formula (B1), all of R ₁₃ may be the same or a part or all of them may be different. In the above formula (B2), R ₁₄ may be the same or different.

Each Z ⁻ in the general formulas (B1) and (B2) is R ₁₅ O ⁻ or R ₁₅ COO ^— .
Examples of the monovalent organic group for R ₁₅ include an alkyl group which may have a substituent and an aryl group which may have a substituent.
In particular, Z ⁻ is preferably CH ₃ COO ⁻ and compounds (Z-1) to (Z-4) represented by the following formulae.

Further, specific examples of the photosensitive basic compound include a triphenylsulfonium compound [compound represented by the above general formula (B1)], in which the anion portion (Z ⁻ ) is CH ₃ COO ⁻ , What is a compound (Z-2) or (Z-3) etc. are mentioned.

  In addition, the said acid diffusion control agent (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, it is preferable that the compounding quantity of an acid diffusion control agent (B) is 15 mass parts or less with respect to 100 mass parts of polymers (A), More preferably, it is 0.001-10 mass parts, More preferably, it is. 0.005 to 5 parts by mass. When the compounding amount of the acid diffusion controller (B) exceeds 15 parts by mass, the sensitivity of the formed resist film and the developability of the exposed part may be deteriorated. On the other hand, if the blending amount is less than 0.001 part by mass, the pattern shape and dimensional fidelity of the formed resist film may be lowered depending on the process conditions.

[1-3] Radiation-sensitive acid generator In addition to the polymer (A), the radiation-sensitive resin composition (i) of the present invention may be decomposed by irradiation with actinic rays or radiation to generate an acid. An acid generating compound may be contained.
The ratio of the total of the repeating units (I) and (II) in the polymer (A) in the present invention to the other acid generating compound is 100/0 to 20/80, preferably 100/0, in molar ratio. -40/60, more preferably 100 / 0-50 / 50.
Other acid-generating compounds include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, or acids by known light used in microresists. Can be selected and used as appropriate.

  For example, S.M. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Diazonium salts described in Baletal, Polymer, 21, 423 (1980), U.S. Pat. Nos. 4,069,055, 4,069,056, Re27,992, and Japanese Patent Application No. 3-140,140. Ammonium salts described in the above, and the like. C. Necker et al., Macromolecules, 17, 2468 (1984), C.I. S. Wenetal, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat. Nos. 4,069,055, 4,069,056, and the like; V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, US Pat. Nos. 339,049, 410,201, JP-A-2-150,848, JP-A-2-296,514, etc. Iodonium salts of V. Crivello et al., Polymer J .; 17, 73 (1985), J. Am. V. Crivello et al. J. et al. Org. Chem. 43, 3055 (1978); R. Wattal, J. et al. PolymerSci. , Polymer Chem. Ed. , 22, 1789 (1984), J. Am. V. Crivello et al., Polymer Bull. 14, 279 (1985), J. Am. V. Crivello et al., Macromolecules, 14 (5), 1141 (1981), J. MoI. V. Crivello et al. PolymerSci. , Polymer Chem. Ed. 17, 2877 (1979), European Patent Nos. 370,693, 3,902,114, 233,567, 297,443, 297,442, US Pat. No. 4,933,377 No. 161,811, No. 410,201, No. 339,049, No. 4,760,013, No. 4,734,444, No. 2,833,827, Yasukuni Patent No. 2, No. 904,626, No. 3,604,580, No. 3,604,581, and the like; V. Crivello et al., Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al. PolymerSci. , Polymer Chem. Ed. , 17, 1047 (1979), etc., selenonium salts, C.I. S. Wenetal, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988) and other onium salts such as arsonium salts, U.S. Pat. No. 3,905,815, JP-B 46-4605, JP-A 48-36281, and JP-A 55-32070. JP, 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62-212401, JP 63-70243, Organic halogen compounds described in JP-A-63-29839 and the like; Meier et al. Rad. Curing, 13 (4), 26 (1986), T.A. P. Gilletal, Inorg. Chem. , 19, 3007 (1980), D.M. Astruc, Acc. Chem. Res. , 19 (12), 377 (1896), JP-A-2-161445, and the like. Hayase et al. PolymerSci. 25, 753 (1987), E.I. Reichmanisetal, J.A. PolymerSci. , Polymer Chem. Ed. , 23, 1 (1985), Q.M. Q. Zhuetal, J. et al. Photochem. 36, 85, 39, 317 (1987), B.R. Amitital, Tetrahedron Lett. , (24) 2205 (1973), D.M. H. R. Bartonetal, J.M. ChemSoc. , 3571 (1965), p. M.M. Collinsetal, J.A. Chem. SoC. Perkin I, 1695 (1975), M .; Rudinstein et al., Tetrahedron Lett. , (17), 1445 (1975), J. MoI. W. Walker et al. Am. Chem. Soc. 110, 7170 (1988), S.A. C. Busmanetal, J.M. ImagingTechnol. 11 (4), 191 (1985), H. et al. M.M. Houlihanetal, Macmolecules, 21, 2001 (1988), P.M. M.M. Collinsetal, J.A. Chem. Soc. , Chem. Commun. 532 (1972), S.A. Hayase et al., Macromolecules, 18, 1799 (1985), E.I. Reichmanisetal, J.A. Electrochem. Soc. , SolidStateSci. Technol. , 130 (6), F.M. M.M. Houlihanetal, Macromolecules, 21, 2001 (1988), European Patent Nos. 0290,750, 046,083, 156,535, 271,851, 0,388,343, U.S. Pat. Photoacid generators having an o-nitrobenzyl type protecting group described in JP-A Nos. 901,710, 4,181,531, JP-A-60-198538, JP-A-53-133022, and the like; TUNOOKA et al., Polymer Preprints Japan, 35 (8), G.M. Berneretal, J. et al. Rad. Curing, 13 (4), W.M. J. et al. Mijsetal, CoatingTechnol. , 55 (697), 45 (1983), Akzo, H .; Adachietal, PolymerPreprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,672, 044,115, 0101,122, US Pat. No. 618,564, Light represented by iminosulfonates described in JP-A-4,371,605, JP-A-4,431,774, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application 3-140109, etc. Examples include compounds that decompose to generate sulfonic acid, and disulfone compounds described in JP-A No. 61-166544.

  Further, a group in which an acid is generated by the light, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, M.P. E. Woodhouse et al. Am. Chem. Soc. 104, 5586 (1982), S .; P. Pappasetal, J.A. ImagingSci. , 30 (5), 218 (1986), S .; Kondo et al., Makromol. Chem. , RapidCommun. , 9, 625 (1988), Y. et al. Yamada et al., Makromol. Chem. 152, 153, 163 (1972), J. Am. V. Crivello et al. PolymerSci. , Polymer Chem. Ed. 17, 3845 (1979), U.S. Pat. No. 3,849,137, Korean Patent No. 3914407, JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, The compounds described in JP-A 63-146038, JP-A 63-163452, JP-A 62-153853, JP-A 63-146029, and the like can be used.

  Further, V.V. N. R. Pillai, Synthesis, (1), 1 (1980), A.M. Abadetal, Tetrahedron Lett. , (47) 4555 (1971), D.M. H. R. Bartonetal, J.M. Chem. Soc. , (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent 126,712, etc., and the like compounds that generate an acid by light can also be used.

Of the other acid-generating compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, those that are particularly effective are described below.
(1) An oxazole derivative represented by the following general formula (PAG1) substituted with a trihalomethyl group or an S-triazine derivative represented by the general formula (PAG2).

In the formula, R ²⁰¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, or —C (Y) ₃ . Y represents a chlorine atom or a bromine atom.

  (2) An iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the general formula (PAG4).

In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Here, preferred substituents include alkyl groups, haloalkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, nitro groups, carboxyl groups, alkoxycarbonyl groups, hydroxy groups, mercapto groups, and halogen atoms.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group. Preferred are aryl groups having 6 to 14 carbon atoms, alkyl groups having 1 to 8 carbon atoms, and substituted derivatives thereof. Preferred substituents are an aryl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group, and a halogen atom. An alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group;

Z ⁻ represents a counter anion and represents a perfluoroalkanesulfonic acid anion such as CF ₃ SO ₃ ^— or a pentafluorobenzenesulfonic acid anion.

Two of R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

  The above onium salts represented by the general formulas (PAG3) and (PAG4) are known. W. Knapczyketal, J. et al. Am. Chem. Soc. 91, 145 (1969), A.A. L. Maycoketal, J.M. Org. Chem. , 35, 2532, (1970), E.I. Goethasetal, Bull. Soc. Chem. Belg. 73, 546 (1964), H .; M.M. Leicester, J.M. Ame. Chem. Soc. 51, 3587 (1929); V. Crivello et al. Polym. Chem. Ed. 18, 2677 (1980), US Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

  (3) A disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6).

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group.

[1-4] Resin having a group that decomposes by the action of an acid and increases the solubility in an alkaline developer. The radiation-sensitive resin composition (i) of the present invention includes, in addition to the polymer (A), A resin having a group that decomposes by the action of an acid and increases the solubility in an alkaline developer (hereinafter, also referred to as other resin (X)) may be contained.
The other resin (X) is a resin having a group that can be decomposed by an acid in the main chain or side chain of the resin, or in both the main chain and the side chain. Among these, a resin having a group capable of decomposing with an acid in the side chain is more preferable.
Preferred groups as the group capable of decomposing with an acid are —COOA ⁰ and —O—B ⁰ groups, and further groups containing these are represented by —R ⁰ —COOA ⁰ or —Ar—O—B ^0. Groups.
Here, A ⁰ is —C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), —Si (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), or —C (R ⁰⁴ ) (R ⁰⁵ ) —O—R. ⁰⁶ groups are shown. B ⁰ represents —A ⁰ or —CO—O—A ⁰ group (R ⁰ , R ^{01 to} R ⁰⁶ , and Ar have the same meanings as described later).

  The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, a tetrahydropyranyl ester group, an enol ether group, an enol ester group, a tertiary alkyl ether group, a tertiary alkyl ether group. An alkyl ester group, a tertiary alkyl carbonate group, and the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group.

Next, as the base resin when these acid-decomposable groups are bonded as side chains, alkali-soluble resins having —OH or —COOH, preferably —R ⁰ —COOH or —Ar—OH groups in the side chains It is. For example, the alkali-soluble resin mentioned later can be mentioned.

The alkali dissolution rate of these alkali-soluble resins is preferably at least 170 kg / sec as measured with 0.261 N tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferred is 330 liters / second or more.
In addition, an alkali-soluble resin having a high transmittance for far ultraviolet light or excimer laser light is preferable from the viewpoint of achieving a rectangular profile. Preferably, the transmittance at 248 nm with a thickness of 1 μm is 20 to 90%.
From such a viewpoint, particularly preferable alkali-soluble resins are o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene). , Part of poly (hydroxystyrene), O-alkylated or O-acylated product, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, and hydrogenated novolac resin.

  Other resins (X) having an acid-decomposable group used in the present invention are disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259 and the like. As described above, the alkali-soluble resin can be obtained by reacting an acid-decomposable group precursor with an acid, or by copolymerizing an acid-decomposable group-bonded alkali-soluble resin monomer with various monomers.

  The content of the group capable of decomposing with an acid includes the number of groups (B) capable of decomposing with an acid in the other resin (X) and the number of alkali-soluble groups not protected by the group capable of decomposing with an acid (S). And represented by B / (B + S). The content is preferably 0.01 to 0.5, more preferably 0.05 to 0.40, and still more preferably 0.05 to 0.30. B / (B + S)> 0.5 is not preferable because it causes film shrinkage after PEB, poor adhesion to the substrate, and scum. On the other hand, B / (B + S) <0.01 is not preferable because a standing wave may remain remarkably on the pattern side wall.

The weight average molecular weight (Mw) of the other resin (X) is preferably in the range of 2,000 to 200,000. If it is less than 2,000, the film loss is large due to the development of the unexposed area. More preferably, it is the range of 5,000-100,000, More preferably, it is the range of 8,000-50,000. Further, the dispersity (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 2.0, and particularly preferably 1.0 to 1.6. , Heat resistance and image formability (pattern profile, defocus latitude, etc.) are improved.
Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.

  Moreover, you may use other resin (X) in mixture of 2 or more types. The amount of the resin (X) used in the present invention is 40 to 99% by mass, preferably 60 to 95% by mass, based on the total mass (excluding the solvent) of the radiation-sensitive resin composition. Furthermore, in order to adjust alkali solubility, you may mix alkali-soluble resin which does not have the group which can be decomposed | disassembled with an acid.

[1-5] Alkali-soluble resin The radiation-sensitive resin composition (i) of the present invention is a resin that is insoluble in water and soluble in an aqueous alkali solution (hereinafter referred to as “polymer (A)” and other resin (X)). , Also referred to as an alkali-soluble resin).
Examples of the alkali-soluble resin include novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen or alkyl-substituted. Polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, partially O-alkylated product of hydroxyl group of polyhydroxystyrene (for example, 5 to 30 mol%) O-methylated product, O- (1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O- (t-butoxycarbonyl) methylated product, etc.) or O- Acylates (eg, 5-30 mol% o-acetate) A styrene-maleic anhydride copolymer, a styrene-hydroxystyrene copolymer, an α-methylstyrene-hydroxystyrene copolymer, a carboxyl group-containing methacrylic resin, and Examples thereof include, but are not limited to, derivatives thereof.
Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrenes, partially O-alkylated polyhydroxystyrenes, Alternatively, O-acylated product, styrene-hydroxystyrene copolymer, and α-methylstyrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a predetermined monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

  Examples of the predetermined monomer include cresols such as phenol, m-cresol, p-cresol, o-cresol, and xylenol such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, and 2,3-xylenol. , Alkylphenols such as m-ethylphenol, p-ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol Alkoxyphenols such as 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, p-butoxyphenol Kind Bisalkylphenols such as 2-methyl-4-isopropylphenol, hydroxyaromatic compounds such as m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, naphthol alone or 2 It can be used by mixing more than one type, but is not limited thereto.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o. -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p -N-butylbenzaldehyde, furfural, chloroacetaldehyde and this These acetals, for example, chloroacetaldehyde diethyl acetal and the like can be used, and among these, formaldehyde is preferably used.
These aldehydes may be used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The novolak resin thus obtained preferably has a weight average molecular weight in the range of 1,000 to 30,000. If it is less than 1,000, the film loss after development in the unexposed area is large, and if it exceeds 30,000, the developing speed becomes low. Particularly preferred is the range of 2,000 to 20,000.
Moreover, the weight average molecular weights of the said polyhydroxystyrene other than a novolak resin, its derivative (s), and a copolymer are 2000 or more, Preferably it is 5000-200000, More preferably, it is 10000-100,000. Moreover, 25000 or more is preferable from a viewpoint of improving the heat resistance of a resist film.
Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.
Two or more kinds of the alkali-soluble resins may be mixed and used. The usage-amount of alkali-soluble resin is 40-97 mass% on the basis of the total mass (except a solvent) of a radiation sensitive resin composition, Preferably it is 60-90 mass%.

[1-6] Low-molecular acid-decomposable dissolution inhibiting compound The radiation-sensitive resin composition (i) of the present invention may contain a low-molecular acid-decomposable dissolution inhibiting compound in addition to the polymer (A). Good.
The acid-decomposable dissolution inhibiting compound has at least two groups capable of decomposing with an acid in its structure, and a bonding atom excluding the acid-decomposable group at a position where the distance between the acid-decomposable groups is farthest. Is a compound that passes through at least eight.
In the present invention, the acid-decomposable dissolution inhibiting compound preferably has at least two groups capable of decomposing with an acid in the structure, and the acid-decomposable group is located at a position where the distance between the acid-decomposable groups is farthest. A compound having at least 10, more preferably at least 11, and more preferably at least 12 linking atoms other than the above, or a position having at least 3 acid-decomposable groups, and the distance between the acid-decomposable groups being the most distant In the compound, at least 9, preferably at least 10, and more preferably at least 11 bonding atoms excluding the acid-decomposable group. Moreover, the upper limit with the said preferable bond atom is 50 pieces, More preferably, it is 30 pieces.
In the present invention, when the acid-decomposable dissolution inhibiting compound has 3 or more, preferably 4 or more acid-decomposable groups, and also has 2 acid-decomposable groups, the acid-decomposable groups are mutually present. In the case where the distance is more than a certain distance, the dissolution inhibiting property for the alkali-soluble resin is remarkably improved.
The distance between the acid-decomposable groups in the present invention is indicated by the number of via-bonded atoms excluding the acid-decomposable group. For example, in the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonding atoms, and in the compound (3), there are 12 bonding atoms.

The acid-decomposable dissolution inhibiting compound may have a plurality of acid-decomposable groups on one benzene ring, but preferably one acid-decomposable group on one benzene ring. It is a compound comprised from the skeleton which has.
Furthermore, the molecular weight of the acid-decomposable dissolution inhibiting compound is 3,000 or less, preferably 500 to 3,000, and more preferably 1,000 to 2,500.

In a preferred embodiment of the present invention, groups capable of decomposing by an acid, i.e. ^-COO-A 0, examples of the group include a ^{-O-B 0 group,} -R ^{0 -COO-A 0,} or -Ar-O- groups represented by B ⁰ the like.
Here, A ⁰ is —C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), —Si (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), or —C (R ⁰⁴ ) (R ⁰⁵ ) —O—. ^R06 group is shown. B ⁰ represents A ⁰ or a —CO—O—A ⁰ group.
R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ⁰⁶ represents an alkyl group Or an aryl group is shown. However, at least two of R ^{01 to} R ⁰³ are groups other than hydrogen atoms, and two groups of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ are bonded to form a ring. Also good. R ⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and —Ar— represents a divalent or higher valent which may have a monocyclic or polycyclic substituent. Indicates an aromatic group.

Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, or a t-butyl group. Those having 3 to 10 carbon atoms such as propyl group, cyclobutyl group, cyclohexyl group and adamantyl group are preferred, and the alkenyl group has 2 to 4 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Those having 6 to 14 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl, and anthracenyl groups are preferable.
Substituents include hydroxyl groups, halogen atoms (fluorine, chlorine, bromine, iodine), nitro groups, cyano groups, the above alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, n -Alkoxy groups such as butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group, cumyl group, and aralkyloxy groups Acyl group such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, valeryl group, acyloxy group such as butyryloxy group, alkenyl group, alkenyl such as vinyloxy group, propenyloxy group, allyloxy group, butenyloxy group, etc. Oxy group, allee above It can be exemplified group, an aryloxy group such as phenoxy group, aryloxycarbonyl group such as benzoyloxy group.

  The group that can be decomposed by an acid is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, or a tertiary alkyl ester group. And tertiary alkyl carbonate groups. More preferred are tertiary alkyl ester groups, tertiary alkyl carbonate groups, cumyl ester groups, and tetrahydropyranyl ether groups.

As the acid-decomposable dissolution inhibiting compound, JP-A-1-289946, JP-A-1-289947, JP-A-2-2560, JP-A-3-128959, JP-A-3-158855, JP-A-3 JP-A-3-179353, JP-A-3-191351, JP-A-3-200251, JP-A-3-2000025, JP-A-3-200233, JP-A-3-200454, JP-A-3-200355, JP-A-3-22035. No. 259149, JP-A-3-279958, JP-A-3-279959, JP-A-4-1650, JP-A-4-1651, JP-A-4-11260, JP-A-4-12356, JP-A-4-12357. No. 3, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-230790, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-52732 No. 4-103215, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1077885, Japanese Patent Application No. 4-1078889, Japanese Patent Application No. 4-152195, etc. Included are compounds in which some or all of the phenolic OH groups are bonded and protected by the groups shown above, -R ⁰ -COO-A ⁰ or B ⁰ groups.

  More preferably, JP-A-1-289946, JP-A-3-128959, JP-A-3-158855, JP-A-3-179353, JP-A-3-200261, JP-A-3-200252, JP-A-3-22052. JP-A No. 200255, JP-A-3-259149, JP-A-3-279958, JP-A-4-1650, JP-A-4-11260, JP-A-4-12356, JP-A-4-12357, JP-A-4-12357. No. 25157, Japanese Patent Application No. 4-103215, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1077885, Japanese Patent Application No. 4-1078889, and Japanese Patent Application No. 4-152195. The thing using is mentioned.

  More specifically, compounds represented by the following general formulas [I] to [XVI] are exemplified.

R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ , R ^130, which may be the same or different, are a hydrogen atom, —R ⁰ —COO—C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or —CO—O—C ( R ⁰¹ ) (R ⁰² ) (R ⁰³ ), provided that R ⁰ , R ⁰¹ , R ⁰² and R ⁰³ are as defined above.

R ¹⁰⁰ : —CO—, —COO—, —NHCONH—, —NHCOO—, —O—, —S—, —SO—, —SO ₂ —, —SO ₃ —, or

Here, G = 2 to 6, provided that when G = 2, at least one of R ¹⁵⁰ and R ¹⁵¹ is an alkyl group,
R ¹⁵⁰ , R ¹⁵¹ may be the same or different and are a hydrogen atom, an alkyl group, an alkoxy group, —OH, —COOH, —CN, a halogen atom, —R ¹⁵² —COOR ¹⁵³ or —R ¹⁵⁴ —OH,
R ¹⁵² , R ¹⁵⁴ : an alkylene group,
R ¹⁵³ : a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group,
^{R 99, R 103 ~R 107,} R 109, R 111 ~R 118, R 121 ~R 123, R 128 ~R 129, R 131 ~R 134, R 138 ~R 141 and ^{R 143:} may be the same or different Well, hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, halogen atom, nitro group, carboxyl group, cyano group, or -N (R ¹⁵⁵ ) ( ^R156 ) ( ^R155 , ^R156 : H, an alkyl group, or an aryl group)
R ¹¹⁰ : a single bond, an alkylene group, or

R ¹⁵⁷ , R ¹⁵⁹ : may be the same or different, a single bond, an alkylene group, —O—, —S—, —CO—, or a carboxyl group,
R ¹⁵⁸ : hydrogen atom, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, nitro group, hydroxyl group, cyano group, or carboxyl group, provided that the hydroxyl group is an acid-decomposable group (for example, t-butoxycarbonylmethyl group) , Tetrahydropyranyl group, 1-ethoxy-1-ethyl group, 1-t-butoxy-1-ethyl group).

R ¹¹⁹ and R ¹²⁰ may be the same or different, and a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group in this application refers to an alkyl group having 1 to 4 carbon atoms,
R ^{124 to} R ¹²⁷ : may be the same or different and each represents a hydrogen atom or an alkyl group,
R ^{135 to} R ¹³⁷ : may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or an acyloxy group,
R ¹⁴² : a hydrogen atom, —R ⁰ —COO—C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or —CO—O—C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), or

R ¹⁴⁴ and R ¹⁴⁵ may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower haloalkyl group, or an aryl group,
R ^{146 to} R ¹⁴⁹ : may be the same or different and are a hydrogen atom, hydroxyl group, halogen atom, nitro group, cyano group, carbonyl group, alkyl group, alkoxy group, alkoxycarbonyl group, aralkyl group, aralkyloxy group, acyl group An acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that each of the four substituents having the same symbol may not be the same group,
Y: —CO— or —SO ₂ —,
Z, B: single bond, or -O-,
A: a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group,
E: single bond or oxymethylene group,
a to z, a1 to y1: when plural, the groups in () may be the same or different,
a to q, s, t, v, g1 to i1, k1 to m1, o1, q1, s1, u1: 0 or an integer of 1 to 5,
r, u, w, x, y, z, a1 to f1, p1, r1, t1, v1 to x1: 0 or an integer of 1 to 4,
j1, n1, z1, a2, b2, c2, d2: 0 or an integer of 1 to 3,
at least one of z1, a2, c2, and d2 is 1 or more,
y1: an integer from 3 to 8,
(A + b), (e + f + g), (k + l + m), (q + r + s), (w + x + y), (c1 + d1), (g1 + h1 + i1 + j1), (o1 + p1),
(S1 + t1) ≧ 2,
(J1 + n1) ≦ 3,
(R + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1 + f1), (p1 + r1), (t1 + v1), (x1 + w1) ≦ 4
However, in the case of the general formula [V], (w + z), (x + a1) ≦ 5,
(A + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q + t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1) ), (O1 + q1), (s1 + u1) ≦ 5,
Represents.

  The addition amount of the dissolution inhibiting compound is 3 to 50% by mass, preferably 5 to 40% by mass, and more preferably 10 to 35% by mass with respect to 100 parts by mass of the polymer (A).

[1-7] Other components The radiation-sensitive resin composition (i) of the present invention may further include a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, and a developer as necessary. A compound having two or more phenolic OH groups that promote solubility can be contained.

  The compound having 2 or more phenolic OH groups (phenol compound) is preferably a phenol compound having a molecular weight of 1000 or less. Further, it is necessary to have at least two phenolic hydroxyl groups in the molecule, but if this exceeds 10, the effect of improving the development latitude is lost. Further, when the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the film thickness dependency is large, and the development latitude tends to be narrow. If this ratio exceeds 1.4, the stability of the composition deteriorates, and it is difficult to obtain high resolution and good film thickness dependency.

  The addition amount of the phenol compound is 2 to 50% by mass, more preferably 5 to 30% by mass with respect to 100 parts by mass of the polymer (A). When the amount exceeds 50% by mass, the development residue is deteriorated, and a new defect that the pattern is deformed during development is not preferable.

  Such a phenol compound having a molecular weight of 1000 or less can be easily synthesized by those skilled in the art with reference to the methods described in, for example, JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. can do.

  Specific examples of the phenol compound include resorcin, phloroglucin, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4,3 ′, 4 ′, 5. '-Hexahydroxybenzophenone, acetone-pyrogallol condensation resin, fluoroglucoside, 2,4,2', 4'-biphenyltetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2 ', 4 , 4′-tetrahydroxydiphenyl ether, 2,2 ′, 4,4′-tetrahydroxydiphenyl sulfoxide, 2,2 ′, 4,4′-tetrahydroxydiphenylsulfone, tris (4-hydroxyphenyl) methane, 1 , 1-bis (4-hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzili ) Bisphenol, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1- Ethyl-4-isopropylbenzene, 1,2,2-tris (hydroxyphenyl) propane, 1,1,2-tris (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, para [α, α, α ′, α′-tetrakis (4- Hydroxyphenyl)]-xylene and the like. In addition, the compound which can be used by this invention is not limited to these.

  Examples of the dye include oily dyes and basic dyes. Specifically, oil yellow # 101, oil yellow # 103, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, oil black T-505 (orientated chemistry) Kogyo Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI522015), and the like.

Further, by adding a spectral sensitizer as listed below, the photoacid generator used is sensitized to a longer wavelength region than the far ultraviolet, which has no absorption, so that the radiation-sensitive resin composition of the present invention is i. Or sensitivity can be given to g line. Specific examples of suitable spectral sensitizers include benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, and pyrene. Perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4 -Nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert- Tyranthraquinone 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5,7 -Dimethoxycarbonylcoumarin) and coronene, but are not limited thereto.
These spectral sensitizers can also be used as a light absorber for far ultraviolet light as a light source. In this case, the light-absorbing agent reduces the reflected light from the substrate and reduces the influence of multiple reflection in the resist film, thereby exhibiting the effect of improving the standing wave.

[1-8] Solvent Examples of the solvent used in the radiation-sensitive resin composition (i) of the present invention include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, and ethylene glycol monomethyl ether. , Ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethoxypropionic acid Ethyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrole Emissions, tetrahydrofuran and the like are preferably used. These solvents may be used alone or in combination of two or more.

In addition, a surfactant can be added to the solvent.
Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene Polyoxyethylene alkyl allyl ethers such as nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as rate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, Ftop EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), MegaFuck F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Florad FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S- 382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and other fluorosurfactants, organosiloxane polymers KP341 (Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or Acrylic acid-based (co) polymer Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.).
The compounding quantity of surfactant is 2 mass parts or less normally with respect to 100 mass parts of solid content in the composition of this invention, Preferably it is 1 mass part or less.
These surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, it is preferable that the compounding quantity of the solvent in the radiation sensitive composition of this invention is a quantity from which the total solid content concentration in a composition will be 1-70 mass%, More preferably, it is 1-15 mass%. In an amount of 1 to 10% by mass.

  The radiation-sensitive composition of the present invention can be prepared by uniformly dissolving necessary components such as the polymer (A) other than the solvent in the solvent so that the total solid content concentration is in the above range. it can. In addition, after preparing in this way, it is preferable to filter with a filter with a pore diameter of about 0.2 μm, for example.

[2] Radiation sensitive resin composition (ii)
The radiation sensitive resin composition (ii) of the present invention is characterized by containing specific polymers (p1) and (p2).

[2-1] Polymer component (P)
The radiation-sensitive resin composition (ii) of the present invention includes, as a polymer component (hereinafter, also referred to as “polymer component (P)”), the repeating unit (I) and the repeating unit (II). The polymer (p1) which has at least one of these is contained.
In the polymer (p1), each of the repeating units (I) and (II) may be included alone or in combination of two or more.
In addition, this polymer (p1) does not contain the said repeating unit (1).

The polymer (p1) may further include at least one of the repeating units (2) to (10) in addition to at least one of the repeating units (I) and (II). .
One of these repeating units (2) to (10) may be included, or two or more thereof may be included.

The total content of the repeating units (I) and (II) in the polymer (p1) is 1 mol% or more when the total of all the repeating units in the polymer (p1) is 100 mol%. Is more preferable, more preferably 1 to 30 mol%, still more preferably 2 to 20 mol%. This content is preferably 1 mol% or more from the viewpoint of obtaining good sensitivity.
The total content of the repeating units (2) to (6) is preferably 10 to 95 mol%, more preferably, when the total of all repeating units in the polymer (p1) is 100 mol%. Is 20 to 95 mol%, more preferably 30 to 95 mol%. When the content is 10 to 95 mol%, the nano edge roughness can be excellent.
The total content of the repeating units (7) to (10) is preferably from 5 to 90 mol%, more preferably when the total of all repeating units in the polymer (p1) is 100 mol%. Is 5 to 80 mol%, more preferably 5 to 70 mol%. When this content is 5-90 mol%, it can be excellent in nano edge roughness.

  Although the synthesis method of a polymer (p1) is not specifically limited, For example, it can obtain by well-known radical polymerization or anionic polymerization. Further, the side chain hydroxystyrene unit in other repeating units can be obtained by subjecting the obtained polymer (p1) to hydrolysis of an acetoxy group or the like in the presence of a base or an acid in an organic solvent.

The polymer (p1) has a polystyrene-reduced weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC), preferably 1000 to 30000, more preferably 1500 to 20000. More preferably, it is 2000-10000.
Further, the ratio (Mw / Mn) of Mw of the polymer (A) to polystyrene-reduced number average molecular weight (hereinafter also referred to as “Mn”) measured by GPC is usually 1 to 5, more preferably 1 To 3, more preferably 1 to 2.5.

Furthermore, the radiation sensitive resin composition (ii) of this invention contains the polymer (p2) which has the said repeating unit (1) as said polymer component (P).
In this polymer (p2), only one type of repeating unit (1) may be contained, or two or more types may be contained.
The polymer (p2) does not contain the repeating unit (I) or (II).

  The polymer (p2) is an alkali-insoluble or hardly alkali-soluble polymer, and is a polymer that becomes readily alkali-soluble by the action of an acid. The term “alkali-insoluble or alkali-insoluble” as used herein refers to alkali development conditions employed when a resist pattern is formed from a resist film formed from a radiation-sensitive resin composition containing the polymer (p2). Below, when a 100 nm-thick film using only the polymer (p2) is developed instead of the resist film, it means that 50% or more of the initial film thickness of the film remains after development.

The polymer (p2) may further contain at least one of the repeating units (2) to (10) in addition to the repeating unit (1).
One of these repeating units (2) to (10) may be included, or two or more thereof may be included.

The content of the repeating unit (1) in the polymer (p2) is preferably 5 mol% or more, more preferably when the total of all repeating units in the polymer (p2) is 100 mol%. It is 5-90 mol%, More preferably, it is 10-60 mol%. When this content is 5 mol% or more, the nano edge roughness can be excellent.
The total content of the repeating units (2) to (6) is preferably 10 to 95 mol%, more preferably, when the total of all repeating units in the polymer (p2) is 100 mol%. Is 20 to 95 mol%, more preferably 30 to 95 mol%. When the content is 10 to 95 mol%, the nano edge roughness can be excellent.
The total content of the repeating units (7) to (10) is preferably from 5 to 90 mol%, more preferably when the total of all repeating units in the polymer (p2) is 100 mol%. Is 5 to 80 mol%, more preferably 10 to 70 mol%. When this content is 5-90 mol%, it can be excellent in nano edge roughness.

  Although the synthesis method of a polymer (p2) is not specifically limited, For example, it can obtain by well-known radical polymerization or anionic polymerization. Further, the side chain hydroxystyrene unit in other repeating units can be obtained by subjecting the obtained polymer (p2) to hydrolysis of an acetoxy group or the like in the presence of a base or an acid in an organic solvent.

The polymer (p2) has a polystyrene-equivalent weight average molecular weight (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC), preferably 1000 to 30000, more preferably 1500 to 20000. More preferably, it is 2000-10000.
Further, the ratio (Mw / Mn) of Mw of the polymer (A) to polystyrene-reduced number average molecular weight (hereinafter also referred to as “Mn”) measured by GPC is usually 1 to 5, more preferably 1 To 3, more preferably 1 to 2.5.

  Since the radiation sensitive resin composition (ii) of the present invention contains the polymers (p1) and (p2) as the polymer component (P), it has excellent sensitivity. From this point of view, this radiation-sensitive resin composition is effectively sensitive to X-rays such as KrF excimer laser, ArF excimer laser, EUV and the like, and X-rays such as synchrotron radiation and electron beams in the lithography process. In addition, it is possible to form a chemically amplified positive resist film having low roughness, excellent sensitivity and resolution, and capable of forming a fine pattern with high accuracy and stability.

[2-2] Acid Diffusion Control Agent In addition to the polymer component (P), the radiation sensitive resin composition (ii) of the present invention includes the acid diffusion described in the radiation sensitive resin composition (i). It is preferable to further contain a control agent (B). This acid diffusion controller (B) may be used alone or in combination of two or more.
The amount of the acid diffusion controller (B) is preferably 15 parts by mass or less, more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass in total of the polymers (p1) and (p2). More preferably, it is 0.005-5 mass parts. When the compounding amount of the acid diffusion controller (B) exceeds 15 parts by mass, the sensitivity of the formed resist film and the developability of the exposed part may be deteriorated. On the other hand, if the blending amount is less than 0.001 part by mass, the pattern shape and dimensional fidelity of the formed resist film may be lowered depending on the process conditions.

[2-3] Radiation-sensitive acid generator The radiation-sensitive resin composition (ii) of the present invention has been described in the above-mentioned radiation-sensitive resin composition (i) in addition to the polymer component (P). You may contain the other acid generator compound which decomposes | disassembles by irradiation of actinic light or a radiation, and generate | occur | produces an acid. These other acid generating compounds may be used alone or in combination of two or more.
The ratio of the sum of the above repeating units (I) and (II) in the polymer (p1) in the present invention to the other acid generating compound is 100/0 to 20/80, preferably 100/0, in molar ratio. -40/60, more preferably 100 / 0-50 / 50.

[2-4] Resin having a group that decomposes by the action of an acid and increases the solubility in an alkali developer. The radiation-sensitive resin composition (ii) of the present invention is not limited to the polymer component (P). And may contain other resin (X) having a group that is decomposed by the action of an acid and increases the solubility in an alkali developer, as described in the above-mentioned radiation-sensitive resin composition (i). . Other resin (X) may be used individually by 1 type, and may be used in combination of 2 or more type.
The usage-amount of resin (X) in this invention is 40-99 mass% on the basis of the total mass (except a solvent) of a radiation sensitive resin composition, Preferably it is 60-95 mass%. Furthermore, in order to adjust alkali solubility, you may mix alkali-soluble resin which does not have the group which can be decomposed | disassembled with an acid.

[2-5] Alkali-soluble resin The radiation-sensitive resin composition (ii) of the present invention includes the above-mentioned radiation-sensitive resin composition (i) in addition to the polymer component (P) and the other resin (X). The resin may contain an alkali-soluble resin that is insoluble in water and soluble in an aqueous alkali solution. This alkali-soluble resin may be used individually by 1 type, and may be used in combination of 2 or more type.
The amount of the alkali-soluble resin used in the present invention is 40 to 97% by mass, preferably 60 to 90% by mass, based on the total mass (excluding the solvent) of the radiation-sensitive resin composition.

[2-6] Low-molecular acid-decomposable dissolution inhibiting compound The radiation-sensitive resin composition (ii) of the present invention is described in the above-described radiation-sensitive resin composition (i) in addition to the polymer component (P). The low-molecular acid-decomposable dissolution inhibiting compound may be contained. This low molecular acid-decomposable dissolution inhibiting compound may be used alone or in combination of two or more.
The addition amount of the dissolution inhibiting compound is 3 to 50% by mass, preferably 5 to 40% by mass, more preferably 10 to 35% by mass with respect to 100 parts by mass of the total of the polymers (p1) and (p2). Range.

[2-7] Other components The radiation-sensitive resin composition (ii) of the present invention may further include a dye, a pigment, and a plasticizer described in the above-described radiation-sensitive resin composition (i) as necessary. , A surfactant, a photosensitizer, a phenol compound having two or more phenolic OH groups that promote solubility in a developer, and the like can be contained.
The addition amount of the phenol compound is 2 to 50% by mass, more preferably 5 to 30% by mass with respect to 100 parts by mass in total of the polymers (p1) and (p2). When the amount exceeds 50% by mass, the development residue is deteriorated, and a new defect that the pattern is deformed during development is not preferable.

[2-8] Solvent As the solvent used in the radiation sensitive resin composition (ii) of the present invention, the solvents described in the above radiation sensitive resin composition (i) can be used. These solvents may be used alone or in combination of two or more.

  Moreover, it is preferable that the compounding quantity of the solvent in the radiation sensitive composition of this invention is a quantity from which the total solid content concentration in a composition will be 1-70 mass%, More preferably, it is 1-15 mass%. In an amount of 1 to 10% by mass.

  And the radiation sensitive composition of this invention melt | dissolves uniformly required components, such as polymers (p1) and (p2) other than a solvent, in a solvent so that total solid content concentration may become the said range. Can be prepared. In addition, after preparing in this way, it is preferable to filter with a filter with a pore diameter of about 0.2 μm, for example.

[3] Method for Forming Resist Pattern The radiation-sensitive resin compositions (i) and (ii) of the present invention are useful as materials capable of forming a chemically amplified positive resist film.
In the chemically amplified positive resist film, the acid dissociable group in the polymer component is removed by the action of the acid generated from the polymer component [the polymer (A) or the polymer (p1)] upon exposure. The polymer component becomes alkali-soluble when released. That is, an alkali-soluble site is generated in the resist film. This alkali-soluble portion is an exposed portion of the resist, and this exposed portion can be dissolved and removed by an alkali developer. In this way, a positive resist pattern having a desired shape can be formed. This will be specifically described below.

  In order to form a resist pattern using the radiation sensitive resin composition of the present invention, first, a resist film is formed with the radiation sensitive resin composition of the present invention. As the radiation-sensitive resin composition, for example, as described above, after adjusting the total solid content concentration, it can be filtered with a filter having a pore diameter of about 0.2 μm. By applying this radiation-sensitive resin composition to a substrate such as a silicon wafer or a wafer coated with aluminum by an appropriate coating means such as spin coating, cast coating or roll coating, a resist film is formed. Form. Thereafter, in some cases, heat treatment (hereinafter referred to as “PB”) may be performed at a temperature of about 70 to 160 ° C. in advance. Next, the resist film is exposed so that a predetermined resist pattern is formed. Examples of radiation that can be used for this exposure include (extreme) far ultraviolet rays such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), EUV (extreme ultraviolet light, wavelength 13.5 nm, etc.), and synchro Examples include X-rays such as tron radiation, and charged particle beams such as electron beams. Moreover, exposure conditions, such as exposure amount, can be suitably selected according to the composition of the radiation-sensitive resin composition, the type of additive, and the like. This exposure can also be immersion exposure.

  In addition, it is preferable to perform heat processing (henceforth "PEB") after exposure. By this PEB, it becomes possible to smoothly proceed with elimination of the acid dissociable group in the polymer component [the polymer (A) or the polymer (p1)]. The heating condition of PEB is appropriately selected depending on the composition of the radiation sensitive resin composition, but is preferably 30 to 200 ° C, more preferably 50 to 170 ° C.

  In the present invention, in order to maximize the potential of the radiation-sensitive resin composition, for example, as disclosed in Japanese Patent Publication No. 6-12252 (Japanese Patent Laid-Open No. 59-93448), etc. An organic or inorganic antireflection film can also be formed on the substrate. Further, in order to prevent the influence of basic impurities contained in the environmental atmosphere, a protective film can be provided on the resist film as disclosed in, for example, JP-A-5-188598. These techniques can be used in combination.

  Next, the exposed resist film is developed to form a predetermined resist pattern. Examples of the developer used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propylamine. , Triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] An alkaline aqueous solution in which at least one of alkaline compounds such as 5-nonene is dissolved is preferable.

The concentration of the alkaline aqueous solution is preferably 10% by mass or less. When the concentration of the alkaline aqueous solution exceeds 10% by mass, the unexposed area may be dissolved in the developer.
Moreover, it is preferable that a developing solution is pH 8-14, More preferably, it is pH 9-14.

  Moreover, an organic solvent can also be added to the developing solution which consists of said alkaline aqueous solution, for example. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol, and n-propyl. Alcohols such as alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol; ethers such as tetrahydrofuran and dioxane Esters such as ethyl acetate, n-butyl acetate and i-amyl acetate; aromatic hydrocarbons such as toluene and xylene; phenol, acetonylacetone and dimethylformamide. These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

The blending amount of the organic solvent is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution. When the blending amount of the organic solvent exceeds 100 parts by volume, the developability is lowered, and there is a possibility that the remaining development in the exposed part increases. In addition, an appropriate amount of a surfactant or the like can be added to the developer composed of an alkaline aqueous solution.
In addition, after developing with the developing solution which consists of alkaline aqueous solution, it can also wash with water and can be dried.

  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. Here, “part” is based on mass unless otherwise specified.

In this example, the following measurements and evaluations in each synthesis example were performed in the following manner.
<Mw (weight average molecular weight) and Mn (number average molecular weight)>
MALLS was used as a detector for measuring the molecular weight (Mw, Mn) of the resin. Using a GPC column (TSKgel α-2500, TSKgel α-M) manufactured by Tosoh Corporation, dimethylformamide in which LiBr was dissolved at 30 mmol / l and H ₃ PO ₄ was dissolved at 10 mmol / l as a flow rate of 1.0 ml / min. The sample was measured by gel permeation chromatography (GPC) using MALLS (manufactured by Wyatt, DAWN DSP, cell type K5, laser wavelength 632.8 nm) as a detector under the analysis conditions with a column temperature of 40 ° C.
< ^13C -NMR analysis>
It measured using the JEOL nuclear magnetic resonance apparatus "JNM-EX270" (model name).

[2] Synthesis of Polymer <Synthesis of Polymer A-1 (Synthesis Example 1)>
20.45 g (10 mol%) of the following compound (P-1), 47.10 g (50 mol%) of the following compound (M-1), 32.43 g (40 mol%) of the following compound (M-2), 2, 2.99 g of 2′-azobisisobutyronitrile (AIBN) was dissolved in 200 g of 2-butanone to prepare a monomer solution. Meanwhile, a 500 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. After the nitrogen purge, the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was added dropwise to the reaction kettle over 3 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled to 30 ° C. or lower by water cooling, and after cooling, it was poured into 2000 g of 2-propanol, and the precipitated white solid was separated by filtration. Next, the filtered white powder was washed twice with 100 g of 2-propanol as a slurry. Then, it filtered and dried at 50 degreeC for 12 hours, and obtained the polymer of the white powder (52g, 52% of yield).
This polymer has Mw of 6000 and Mw / Mn of 2.3. As a result of ¹³ C-NMR analysis, the polymer (P-1) -derived repeating unit: compound (M-1) -derived repeating unit: compound ( The content ratio (molar ratio) of the repeating unit derived from M-2) was a copolymer of 11:48:41. Hereinafter, this polymer is referred to as “polymer (A-1)”.

<Synthesis of Polymer A-2 (Synthesis Example 2)>
The following compound (P-2) 20.42 g (10 mol%), the following compound (M-1) 39.19 g (40 mol%), the following compound (M-2) 33.71 g (40 mol%), the following compound (M-3) 6.68 g (10 mol%) and 2,2′-azobisisobutyronitrile (AIBN) 6.23 g were dissolved in 200 g of 2-butanone to prepare a monomer solution. Meanwhile, a 500 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. After the nitrogen purge, the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was added dropwise to the reaction kettle over 3 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled to 30 ° C. or lower by water cooling, and after cooling, it was poured into 2000 g of 2-propanol, and the precipitated white solid was separated by filtration. Next, the filtered white powder was washed twice with 100 g of 2-propanol as a slurry. Then, it filtered and dried at 50 degreeC for 12 hours, and obtained the polymer of the white powder (55g, yield 55%).
This polymer has Mw of 6100 and Mw / Mn of 2.2, and as a result of ¹³ C-NMR analysis, the repeating unit derived from the compound (P-2): the repeating unit derived from the compound (M-1): the compound ( The content ratio (molar ratio) of the repeating unit derived from M-2) to the repeating unit derived from the compound (M-3) was a copolymer of 11: 37: 42: 10. Hereinafter, this polymer is referred to as “polymer (A-2)”.

<Synthesis of Polymer A-3 (Synthesis Example 3)>
Mw was 7000, Mw / Mw / similar to Synthesis Example 1 except that 47.10 g (50 mol%) of compound (M-1) and 40.54 g (50 mol%) of compound (M-2) were used. Mn is 2.4, and as a result of ¹³ C-NMR analysis, the content ratio (molar ratio) of the repeating unit derived from the compound (M-1) to the repeating unit derived from the compound (M-2) is 50:50. A copolymer was synthesized. Hereinafter, this polymer is referred to as “polymer (A-3)”.

<Synthesis of Polymer A-4 (Comparative Synthesis Example 1)>
The following compound (P-1) 23.74 g (10 mol%), the following compound (M-4) 38.60 g (50 mol%), the following compound (M-2) 37.65 g (40 mol%), 2, 6.96 g of 2′-azobisisobutyronitrile (AIBN) was dissolved in 200 g of 2-butanone to prepare a monomer solution. Meanwhile, a 500 ml three-necked flask charged with 100 g of 2-butanone was purged with nitrogen for 30 minutes. After the nitrogen purge, the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was added dropwise to the reaction kettle over 3 hours using a dropping funnel. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled to 30 ° C. or lower by water cooling, and after cooling, it was poured into 2000 g of 2-propanol, and the precipitated white solid was separated by filtration. Next, the filtered white powder was washed twice with 100 g of 2-propanol as a slurry. Then, it filtered and dried at 50 degreeC for 12 hours, and obtained the polymer of the white powder (50g, yield 50%).
This polymer has Mw of 5500 and Mw / Mn of 2.0, and as a result of ¹³ C-NMR analysis, the repeating unit derived from compound (P-1): the repeating unit derived from compound (M-4): compound ( The content ratio (molar ratio) of the repeating unit derived from M-2) was a copolymer of 11:47:42. Hereinafter, this polymer is referred to as “polymer (A-4)”.

[3] Preparation of radiation-sensitive resin composition <Examples 1 to 3 and Comparative Example 1>
Example 1 was prepared by mixing (A) the polymer, (B) the acid diffusion controller, and (D) the solvent at the ratio shown in Table 1 and filtering the resulting mixture with a membrane filter having a pore size of 200 nm. -3 and each composition solution (radiation sensitive resin composition) of Comparative Example 1 were prepared.

Details of the (A) polymer, (B) acid diffusion controller, and (D) solvent are shown below.
(A) Polymer (A-1) to (A-4): The above polymers (A-1) to (A-4)
(B) Acid diffusion controller (B-1): Tri-n-octylamine (D) Solvent (D-1): Propylene glycol monomethyl ether acetate (D-2): Cyclohexanone

[4] Evaluation of Radiation Sensitive Resin Composition Each composition solution (each radiation sensitive resin of Examples 1 to 3 and Comparative Example 1) on a silicon wafer in “Clean Track ACT-8” manufactured by Tokyo Electron Ltd. After the composition was spin-coated, PB (heat treatment) was performed under the conditions shown in Table 2 to form a resist film having a thickness of 60 nm. Thereafter, the resist film was irradiated with an electron beam using a simple electron beam drawing apparatus (manufactured by Hitachi, Ltd., model “HL800D”, output: 50 KeV, current density: 5.0 amperes / cm ² ). After the electron beam irradiation, PEB was performed under the conditions shown in Table 2. Thereafter, using a 2.38% tetramethylammonium hydroxide aqueous solution, development was carried out at 23 ° C. for 1 minute by the paddle method, followed by washing with pure water and drying to form a resist pattern. The following items were evaluated for the resist thus formed. In addition, the evaluation result of each radiation sensitive resin composition of Examples 1-3 and Comparative Example 1 is written together in Table 2.

(1) Sensitivity (L / S)
A pattern [a so-called line-and-space pattern (1L1S)] composed of a line portion having a line width of 150 nm and a space portion (that is, a groove) having an interval of 150 nm formed by adjacent line portions is 1: 1. The exposure amount formed in the line width was set as the optimum exposure amount, and the sensitivity was evaluated based on the optimum exposure amount.
FIG. 1 is a plan view schematically showing the shape of a line and space pattern. FIG. 2 is a cross-sectional view schematically showing the shape of the line and space pattern.

(2) Nano-edge roughness A line-and-space pattern (1L1S) with a design line width of 150 nm is scanned with a scanning electron microscope for semiconductors (high resolution FEB measuring device, trade name “S-9220”, manufactured by Hitachi, Ltd.) ). With respect to the observed shape, as shown in FIG. 1 and FIG. 2, the line width and the design line at the most conspicuous portion of the unevenness generated along the lateral surface 2a of the line part 2 of the resist film formed on the silicon wafer 1 are shown. The difference “ΔCD” from the width of 150 nm was measured by CD-SEM (manufactured by Hitachi High-Technologies Corporation, “S-9220”) to evaluate nanoedge roughness.

(3) Resolution (L / S)
For the line-and-space pattern (1L1S), the minimum line width (nm) of the line pattern resolved with the optimum exposure dose was taken as the resolution.

  According to Table 2, the radiation sensitive of Examples 1-3 containing the polymer (A-1) which has a specific repeating unit, (A-2), or (A-1) and (A-3). Compared to the radiation-sensitive resin composition of Comparative Example 1, the photosensitive resin composition is more sensitive to electron beams or extreme ultraviolet rays, has low roughness and excellent resolution, and has a fine pattern with high accuracy. It was confirmed that a chemically amplified positive resist film that can be stably formed can be formed.

  The radiation-sensitive resin composition of the present invention is not only excellent in the resolution of the line and space pattern at the time of pattern formation, but is also excellent in nano edge roughness, so it is useful for forming a fine pattern by an electron beam or extreme ultraviolet rays. . Therefore, the radiation-sensitive resin composition of the present invention is extremely useful as a material capable of forming a chemically amplified resist for manufacturing semiconductor devices, which is expected to be further miniaturized in the future.

DESCRIPTION OF SYMBOLS 1; Base material 2; Resist pattern 2a;

Claims (5)

At least one of a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II);
A radiation-sensitive resin composition comprising a polymer having a repeating unit represented by the following general formula (1).

[In General Formulas (I) and (II), R _{1 to} R ₃ each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, —S -R ₆ group (R ₆ represents an optionally substituted alkyl group, or an aryl group.), or a group having a hetero atom or two or more. l represents an integer of 0 to 5. m shows the integer of 0-5. n shows the integer of 0-5. R ₇ and R ₁₁ each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R _{8 to} R ₁₀ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group that may have a substituent, an aralkyl group, or an alkoxy group. A represents an —O— group or an —NR ₁₂ — group (R ₁₂ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group). E shows the methylene group, alkylene group, or arylene group which may have a substituent. ]

[In General Formula (1), R ₁₅ represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group. R ₁₆ represents an aryl group having 6 to 22 carbon atoms which may have a substituent. X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y, and Y is a carbon atom. ] The radiation sensitive resin composition according to claim 1, wherein the polymer further contains at least one of repeating units represented by the following general formulas (2) to (6).

[In General Formulas (2) to (6), R ₃₁ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R ₃₂ and R ₃₃ each independently represent a hydrogen atom or a hydroxyl group. X represents an acid labile group. Z represents a substituent having a lactone structure. J represents a hydrogen atom, a fluoroalkyl group having 1 to 15 carbon atoms, or a substituent containing a fluoroalcohol structure having 1 to 15 carbon atoms. ] The radiation sensitive resin composition according to claim 1 or 2, wherein the polymer further contains at least one of repeating units represented by the following general formulas (7) to (10).

[In General Formulas (7) to (10), R ₃₁ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. X represents an acid labile group. G represents an oxygen atom or a carbonyloxy group (—C (═O) O—). ] A polymer (p1) having at least one of a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II);
A radiation-sensitive resin composition comprising a polymer (p2) having a repeating unit represented by the following general formula (1).

[In General Formulas (I) and (II), R _{1 to} R ₃ each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, —S -R ₆ group (R ₆ represents an optionally substituted alkyl group, or an aryl group.), or a group having a hetero atom or two or more. l represents an integer of 0 to 5. m shows the integer of 0-5. n shows the integer of 0-5. R ₇ and R ₁₁ each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R _{8 to} R ₁₀ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group that may have a substituent, an aralkyl group, or an alkoxy group. A represents an —O— group or an —NR ₁₂ — group (R ₁₂ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group). E shows the methylene group, alkylene group, or arylene group which may have a substituent. ]

[In General Formula (1), R ₁₅ represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group. R ₁₆ represents an aryl group having 6 to 22 carbon atoms which may have a substituent. X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y, and Y is a carbon atom. ] At least one of a repeating unit represented by the following general formula (I) and a repeating unit represented by the following general formula (II);
And a repeating unit represented by the following general formula (1).

[In General Formulas (I) and (II), R _{1 to} R ₃ each independently represents a hydroxy group, a halogen atom, an optionally substituted alkyl group, a cycloalkyl group, an alkoxy group, —S -R ₆ group (R ₆ represents an optionally substituted alkyl group, or an aryl group.), or a group having a hetero atom or two or more. l represents an integer of 0 to 5. m shows the integer of 0-5. n shows the integer of 0-5. R ₇ and R ₁₁ each independently represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R _{8 to} R ₁₀ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a carboxyl group, an alkyl group that may have a substituent, an aralkyl group, or an alkoxy group. A represents an —O— group or an —NR ₁₂ — group (R ₁₂ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group). E shows the methylene group, alkylene group, or arylene group which may have a substituent. ]

[In General Formula (1), R ₁₅ represents a hydrogen atom, a methyl group, a fluorine atom, or a trifluoromethyl group. R ₁₆ represents an aryl group having 6 to 22 carbon atoms which may have a substituent. X is an atomic group necessary for forming an alicyclic hydrocarbon group together with Y, and Y is a carbon atom. ]

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