JP5729180B2 - Radiation sensitive resin composition - Google Patents

Description

The present invention relates to a radiation sensitive resin composition. 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.

  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.

  With respect to these positive resists, a compound that generates an acid-dissociable group copolymerized with an acid-decomposable acrylate monomer and generates sulfonic acid upon irradiation with actinic rays or radiation (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 positive resist composition and the like, at present, high sensitivity, high resolution, and good nano edge roughness (low roughness) in the ultrafine region are not satisfied at the same time.

  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. An object of the present invention is to provide a radiation-sensitive resin composition that is excellent in edge roughness, sensitivity, and resolution, and that can form a chemically amplified positive resist film capable of forming a fine pattern with high accuracy and stability. .

〔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（Ｂ１）において、Ｒ_１３は、各々独立に、水素原子、ハロゲン原子、又は１価の有機基を示す。Ｚ⁻は、ＣＨ _３ ＣＯＯ ⁻ 、及び下記式で表される化合物（Ｚ−１）〜（Ｚ−６）のうちのいずれかを示す。〕

〔一般式（７）〜（１２）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は酸の作用により解離する酸不安定基を示す。Ｇは酸素原子又はカルボニルオキシ基（−Ｃ（＝Ｏ）Ｏ−）を示す。〕
［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基を示す。Ｘは酸の作用により解離する酸不安定基を示す。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］前記一般式（Ｉ）及び（ＩＩ）のＲ _１ 〜Ｒ _３ におけるヘテロ原子を２つ以上有する基が、−ＯＳＯ _２ −Ｒｘ、及び、−ＳＯ _２ −Ｒｘ（Ｒｘは、各々独立に、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、又はアリール基を示す。）のうちの少なくとも一方である前記［１］又は［２］に記載の感放射線性樹脂組成物。
［４］前記一般式（Ｉ）で表される繰り返し単位、及び前記一般式（ＩＩ）で表される繰り返し単位の含有量の合計が、前記重合体における全繰り返し単位の合計を１００モル％とした場合に、１〜２０モル％である前記［１］に記載の感放射線性樹脂組成物。
［５］前記一般式（２）で表される繰り返し単位の含有量が、前記重合体における全繰り返し単位の合計を１００モル％とした場合に、１０〜７０モル％である前記［２］に記載の感放射線性樹脂組成物。
［６］前記一般式（３）〜（６）で表される繰り返し単位の含有量の合計が、前記重合体における全繰り返し単位の合計を１００モル％とした場合に、５〜９９モル％である前記［２］に記載の感放射線性樹脂組成物。
［７］前記一般式（７）〜（１２）で表される繰り返し単位の含有量の合計が、前記重合体における全繰り返し単位の合計を１００モル％とした場合に、５〜９９モル％である前記［１］に記載の感放射線性樹脂組成物。
［８］更に、活性光線又は放射線の照射により分解して酸を発生する酸発生化合物（但し、前記重合体を除く）を含有する前記［１］乃至［７］のうちのいずれかに記載の感放射線性樹脂組成物。
［９］更に、含窒素化合物を含有する前記［１］乃至［８］のうちのいずれかに記載の感放射線性樹脂組成物。 The present invention is as follows.
[1] A polymer 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 containing a compound (X1) represented by the following general formula (B1) ,
The said polymer further contains at least 1 sort (s) of the repeating units represented by the following general formula (7)-(12), The radiation sensitive resin composition characterized by the above-mentioned.

[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 (B1), each R ₁₃ independently represents a hydrogen atom, a halogen atom, or a monovalent organic group. Z ⁻ represents CH ₃ COO ⁻ or any one of compounds (Z-1) to (Z-6) represented by the following formulae . ]

[In General Formulas (7) to (12), 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 that is dissociated by the action of an acid. G represents an oxygen atom or a carbonyloxy group (—C (═O) O—). ]
[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 hydroxy group. X represents an acid labile group that is dissociated by the action of an acid. 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 groups having two or more hetero atoms in R _{1 to} R ₃ in the general formulas (I) and (II) are each —OSO ₂ —Rx and —SO ₂ —Rx (Rx is independently Or an optionally substituted alkyl group, cycloalkyl group, alkoxy group, or aryl group.) The radiation-sensitive resin composition according to the above [1] or [2] object.
[4] The total content of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) is 100 mol% with respect to the total of all the repeating units in the polymer. The radiation-sensitive resin composition according to [1], which is 1 to 20 mol%.
[5] In the above [2], the content of the repeating unit represented by the general formula (2) is 10 to 70 mol% when the total of all repeating units in the polymer is 100 mol%. The radiation sensitive resin composition as described.
[6] The total content of the repeating units represented by the general formulas (3) to (6) is 5 to 99 mol% when the total of all the repeating units in the polymer is 100 mol%. The radiation-sensitive resin composition according to [2].
[7] The total content of the repeating units represented by the general formulas (7) to (12) is 5 to 99 mol% when the total of all the repeating units in the polymer is 100 mol%. The radiation-sensitive resin composition according to [1].
[8] The method according to any one of [1] to [7], further comprising an acid-generating compound that decomposes upon irradiation with actinic rays or radiation to generate an acid (excluding the polymer). Radiation sensitive resin composition.
[9] The radiation sensitive resin composition according to any one of [1] to [8], further including a nitrogen-containing compound.

  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.

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 The radiation sensitive resin composition of the present invention is characterized by containing a specific polymer and a specific compound.

[1-1] Polymer (A)
The radiation-sensitive resin composition of the present invention includes a polymer component 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 polymer (hereinafter, also referred to as “polymer (A)”).
This polymer (A) is an alkali-insoluble or hardly-alkali-soluble polymer that becomes readily alkali-soluble by the action of an acid.

〔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. When Rx has a substituent, a halogen atom is preferable.
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.

  However, in this case, the total (l + m + n) of l, m and n is preferably 0-2.

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 methylene group and alkylene group having the substituent include a group in which a hydrogen atom of the methylene group or alkylene group is substituted with a fluorine atom, an alkyl group having 1 to 3 carbon atoms, and a fluorinated alkyl group having 1 to 3 carbon atoms. And a group substituted with. Examples of the substituted alkylene group include 1,1,2,2-tetrafluorobutylene group, 1,1,2-trifluorobutylene group, and 1,1-difluoro-2-trifluoromethylethylene group. be able to.
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.

  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.

  In addition, the polymer (A) in the present invention contains, in addition to the above repeating units (I) and (II), repeating units represented by the following general formulas (2) to (6) [hereinafter referred to as “repeating 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基を示す。Ｘは酸の作用により解離する酸不安定基を示す。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 hydroxy group. X represents an acid labile group that is dissociated by the action of an acid. 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 the general formula (2) is not particularly limited, specifically, groups represented by the following general formulas (L1) to (L5), a carbon number of 4 to 20 (preferably 4 to 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 alicyclic hydrocarbon 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 hydrogen atoms in these alkyl groups are substituted with hydroxy 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-methylcyclopentyl group, 1-ethylcyclopentyl Group, 1-butylcyclopentyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, 2-methyl- Examples thereof include 2-adamantyl group and 2-ethyl-2-adamantyl group.
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 1-6.

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 hydroxy 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 hydroxy 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.).

In General Formula (L5), each R ^L51 independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms. Specifically, the same thing as ^RL07 can be illustrated.

  Here, specific examples of the acid labile group 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.

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

  Specific examples of the acid labile group represented by the general formula (L5) include 2-methyladamantan-2-yl, 2-ethyladamantan-2-yl, 2-n-propyladamantan-2-yl, Examples include 2-isopropyladamantan-2-yl, 2-n-butyladamantan-2-yl, 2-sec-butyladamantan-2-yl, 2- (4-methoxy-n-butyl) adamantan-2-yl, etc. it can.

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.

In addition, the polymer (A) in the present invention contains, in addition to the repeating units (I) and (II), repeating units represented by the following general formulas (7) to (12) [hereinafter referred to as “repeating units ( 7) to (12) ". It is further Dressings containing at least one of].

〔一般式（７）〜（１２）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は酸の作用により解離する酸不安定基を示す。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 (12), 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 that is dissociated by the action of an acid. 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 hydroxy 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 (2) is preferably 10 to 70 mol%, more preferably 20 to 60 mol%, when the total of all repeating units in the polymer (A) is 100 mol%. It is. When this content is in the above range, the nano edge roughness can be excellent.
The total content of the repeating units (3) to (6) is preferably from 5 to 99 mol%, more preferably when the total of all repeating units in the polymer (A) is 100 mol%. Is 30 to 98 mol%, more preferably 40 to 98 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 (12) is preferably 5 to 99 mol%, more preferably when the total of all repeating units in the polymer (A) is 100 mol%. Is from 5 to 90 mol%, more preferably from 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.

  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.

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 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] Photosensitive basic compound In addition to the polymer (A), the radiation-sensitive resin composition of the present invention includes a photosensitive basic compound (hereinafter referred to as "compound") represented by the following general formula (B1). (X1) "). The photosensitive basic compound (photo-degradable basic compound) is a component that decomposes and loses basicity in an exposed region and remains as it is without being decomposed in an unexposed portion. Such a photosensitive basic compound can effectively use an acid generated in an exposed area (that is, an exposed area) as compared with a non-photosensitive basic compound, and an action of an excess acid in an unexposed area. Therefore, nano edge roughness and resolution can be improved.

〔一般式（Ｂ１）において、Ｒ_１３は、各々独立に、水素原子、ハロゲン原子、又は１価の有機基を示す。Ｚ⁻は、ＣＨ _３ ＣＯＯ ⁻ 、及び下記式で表される化合物（Ｚ−１）〜（Ｚ−６）のうちのいずれかを示す。〕

[In General Formula (B1), each R ₁₃ independently represents a hydrogen atom, a halogen atom, or a monovalent organic group. Z ⁻ represents CH ₃ COO ⁻ or any one of compounds (Z-1) to (Z-6) represented by the following formulae . ]

As the halogen atom in R ₁₃ in formula (B1), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As monovalent organic group in R < ₁₃ > in the said general formula (B1), the C1-C10 alkyl group which may have a substituent, or the alicyclic carbonization which may have a substituent, for example. A hydrogen group etc. 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. The alkyl group includes a hydroxy group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, chlorine atom, iodine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc.) ), An alkyloxycarbonyl group (such as t-butoxycarbonylmethyloxy group) and the like.
Moreover, as an alicyclic hydrocarbon group which may have the said substituent, a C5-C25 alicyclic hydrocarbon group etc. are mentioned. Specifically, a cyclopentyl group, a cyclohexyl group, etc. are mentioned, for example. The alicyclic hydrocarbon group includes a hydroxy group, a carboxyl group, a halogen atom (fluorine atom, bromine atom, chlorine atom, iodine atom, etc.), an alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, t -Butoxy group and the like) and alkyloxycarbonyl group (t-butoxycarbonylmethyloxy group and the like) and the like.

Of these, R ₁₃ is preferably a hydrogen atom or 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 addition, a compound (X1) may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, the radiation sensitive resin composition of this invention may contain other photosensitive basic compounds other than the said compound (X1). Specific examples of the other photosensitive basic compound include a compound represented by the following general formula (B2) (hereinafter also referred to as “compound (X2)”).

〔一般式（Ｂ２）において、Ｒ_１４は、それぞれ、水素原子、ハロゲン原子、又は１価の有機基である。Ｚ⁻は、Ｒ_１５Ｏ⁻、Ｒ_１５ＣＯＯ⁻、Ｒ_１５ＳＯ_３ ⁻、Ｒ_１５−Ｎ⁻−ＳＯ_２Ｒ_１６を示す（Ｒ_１５及びＲ_１６は、それぞれ、１価の有機基を示す。）。〕

[In General Formula (B2), each of R ₁₄ represents a hydrogen atom, a halogen atom, or a monovalent organic group. Z ^{- _{is, R 15 O -, R 15}} COO -, R 15 SO 3 -, R 15 -N - shows a -SO _{2 R 16 (R 15} and _{R 16} are each a monovalent organic group. ). ]

The general formula in _(B2), For a halogen atom _{R 14,} and a monovalent organic group, can be directly applied to the description of _{R 13} in the general formula (B1). R ₁₄ may be the same or different.
Examples of Z ⁻ in the general formula (B2) include R ₁₅ O ⁻ , R ₁₅ COO ⁻ , R ₁₅ SO ₃ ⁻ , and R ₁₅ —N ⁻ —SO ₂ R ₁₆ .
Examples of the monovalent organic group for R ₁₅ include an alkyl group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent, and an aryl group which may have a substituent. Can be mentioned.
Examples of the monovalent organic group for R ¹⁶ include a fluorinated alkyl group that may have a substituent, a fluorinated alicyclic hydrocarbon group that may have a substituent, and a substituent. Mention may be made of fluorinated aryl groups which may be present.
In particular, the Z ⁻ is preferably CH ₃ COO ⁻ and the above-mentioned compounds (Z-1) to (Z-6).
Moreover, the said compound (X2) may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that the compounding quantity of the said compound (X1) is 1-50 mass parts with respect to 100 mass parts of polymers (A), More preferably, it is 1-35 mass parts, More preferably, it is 1-20 mass parts. It is. When the compounding amount of the compound (X1) is in the above range, appropriate sensitivity of the formed resist film and developability of the exposed portion can be ensured, and good pattern shape and dimensional fidelity can be obtained.
Moreover, it is preferable that the compounding quantity of the said compound (X2) is 50 mass parts or less with respect to 100 mass parts of polymers (A), More preferably, it is 1-35 mass parts.

[1-3] Acid diffusion controller (B)
It is preferable that the radiation sensitive resin composition of the present invention further contains an acid diffusion control agent (B) in addition to the polymer (A).
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.

Examples of the acid diffusion controller (B) include nitrogen-containing organic compounds.
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.

  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.

[1-4] Radiation-sensitive acid generator In addition to the polymer (A), the radiation-sensitive resin composition of the present invention is another acid-generating compound that decomposes upon irradiation with actinic rays or radiation to generate an acid. 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.

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.

[1-5] Other components In the radiation sensitive resin composition of the present invention, a fluorine-containing polymer, an alicyclic skeleton-containing compound, a dye, a pigment, a plasticizer, a surfactant, A photosensitizer, a compound having two or more phenolic OH groups that promote solubility in a developer, and the like can be contained.

<Fluorine atom-containing polymer>
The radiation-sensitive resin composition may contain a fluorine atom-containing polymer (excluding [A] polymer). When the radiation-sensitive resin composition contains a fluorine atom-containing polymer, when the resist film is formed, the distribution is unevenly distributed on the resist film surface due to the oil-repellent characteristics of the fluorine atom-containing polymer. Due to the tendency, elution of the acid generator and the acid diffusion controller in the film into the immersion medium can be suppressed during the immersion exposure.

[1-6] Solvent The solvent is not particularly limited as long as it is a solvent that can dissolve the components of the radiation-sensitive resin composition. For example, alcohol solvents, ether solvents, ketone organic solvents, amide solvents, ester organic solvents, hydrocarbon solvents and the like can be used.

Examples of alcohol solvents include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-pentanol, i-pentanol, and 2-methylbutanol. , Sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethyl Hexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptade Alcohol, furfuryl alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, mono-alcohol solvents such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 -Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether.

  Examples of the ether solvent include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether and the like.

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n. -Ketone solvents such as hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, etc. It is done.

  Examples of amide solvents include N, N′-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide. , N-methylpropionamide, N-methylpyrrolidone and the like.

  Examples of the ester solvent include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetic acid. sec-butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, aceto Methyl acetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol acetate Mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate Methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, Examples include diethyl malonate, dimethyl phthalate, and diethyl phthalate.

Examples of the hydrocarbon solvent include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, Aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane;
Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene Group hydrocarbon solvents and the like.

  These organic solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

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 (manufactured by Asahi Glass Co., Ltd.), etc., organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid type or meta 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] Method for Forming Resist Pattern The radiation-sensitive resin composition of the present invention is useful as a material capable of forming a chemically amplified positive resist film.
In the above chemically amplified positive resist film, the acid-dissociable group in the polymer (A) is eliminated by the action of the acid generated from the polymer (A) by exposure, and the polymer (A) is alkali-soluble. Become. 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 (A). 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).

[1] Synthesis of Polymer <Synthesis of Polymer A-1 (Synthesis Example 1)>
15.11 g (6 mol%) of the following compound (P-1), 40.95 g (50 mol%) of the following compound (M-1), 43.94 g (44 mol%) of the following compound (M-2), 2, A monomer solution was prepared by dissolving 7.38 g of 2′-azobisisobutyronitrile (AIBN) in 200 g of 2-butanone. 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 (60g, yield 60%).
This polymer has Mw of 7000 and Mw / Mn of 2.5, and as a result of ¹³ C-NMR analysis, the repeating unit derived from compound (P-1): the repeating unit derived from compound (M-1): compound ( The content ratio (molar ratio) of the repeating unit derived from M-2) was a copolymer of 6:49:45. Hereinafter, this polymer is referred to as “polymer (A-1)”.

<Synthesis of Polymer A-2 (Synthesis Example 2)>
14.52 g (6 mol%) of the following compound (P-2), 40.93 g (50 mol%) of the following compound (M-1), 33.94 g (34 mol%) of the following compound (M-2), and the following compound (M-4) 10.61 g (10 mol%) and 2,2′-azobisisobutyronitrile (AIBN) 7.38 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 6800 and Mw / Mn of 2.5, and as a result of ¹³ C-NMR analysis, the repeating unit derived from compound (P-2): the repeating unit derived from compound (M-1): 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 6: 48: 36: 10. Hereinafter, this polymer is referred to as “polymer (A-2)”.

<Synthesis of Polymer A-3 (Synthesis Example 3)>
15.27 g (7 mol%) of the following compound (P-3), 24.54 g, (30 mol%) of the following compound (M-2), 16.79 g (20 mol%) of the following compound (M-4), Compound (M-5) 43.41 g (43 mol%) and 2,2′-azobisisobutyronitrile (AIBN) 6.04 g were dissolved in 267 g of 2-butanone to prepare a monomer solution. Meanwhile, a 1000 ml three-necked flask charged with 133 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 less by water cooling, and after cooling, it was poured into 2500 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 (63g, yield 63%).
This polymer has Mw of 7700 and Mw / Mn of 2.4, and as a result of ¹³ C-NMR analysis, the repeating unit derived from compound (P-3): the repeating unit derived from compound (M-2): compound ( The content ratio (molar ratio) of the repeating unit derived from M-4) to the repeating unit derived from the compound (M-5) was a copolymer of 8: 32: 21: 39. Hereinafter, this polymer is referred to as “polymer (A-3)”.

<Synthesis of Polymer A-4 (Synthesis Example 4)>
14.67 g (7 mol%) of the following compound (P-1), 25.81 g of the following compound (M-2), (30 mol%), 13.81 g (20 mol%) of the following compound (M-6), Compound (M-5) 45.67 g (43 mol%) and 2,2′-azobisisobutyronitrile (AIBN) 6.36 g were dissolved in 267 g of 2-butanone to prepare a monomer solution. Meanwhile, a 1000 ml three-necked flask charged with 133 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 less by water cooling, and after cooling, it was poured into 2500 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 (63g, yield 63%).
This polymer has Mw of 7800 and Mw / Mn of 2.5, and as a result of ¹³ C-NMR analysis, the repeating unit derived from compound (P-1): the repeating unit derived from compound (M-2): compound ( The content ratio (molar ratio) of the repeating unit derived from M-6) to the repeating unit derived from the compound (M-5) was 7: 31: 22: 40. Hereinafter, this polymer is referred to as “polymer (A-4)”.

[2] The radiation-sensitive preparation of the resin composition <Experimental Examples 1-5 and Comparative Example 1>
In the ratio shown in Table 1, (A) the polymer, (B) the acid diffusion controller, (X) the photosensitive basic compound and (D) the solvent were mixed, and the resulting mixture was filtered with a membrane filter having a pore size of 200 nm. by filtration, to prepare the composition solution experiments examples 1-5 and Comparative example 1 (radiation-sensitive resin composition). However, among Experimental Examples 1 to 5, Experimental Examples 3 and 4 are Examples, and Experimental Examples 1, 2, and 5 are Reference Examples.

The details of the above (A) polymer, (B) acid diffusion controller, (X) photosensitive basic compound 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

(X) Photosensitive basic compound (X-1): Compound represented by the following formula (X-1) (X-2): Compound represented by the following formula (X-2)

(D) Solvent (D-1): Propylene glycol monomethyl ether acetate (D-2): Cyclohexanone

[3] a sense of radiation-sensitive resin composition evaluated Tokyo Electron Ltd. in the "Clean Track ACT-8", each composition solution on a silicon wafer (the radiation-sensitive experiments Examples 1-5 and Comparative Example 1 The resin composition was spin-coated, and then 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. Incidentally, also shown the evaluation results of the radiation-sensitive resin composition of Experiment Examples 1 to 5 and Comparative Example 1 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. However, the unevenness shown in FIGS. 1 and 2 is exaggerated from the actual.

(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, experimental examples containing a polymer having a specific repeating unit (A-1) ~ (A -4), and the photosensitive basic compound (X-1) ~ (X -2) 1 The radiation sensitive resin composition of -5 is more sensitive to electron beams or extreme ultraviolet rays than the radiation sensitive resin composition of Comparative Example 1, has low roughness and excellent resolution, and has a fine pattern. It was confirmed that a chemically amplified positive resist film capable of forming a highly accurate and stable film 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 (9)

A polymer 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 containing a compound (X1) represented by the following general formula (B1) ,
The said polymer further contains at least 1 sort (s) of the repeating units represented by the following general formula (7)-(12), The radiation sensitive resin composition characterized by the above-mentioned.

[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 (B1), each R ₁₃ independently represents a hydrogen atom, a halogen atom, or a monovalent organic group. Z ⁻ represents CH ₃ COO ⁻ or any one of compounds (Z-1) to (Z-6) represented by the following formulae . ]

[In General Formulas (7) to (12), 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 that is dissociated by the action of an acid. G represents an oxygen atom or a carbonyloxy group (—C (═O) O—). ] 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 hydroxy group. X represents an acid labile group that is dissociated by the action of an acid. 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. ] R in the general formulas (I) and (II) ₁ ~ R ₃ And the group having two or more heteroatoms in —OSO ₂ -Rx and -SO ₂ 3. The method according to claim 1, wherein each is at least one of —Rx (Rx independently represents an optionally substituted alkyl group, cycloalkyl group, alkoxy group, or aryl group). Radiation sensitive resin composition. When the total content of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) is 100 mol%, based on the total of all the repeating units in the polymer. The radiation sensitive resin composition according to claim 1, which is 1 to 20 mol%. The radiation sensitive composition according to claim 2, wherein the content of the repeating unit represented by the general formula (2) is 10 to 70 mol% when the total of all repeating units in the polymer is 100 mol%. Resin composition. The total content of repeating units represented by the general formulas (3) to (6) is 5 to 99 mol% when the total of all repeating units in the polymer is 100 mol%. 2. The radiation sensitive resin composition according to 2. The total content of the repeating units represented by the general formulas (7) to (12) is 5 to 99 mol% when the total of all the repeating units in the polymer is 100 mol%. 1. The radiation sensitive resin composition according to 1. Furthermore, the radiation sensitive resin as described in any one of Claims 1 thru | or 7 containing the acid generating compound (however, except the said polymer) which decomposes | disassembles by irradiation of actinic light or a radiation. Composition. Furthermore, the radiation sensitive resin composition as described in any one of Claims 1 thru | or 8 containing a nitrogen-containing compound.

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