JP5676866B2 - Actinic ray-sensitive or radiation-sensitive resin composition, pattern forming method using the composition, and method for purifying resin used in the composition - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in an ultramicrolithography process such as the manufacture of VLSI and high-capacity microchips and other photofabrication processes, and a pattern using the composition More particularly, the present invention relates to a resin composition for electron beam, X-ray or EUV light, a pattern formation method using the same, and a method for purifying a resin used in the composition. Is.

Conventionally, in the manufacturing process of semiconductor devices such as IC and 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, and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV light is also being developed. Further, microfabrication by lithography is not limited to the manufacturing process of semiconductor devices in a narrow sense, and recently, application to the manufacture of a mold structure for a so-called imprint process has been studied.
In particular, electron beam lithography is positioned as a next-generation or next-generation pattern forming technique, and a positive resist with high sensitivity and high resolution is desired. In particular, high sensitivity is an extremely important issue for shortening the wafer processing time. However, in positive resists for electron beams, when trying to increase sensitivity, not only the resolution is lowered, but also the line edge. Roughness deteriorates, and development of a resist that satisfies these characteristics at the same time is strongly desired. Here, the line edge roughness means that 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. Say that the edge looks uneven. The unevenness is transferred by an etching process using a resist as a mask, and the electrical characteristics are deteriorated, so that the yield is lowered. Particularly in the ultrafine region of 0.25 μm or less, the line edge roughness is an extremely important improvement issue. High sensitivity, high resolution, good pattern shape, and good line edge roughness are in a trade-off relationship, and it is very important how to satisfy them simultaneously.
Similarly, in lithography using X-rays or EUV light, it is important to satisfy high sensitivity, high resolution, good pattern shape, and good line edge roughness at the same time. is necessary.

As one method for solving these problems, use of a resin having a photoacid generator in a polymer side chain has been studied (Patent Documents 1 and 2, Non-Patent Document 1).
Patent Document 1 discloses a resist material containing a polymer compound containing a repeating unit having a sulfonium salt in the side chain so as to enable a pattern with high sensitivity, high resolution, and low line edge roughness (LER). ing.
Also in Patent Document 2, a radiation-sensitive resin containing a polymer in which a photoacid generator is introduced into a side chain in order to realize a high resolution, wide DOF, excellent LER, and an excellent pattern shape during immersion exposure. A composition is disclosed.
Non-Patent Document 1 describes a hydroxystyrene polymer in which a photoacid generator is introduced into a polymer side chain, and it is said that high sensitivity, high resolution, and excellent LER can be realized in lithography using an electron beam. .
On the other hand, studies have been made to suppress the generation of foreign substances by removing unreacted monomers in the polymer (Patent Document 3) or to achieve desired resist performance (Patent Documents 4 to 5). ).

  In Non-Patent Document 2, the influence of a monomer containing a photoacid generator remaining in a resin having a photoacid generator in the polymer side chain is studied, and a monomer containing a remaining photoacid generator is studied. It has been clarified that the sensitivity decreases when the is removed.

JP 2006-215526 A International Publication No. 06/121096 JP 2003-270788 A JP 2007-51299 A Japanese Patent Laid-Open No. 2008-1914

Proc. Of SPIE Vol. 6923, 692312, 2008 J. Photopolym. Sci. Technol., Vol.22, No.1 (2009), 25-29

  The present inventors use a resin (P) containing a repeating unit having a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid, and has high sensitivity, high resolution, good pattern shape and good The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition that can simultaneously satisfy the desired line edge roughness, a pattern formation method using the composition, and a method for purifying a resin used in the composition.

（上記一般式（１）中、Ｒ^１は水素原子、メチル基、又はトリフルオロメチル基を示し、Ｚは放射線照射により酸を発生する機能を有する一価の基を示す。）

（上記一般式（２）、（３）、及び（４）中、Ｒ^２は、それぞれ独立に、水素原子、メチル基、又はトリフルオロメチル基を示す。上記一般式（２）及び（４）中、Ａは、それぞれ独立に、メチレン基、炭素数２〜１０の直鎖状若しくは分岐状のアルキレン基、又は炭素数３〜１０のアリーレン基を示す。上記一般式（２）中、Ｙは下記一般式（ｉ）で表される構造を有する基を示し、ａは０又は１を示す。上記一般式（３）中、Ｒ^３は炭素数１〜１０の直鎖状若しくは分岐状のアルキル基を示す。上記一般式（４）中、ｂは２〜４の整数を示し、ｃは０又は１を示す。）

（上記一般式（ｉ）中、Ｒ^４は水素原子又は炭素数１〜５の直鎖状若しくは分岐状のアルキル基を示し、ｐは１又は２を示し、ｑは１又は２を示す。但し、ｐ＝２である場合は、２つのＲ^４は同一であっても、異なっていてもよい。）
〔２〕
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構造部位（Ｘ）を有する繰り返し単位（Ａ）を有し、ゲルろ過クロマトグラフィー法で精製された樹脂（Ｐ）を含有する感活性光線性又は感放射線性樹脂組成物であって、前記組成物中の、前記樹脂（Ｐ）中に含まれる繰り返し単位（Ａ）を構成する単量体（ａ）の存在量が、前記感活性光線性又は感放射線性樹脂組成物の質量に対して０．０５質量％以下であることを特徴とする感活性光線性又は感放射線性樹脂組成物。
〔３〕
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構造部位（Ｘ）を有する繰り返し単位（Ａ）及び下記一般式（ＶＩ）で表される繰り返し単位を有する樹脂（Ｐ）を含有する感活性光線性又は感放射線性樹脂組成物であって、前記組成物中の、前記樹脂（Ｐ）中に含まれる繰り返し単位（Ａ）を構成する単量体（ａ）の存在量が、前記感活性光線性又は感放射線性樹脂組成物の質量に対して０．０５質量％以下であることを特徴とする感活性光線性又は感放射線性樹脂組成物。

ここで、Ｒ_６１、Ｒ_６２及びＲ_６３は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。またＲ_６２は、アルキレン基を表し、Ａｒ_６と結合して５員若しくは６員環を形成していても良い。
Ａｒ_６は、芳香環基を表す。
ｎ個のＹは、各々独立に、水素原子又は酸の作用により脱離する基を表す。但し、Ｙの少なくとも１つは、酸の作用により脱離する基を表す。
ｎは、１〜４の整数を表す。
〔４〕
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構造部位（Ｘ）を有する繰り返し単位（Ａ）及び下記一般式（ＩＶ）で表される繰り返し単位を有する樹脂（Ｐ）を含有する感活性光線性又は感放射線性樹脂組成物であって、前記組成物中の、前記樹脂（Ｐ）中に含まれる繰り返し単位（Ａ）を構成する単量体（ａ）の存在量が、前記感活性光線性又は感放射線性樹脂組成物の質量に対して０．０５質量％以下であることを特徴とする感活性光線性又は感放射線性樹脂組成物。

ここで、Ｒ_４１、Ｒ_４３は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
Ｒ_４２は、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。また、Ｒ_４２は、アルキレン基を表し、Ａｒ_４と結合して５員若しくは６員環を形成していても良い。
Ａｒ_４は、芳香環基を表す。ｎは、１〜４の整数を表す。
〔５〕
前記樹脂（Ｐ）が、更に、アルカリ可溶性基を有する繰り返し単位（Ｂ）を有することを特徴とする〔１〕〜〔４〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔６〕
前記樹脂（Ｐ）が、ゲルろ過クロマトグラフィー法で精製されたことを特徴とする〔１〕、〔３〕又は〔４〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔７〕
前記樹脂（Ｐ）が、下記一般式（ＶＩ）で表される繰り返し単位を更に有する、〔１〕、〔２〕及び〔４〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。

ここで、Ｒ_６１、Ｒ_６２及びＲ_６３は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。またＲ_６２は、アルキレン基を表し、Ａｒ_６と結合して５員若しくは６員環を形成していても良い。
Ａｒ_６は、芳香環基を表す。
ｎ個のＹは、各々独立に、水素原子又は酸の作用により脱離する基を表す。但し、Ｙの少なくとも１つは、酸の作用により脱離する基を表す。
ｎは、１〜４の整数を表す。
〔８〕
前記樹脂（Ｐ）が、下記一般式（ＩＶ）で表される繰り返し単位を更に有する、〔１〕〜〔３〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。

ここで、Ｒ_４１、Ｒ_４３は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
Ｒ_４２は、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。また、Ｒ_４２は、アルキレン基を表し、Ａｒ_４と結合して５員若しくは６員環を形成していても良い。
Ａｒ_４は、芳香環基を表す。ｎは、１〜４の整数を表す。
〔９〕
前記構造部位（Ｘ）が、活性光線又は放射線の照射により樹脂の側鎖に酸アニオンを生じる構造部位である〔１〕〜〔８〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔１０〕
前記樹脂（Ｐ）中に含まれる繰り返し単位（Ａ）を構成する単量体（ａ）が、樹脂（Ｐ）の固形分に対して１．０質量％以下であることを特徴とする〔１〕〜〔９〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔１１〕
前記樹脂（Ｐ）が、更に、酸の作用により分解し、アルカリ可溶性基を生じる基を有する繰り返し単位（Ｃ）を有することを特徴とする〔１〕〜〔１０〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔１２〕
前記樹脂（Ｐ）が、更に、アルカリ現像液の作用で分解しアルカリ現像液中への溶解速度が増大する基を有する繰り返し単位（Ｄ）を有することを特徴とする〔１〕〜〔１１〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔１３〕
露光光源として、電子線、Ｘ線又はＥＵＶ光を用いることを特徴とする〔１〕〜〔１２〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
〔１４〕
〔１〕〜〔１３〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物を用いて形成されたレジスト膜。
〔１５〕
〔１〕〜〔１３〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物を用いてレジスト膜を形成し、露光、現像する工程を有することを特徴とするパターン形成方法。
〔１６〕
前記樹脂（Ｐ）がゲルろ過クロマトグラフィー法で精製した樹脂であって、樹脂（Ｐ）を用いて、感活性光線性又は感放射線性樹脂組成物を調製し、該組成物によりレジスト膜を形成し、露光、現像する工程を有することを特徴とする〔１５〕に記載のパターン形成方法。
〔１７〕
〔１〕〜〔１３〕のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物に含まれる樹脂（Ｐ）の精製方法が、ゲルろ過クロマトグラフィー法であることを特徴とする樹脂の精製方法。
本発明は、前記〔１〕〜〔１７〕に係る発明であるが、以下、それ以外の事項（例えば、下記（１）〜（１４））についても記載している。
（１）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構造部位（Ｘ）を有する繰り返し単位（Ａ）を有する樹脂（Ｐ）を含有する感活性光線性又は感放射線性樹脂組成物であって、前記組成物中の、前記樹脂（Ｐ）中に含まれる繰り返し単位（Ａ）を構成する単量体（ａ）の存在量が、前記感活性光線性又は感放射線性樹脂組成物の質量に対して０．０５質量％以下であることを特徴とする感活性光線性又は感放射線性樹脂組成物。
（２）前記樹脂（Ｐ）中に含まれる繰り返し単位（Ａ）を構成する単量体（ａ）が、樹脂（Ｐ）の固形分に対して１．０質量％以下であることを特徴とする上記（１）に記載の感活性光線性又は感放射線性樹脂組成物。 The present invention is as follows.
[1]
An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (P) having a repeating unit (A) having a structural site (X) that decomposes upon irradiation with actinic rays or radiation to generate an acid, The abundance of the monomer (a) constituting the repeating unit (A) contained in the resin (P) in the composition is based on the mass of the actinic ray-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition (however, the repeating unit (1) represented by the following general formula (1) and the following general formula (2) ), A repeating unit (2) represented by the following general formula (3), and a repeating unit (4) represented by the following general formula (4). A polymer containing at least one repeating unit and a solvent Excluding radiation-sensitive resin composition comprising a.).

(In the general formula (1), R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and Z represents a monovalent group having a function of generating an acid upon irradiation).

(In the above general formulas (2), (3), and (4), R ² independently represents a hydrogen atom, a methyl group, or a trifluoromethyl group. The above general formulas (2) and (4) In the formula, each A independently represents a methylene group, a linear or branched alkylene group having 2 to 10 carbon atoms, or an arylene group having 3 to 10 carbon atoms. represents a group having the structure represented by the following general formula (i), a is 0 or 1. in formula (3), R ³ is a linear or branched alkyl having 1 to 10 carbon atoms (In the general formula (4), b represents an integer of 2 to 4, and c represents 0 or 1).

(In the above general formula (i), R ⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, p represents 1 or 2, and q represents 1 or 2. , P = 2, the two R ⁴ may be the same or different. )
[2 ]
Actinic ray-sensitive containing resin (P) having a repeating unit (A) having a structural site (X) that decomposes upon irradiation with actinic rays or radiation to generate an acid, and purified by gel filtration chromatography Or it is a radiation sensitive resin composition, Comprising: The abundance of the monomer (a) which comprises the repeating unit (A) contained in the said resin (P) in the said composition is said actinic-ray-sensitive Or the actinic-ray-sensitive or radiation-sensitive resin composition characterized by being 0.05 mass% or less with respect to the mass of a radiation-sensitive resin composition.
[ 3 ]
An activity containing a repeating unit (A) having a structural site (X) that decomposes upon irradiation with actinic rays or radiation to generate an acid and a resin (P) having a repeating unit represented by the following general formula (VI) A light-sensitive or radiation-sensitive resin composition, wherein the abundance of the monomer (a) constituting the repeating unit (A) contained in the resin (P) in the composition is the activity-sensitive An actinic ray-sensitive or radiation-sensitive resin composition, which is 0.05% by mass or less based on the mass of the light-sensitive or radiation-sensitive resin composition.

Here, R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ represents an alkylene group and may be bonded to Ar ₆ to form a 5-membered or 6-membered ring.
Ar ₆ represents an aromatic ring group.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.
[ 4 ]
An activity containing a repeating unit (A) having a structural site (X) that decomposes upon irradiation with actinic rays or radiation to generate an acid and a resin (P) having a repeating unit represented by the following general formula (IV) A light-sensitive or radiation-sensitive resin composition, wherein the abundance of the monomer (a) constituting the repeating unit (A) contained in the resin (P) in the composition is the activity-sensitive An actinic ray-sensitive or radiation-sensitive resin composition, which is 0.05% by mass or less based on the mass of the light-sensitive or radiation-sensitive resin composition.

Here, R ₄₁ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
R ₄₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ represents an alkylene group and may be bonded to Ar ₄ to form a 5-membered or 6-membered ring.
Ar ₄ represents an aromatic ring group. n represents an integer of 1 to 4.
[ 5 ]
The actinic ray-sensitive or radiation-sensitive resin according to any one of [1 ] to [ 4 ], wherein the resin (P) further has a repeating unit (B) having an alkali-soluble group. Composition.
[ 6 ]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1] , [3 ] or [ 4 ], wherein the resin (P) is purified by a gel filtration chromatography method.
[ 7 ]
The actinic ray-sensitive or radiation-sensitive property according to any one of [1 ], [2] and [ 4 ], wherein the resin (P) further has a repeating unit represented by the following general formula (VI): Resin composition.

Here, R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ represents an alkylene group and may be bonded to Ar ₆ to form a 5-membered or 6-membered ring.
Ar ₆ represents an aromatic ring group.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.
[ 8 ]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [ 3 ], wherein the resin (P) further has a repeating unit represented by the following general formula (IV).

Here, R ₄₁ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
R ₄₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ represents an alkylene group and may be bonded to Ar ₄ to form a 5-membered or 6-membered ring.
Ar ₄ represents an aromatic ring group. n represents an integer of 1 to 4.
[ 9 ]
The actinic ray sensitive or radiation sensitive material according to any one of [1] to [ 8 ], wherein the structural moiety (X) is a structural moiety that generates an acid anion in a side chain of the resin upon irradiation with actinic rays or radiation. Resin composition.
[1 0 ]
The monomer (a) constituting the repeating unit (A) contained in the resin (P) is 1.0% by mass or less based on the solid content of the resin (P) [1. ] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [ 9 ] to [ 9 ].
[1 1 ]
Any one of [1] to [1 0 ], wherein the resin (P) further has a repeating unit (C) having a group that decomposes by the action of an acid to generate an alkali-soluble group. The actinic ray-sensitive or radiation-sensitive resin composition described.
[1 2 ]
The resin (P) further has a repeating unit (D) having a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer, [1] to [1 1 ] The actinic-ray-sensitive or radiation-sensitive resin composition of any one of.
[1 3 ]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [1 2 ], wherein an electron beam, X-ray or EUV light is used as an exposure light source.
[1 4 ]
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [1 3 ].
[1 5 ]
[1]-[1 3 ] The pattern formation which has a process which forms a resist film using the actinic-ray-sensitive or radiation-sensitive resin composition of any one of, and exposes and develops. Method.
[1 6 ]
The resin (P) is a resin purified by gel filtration chromatography, and an actinic ray-sensitive or radiation-sensitive resin composition is prepared using the resin (P), and a resist film is formed from the composition. The pattern forming method according to [ 15 ], further comprising a step of exposing and developing.
[1 7 ]
The method for purifying the resin (P) contained in the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [1 3 ] is a gel filtration chromatography method, To purify the resin.
Although this invention is invention which concerns on said [1]-[1 7 ], below, other matters (for example, following (1)-(14)) are also described below.
(1) An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (P) having a repeating unit (A) having a structural site (X) that decomposes upon irradiation with actinic rays or radiation to generate an acid The abundance of the monomer (a) constituting the repeating unit (A) contained in the resin (P) in the composition is that of the actinic ray-sensitive or radiation-sensitive resin composition. An actinic ray-sensitive or radiation-sensitive resin composition, which is 0.05% by mass or less based on mass.
(2) The monomer (a) constituting the repeating unit (A) contained in the resin (P) is 1.0% by mass or less based on the solid content of the resin (P). The actinic ray-sensitive or radiation-sensitive resin composition according to (1) above.

(3) The resin (P) further has a repeating unit (C) having a group capable of decomposing under the action of an acid to generate an alkali-soluble group, as described in (1) or (2) above An actinic ray-sensitive or radiation-sensitive resin composition.
(4) The actinic ray-sensitive or radiation-sensitive composition according to any one of (1) to (3) above, wherein the resin (P) further has a repeating unit (B) having an alkali-soluble group. Resin composition.

(5) The above (1), wherein the resin (P) further has a repeating unit (D) having a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of to (4).
(6) The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of (1) to (5) above, wherein an electron beam, X-ray or EUV light is used as the exposure light source.

(7) A pattern comprising a step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (6) above, and exposing and developing the resist film. Forming method.
(8) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (2) to (6) above, wherein the resin (P) is purified by a gel filtration chromatography method.

(9) The resin (P) is a resin purified by gel filtration chromatography, and an actinic ray-sensitive or radiation-sensitive resin composition is prepared using the resin (P). The pattern forming method as described in (7) above, which comprises a step of forming a film, exposing and developing.
(10) The resin characterized in that the purification method of the resin (P) contained in the actinic ray-sensitive or radiation-sensitive resin composition according to the above (1) to (6) is a gel filtration chromatography method Purification method.

  The preferred embodiments of the present invention will be further described below.

(11) The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of (1) to (6) above, wherein the structural moiety (X) is an ionic structural moiety.
(12) Any one of (1) to (6) and (11) above, wherein the structural site (X) is a structural site that generates an acid anion in a side chain of the resin upon irradiation with actinic rays or radiation The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1.

(13) The repeating unit (B) having an alkali-soluble group is a repeating unit having an aromatic ring, as described in any one of (4) to (6), (11) and (12) above An actinic ray-sensitive or radiation-sensitive resin composition.
(14) The activity according to any one of (1) to (6) and (11) to (13) above, wherein the resin (P) has a weight average molecular weight in the range of 1000 to 100,000. A light-sensitive or radiation-sensitive resin composition.

  According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition that can simultaneously satisfy high sensitivity, high resolution, good pattern shape, and good line edge roughness, a pattern formation method using the composition, and the method A method for purifying a resin used in the composition can be provided.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. . For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.
The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is preferably a positive chemically amplified resist composition.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin (P) having a repeating unit (A) having a structural site (X) that decomposes upon irradiation with actinic rays or radiation described below to generate an acid. And the abundance of the monomer (a) constituting the repeating unit (A) contained in the resin (P) in the composition is relative to the mass of the composition (including the solvent). 0.05 mass% or less. In addition, the mass of the said composition includes the mass of a solvent.
The amount of the monomer (a) present is preferably as small as possible, more preferably 0.02% by mass or less, and particularly preferably 0.01% by mass or less, based on the mass of the composition.
The abundance of the monomer (a) constituting the repeating unit (A) contained in the resin (P) in the actinic ray-sensitive or radiation-sensitive resin composition is measured by high performance liquid chromatography (HPLC). can do.
Residue of the monomer containing the photoacid-generating structure in the resist composition and in the resin cannot sufficiently control the acid diffusibility, or the elution into the immersion liquid cannot be suppressed. It is estimated that the performance is hindered. According to this point, a resist containing a resin having a photoacid generating structure is preferred to a resist containing a general low molecular photoacid generator.

[1] Resin (P)
The resin (P) contained in the actinic ray-sensitive or radiation-sensitive resin composition used in the present invention is a repeating unit having a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid as described below. (A).
The abundance of the monomer (a) constituting the repeating unit (A) contained in the resin (P) in the composition is based on the mass of the actinic ray-sensitive or radiation-sensitive resin composition. Therefore, the resin (P) contains the monomer (a) constituting the repeating unit (A) contained in the resin (P) in a solid content of the resin (P). It is preferable that it is 1.0 mass% or less with respect to.
The solid content of the resin (P) refers to a resin (P) obtained by purifying the polymer after polymerization (for example, reprecipitation, gel filtration chromatography, etc.) and then vacuum drying (130 ° C., 2 hours). The content of the monomer (a) relative to the solid content of the resin (P) can be measured by high performance liquid chromatography (HPLC).
The content of the monomer (a) is preferably as small as possible, more preferably 0.2% by mass or less, and particularly preferably 0.05% by mass or less, based on the solid content of the resin (P).

In order to obtain a resin in which the monomer (a) constituting the repeating unit (A) contained in the resin (P) is 1.0% by mass or less with respect to the solid content of the resin (P), Performs purification on the synthesized resin.
The purification method is not particularly limited, but it is preferable to use a gel filtration chromatography method or a reprecipitation method, and it is particularly preferable to use a gel filtration chromatography method.
In the gel filtration chromatography method, since the high molecular weight compound is eluted in the order of the low molecular weight compound, it is divided into several fractions, for example, 30 fractions, and the presence of a specific monomer is confirmed by HPLC for all the fractions, for example, It is advantageous in that it is possible to reliably obtain a purified polymer containing no specific monomer by collecting the 15 fractions and concentrating under reduced pressure after confirming that the first 15 fractions are free of the specific monomer.

The gel filtration chromatography method is a method in which a resin (P) is passed through a carrier packed in a column to separate molecules according to the difference in size, and since small molecules can be excluded from large molecules, resin (P) and It is possible to separate the residual monomer. The carrier is a spherical porous particle.For example, a dextran carrier with high molecular weight selectivity, which is more porous than dextran, agarose carrier that can increase the separation rate, allyl dextran is cross-linked with N, N'-methylenebisacrylamide A carrier, a carrier obtained by covalently binding dextran to crosslinked agarose, or the like can be used.
As a developing solvent for gel filtration, for example, a solvent having a carrier swelling volume (ml / g dry gel) of 2.5 or more is preferable. Specifically, for example, dimethyl sulfoxide, dimethylformamide, pyridine, methanol, ethylene Examples thereof include dichloride, propanol, isobutanol, formamide, methylene dichloride, butanol, isopropanol, tetrahydrofuran, 1-methoxy-2-propanol, and mixed solvents thereof.

As the reprecipitation method, a known method such as the reprecipitation method described in Patent Document 4 or 5 can be used.
For example, a method in which a solution (for example, a polymerization solution) of the resin (P) is supplied from a nozzle (for example, a diameter of 0.1 to 6 mmφ) into a poor solvent for the resin (P), and is precipitated or re-precipitated. Can be mentioned. The precipitated or re-precipitated particulate polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use.
Examples of the poor solvent for the resin (P) include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; benzene, Aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (Nitromethane, nitroethane, etc.), nitriles (acetonitrile, benzonitrile, etc.), ethers (chain ethers such as diethyl ether, diisopropyl ether, dimethoxyethane; cyclic ethers such as tetrahydrofuran, dioxane), ketones (acetone, methylethyl) , Diisobutyl ketone, etc.), ester (ethyl acetate, butyl acetate, etc.), carbonate (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohol (methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), carboxylic acid (Acetic acid etc.), water, a mixed solvent containing these solvents, etc., can be appropriately selected and used.
Among these, as the reprecipitation solvent, a solvent containing at least a hydrocarbon (particularly an aliphatic hydrocarbon such as hexane) or a solvent containing at least an alcohol is preferable.
In the solvent containing at least hydrocarbon, the ratio of hydrocarbon (for example, aliphatic hydrocarbon such as hexane) and other solvent (for example, ester such as ethyl acetate) is, for example, the former / the latter (volume ratio; 25 ° C) = 5/95 to 95/5, preferably the former / the latter (volume ratio; 25 ° C.) = 20/80 to 90/10, more preferably the former / the latter (volume ratio; 25 ° C.) = 40/60 to It is about 85/15.
In a solvent containing at least an alcohol, the ratio of the alcohol (for example, methanol) and the other solvent (for example, water) is, for example, the former / the latter (volume ratio; 25 ° C.) = 2 / 98-100 / 0, The former / the latter (volume ratio; 25 ° C.) = 5 / 95−98 / 2, more preferably the former / the latter (volume ratio; 25 ° C.) = 10 / 90−95 / 5.
The amount of the reprecipitation solvent can be appropriately selected in consideration of efficiency, yield, etc. Generally, it is generally 100 to 10000 parts by weight, preferably 200 to 5000 parts by weight, more preferably 100 parts by weight of the polymer solution. Is 300 to 3000 parts by mass.
Moreover, after reprecipitating resin (P) once, after dispersing the obtained solid in alcohol, the method of isolate | separating the said resin can also be mentioned. The temperature in this reprecipitation method is preferably 30 to 70 ° C., and the dispersion is preferably performed for 1 minute or more. As alcohol, C1-C3, such as methanol, ethanol, 1-propanol, 2-propanol, is mentioned, for example. The amount of alcohol used is usually 0.5 to 1000 times, preferably 2 to 100 times, particularly preferably 5 to 30 times the mass of the resin (P). The method for separating the resin and alcohol after reprecipitation is not particularly limited, and examples thereof include filtration by filtration, centrifugation, and decantation.
In addition, as described in Non-Patent Document 2, as a reprecipitation method, reprecipitation with a nonaqueous solvent (for example, a mixed solvent of a hydrocarbon solvent such as hexane and an ester solvent such as ethyl acetate), an aqueous system, It is also possible to use a method in which reprecipitation with a solvent (for example, a mixed solvent of water and an alcohol solvent such as methanol) is combined.
The monomer corresponding to the repeating unit (A) (especially in the case of an ionic structure), unlike other monomers, tends to be difficult to dissolve in a hydrocarbon solvent, and in this case, removal by reprecipitation is difficult. When alcohol is used, the monomer corresponding to the repeating unit (A) (particularly in the case of an ionic structure) may dissolve well, or the polymer may dissolve.
In the reprecipitation method, it is preferable to select a solvent in which the monomer corresponding to the repeating unit (A) is easily dissolved and the polymer is difficult to dissolve, and as described above, reprecipitation with a non-aqueous solvent and an aqueous solvent. It is preferable to do both. As described above, purification by gel filtration is most preferable.

  Hereinafter, the repeating unit such as the repeating unit (A) having a structural site (X) which is decomposed by irradiation with actinic rays or radiation to generate an acid and the synthesis method contained in the resin (P) will be described.

Repeating unit (A)
As the repeating unit (A), any repeating unit having a structural moiety (X) that decomposes upon irradiation with actinic rays or radiation to generate an acid can be used.

  As the repeating unit (A), for example, a repeating unit represented by any one of the following general formulas (III) to (V) is preferable.

In the general formulas (III) to (V), R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Represent.
R ₀₆ represents a cyano group, a carboxyl group, —CO—OR ₂₅ or —CO—N (R ₂₆ ) (R ₂₇ ). R ₂₆ and R ₂₇ may combine to form a ring together with the nitrogen atom.
L _{1 to} L ₃ are each independently a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R ₃₃ ) —, or a combination thereof. Represents a divalent linking group.
R ₂₅ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.
R ₂₆ , R ₂₇ and R ₃₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or an aralkyl group.
X represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid.

In the general formulas (III) to (V), the alkyl groups represented by R _{04 to} R ₀₅ and R _{07 to} R ₀₉ are preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group that may have a substituent. Group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a dodecyl group and the like, and an alkyl group having 20 or less carbon atoms, and more preferably an alkyl group having 8 or less carbon atoms. .
Examples of the cycloalkyl group include cycloalkyl groups that may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.
As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R _{04 to} R ₀₅ and R _{07 to} R ₀₉ are preferable.
As the alkyl group for R _{25 to} R ₂₇ and R ₃₃ , an optionally substituted methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, An alkyl group having 20 or less carbon atoms such as 2-ethylhexyl group, octyl group or dodecyl group is exemplified, and an alkyl group having 8 or less carbon atoms is more preferable.
Examples of the cycloalkyl group include cycloalkyl groups that may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent.
Preferred examples of the alkenyl group include those having 2 to 6 carbon atoms, such as a vinyl group, propenyl group, allyl group, butenyl group, pentenyl group, hexenyl group, and cyclohexenyl group which may have a substituent. It is done.
As the aryl group, a monocyclic or polycyclic aromatic group having 6 to 14 carbon atoms which may have a substituent is preferable. Specifically, a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, A naphthyl group etc. are mentioned. In addition, aryl groups may be bonded to form a multicycle.
Examples of the aralkyl group include those having 7 to 15 carbon atoms which may have a substituent such as a benzyl group, a phenethyl group, or a cumyl group.
The ring formed by combining R ₂₆ and R ₂₇ together with the nitrogen atom is preferably a ring that forms a 5- to 8-membered ring, and specific examples include pyrrolidine, piperidine, and piperazine.
The arylene group of L _{1 to} L ₃ is preferably an arylene group having 6 to 14 carbon atoms which may have a substituent, and specific examples thereof include a phenylene group, a tolylene group and a naphthylene group.
The alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group.
Preferred examples of the cycloalkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent.
Preferred substituents for each group in the general formulas (III) to (V) are a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, R ₀₄ to R ₀₉ , R _{25 to} R ₂₇ , R ₃₃ , alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups, alkoxy groups, methoxycarbonyl groups, ethoxycarbonyl groups, etc. Examples include an acyl group such as an alkoxycarbonyl group, formyl group, acetyl group and benzoyl group, an acyloxy group such as an acetoxy group and a butyryloxy group, and a carboxy group. The substituent preferably has 8 or less carbon atoms.

  Specific examples of the structural site (X) include photo-initiators for cationic photopolymerization, photo-initiators for photo-radical polymerization, photo-decoloring agents for dyes, photo-discoloring agents, and microresists. The compound which generate | occur | produces an acid by this light can be mentioned. Although it does not specifically limit as structural site | part (X), For example, the structural site | part which the following photo-acid generator has can be mentioned.

A diazonium salt described in SI Schlesinger, Photogr. Sci. Eng., 18,387 (1974), TSBal etal, Polymer, 21, 423 (1980) and the like.
Ammonium salts described in U.S. Pat. Nos. 4,069,055, 4,069,056, Re 27,992, and Japanese Patent Application No. 3-140,140.
Phosphonium salts described in DCNecker etal, Macromolecules, 17, 2468 (1984), CSWen etal, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.

JVCrivello etal, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng.News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Pat. -Iodonium salts described in JP-A No. 150,848 and JP-A-2-296514.
JVCrivello etal, Polymer J. 17, 73 (1985), JVCrivello et. Al. J. Org. Chem., 43, 3055 (1978), WRWatt etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), JVCrivello etal, Polymer Bull., 14,279 (1985), JVCrivello etal, Macromorecules, 14 (5), 1141 (1981), JVCrivello etal, J. PolymerSci., PolymerChem. Ed., 17, 2877 (1979) European Patent Nos. 370,693, 3,902,114, 233,567, 297,443, 297,442, U.S. Patents 4,933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, Sulfonium salts described in 2,833,827, Yasukuni Patent Nos. 2,904,626, 3,604,580, 3,604,581 and the like.

Selenonium salts described in JVCrivello etal, Macromorecules, 10 (6), 1307 (1977), JVCrivello etal, J. PolymerSci., Polymer Chem. Ed., 17, 1047 (1979).
Onium salts such as arsonium salts described in CSWen etal, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988).
U.S. Pat.No. 3,905,815, JP 46-4605, JP 48-36281, JP 55-32070, JP 60-239736, JP 61-169835, JP 61- Organic halogen compounds described in 169837, JP 62-58241, JP 62-212401, JP 63-70243, JP 63-298339, and the like. K. Meier etal, J. Rad. Curing, 13 (4), 26 (1986), TPGill etal, Inorg. Chem., 19, 3007 (1980), D. Astruc, Acc. Chem. Res., 19 (12 ), 377 (1896), JP-A-2-16145, and the like.

  S. Hayase etal, J. Polymer Sci., 25, 753 (1987), E. Reichmanis etal, J. Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhu etal, J. Photochem., 36 85, 39, 317 (1987), B. Amit etal, Tetrahedron Lett., (24) 2205 (1973), DHR Barton etal, J. Chem Soc., 3571 (1965), PMCollins etal, J. Chem. SoC. Perkin I, 1695 (1975), M. Rudinstein etal, Tetrahedron Lett., (17), 1445 (1975), JWWalker etal, J. Am. Chem. Soc., 110, 7170 (1988), SCBusman etal , J. Imaging Technol., 11 (4), 191 (1985), HMHoulihan etal, Macormolecules, 21, 2001 (1988), PMCollins etal, J. Chem. Soc., Chem. Commun., 532 (1972) , S. Hayase etal, Macromolecules, 18, 1799 (1985), E. Reichmanis etal, J. Electrochem. Soc., Solid State Sci. Technol., 130 (6), FM Houlihan etal, Macromolcules, 21,2001 (1988) ), European Patent Nos. 0290,750, 046,083, 156,535, 271,851, 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP 60-198538, JP 53-133022 Photoacid having o-nitrobenzyl type protecting group as described in No. Namazai.

  M. TUNOOKA etal, Polymer Preprints Japan, 35 (8), G. Berner etal, J. Rad. Curing, 13 (4), WJMijs etal, Coating Technol., 55 (697), 45 (1983), Akzo, H. Adachietal, Polymer Preprints, Japan, 37 (3), European Patent No. 0199,672, No. 84515, No. 199,672, No. 044,115, No. 0101,122, U.S. Patent Nos. 618,564, No. 4,371,605, Compounds that generate sulfonic acid by photolysis, such as iminosulfonates described in JP-A-4,431,774, JP-A-64-18143, JP-A-2-245756, and Japanese Patent Application 3-140109.

Disulfone compounds described in JP-A-61-166544.
Furthermore, VNRPillai, Synthesis, (1), 1 (1980), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971), DHR Barton etal, J. Chem. Soc., (C), 329 (1970) , U.S. Pat.No. 3,779,778,
Compounds that generate an acid by light as described in European Patent No. 126,712 and the like.

  The structural site (X) is preferably an ionic structural site, more preferably an ionic structural site containing a sulfonium salt or an iodonium salt.

  The structural site (X) is more preferably a structural site that generates an acid anion in the side chain of the resin upon irradiation with actinic rays or radiation, and is represented by the following general formula (ZI) or (ZII). Are particularly preferred.

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
Z ⁻ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion. Examples of the non-nucleophilic anion include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methide anion. (Alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion are preferable, and sulfonate anion is more preferable. Here, the alkyl is preferably substituted with a fluorine atom.
A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. As a result, the temporal stability of the resin is improved, and the temporal stability of the resist is also improved.

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the groups represented by (ZI-1), (ZI-2) and (ZI-3) described later. .
More preferable examples of the group represented by (ZI) include a (ZI-1) group, a (ZI-2) group, and a (ZI-3) group described below.
The (ZI-1) group is a group having an arylsulfonium as a cation, wherein at least one of R _{201 to} R ₂₀₃ in the general formula (ZI) is an aryl group.
All of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.
For example, groups corresponding to triarylsulfonium, diarylalkylsulfonium, aryldialkylsulfonium, diarylcycloalkylsulfonium, aryldicycloalkylsulfonium can be exemplified.
The aryl group in the arylsulfonium is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of this heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like. When arylsulfonium has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group that arylsulfonium has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group or ethyl group. Group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like.
The aryl group, alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ are an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms). , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon. These are an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, the (ZI-2) group will be described.
The (ZI-2) group is a group in which R _{201 to} R ₂₀₃ in the general formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group not containing an aromatic ring as R _{201 to} R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.
As the alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ , a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.
The 2-oxoalkyl group may be either linear or branched, and a group having> C = O at the 2-position of the above alkyl group is preferable.
The 2-oxocycloalkyl group is preferably a group having> C═O at the 2-position of the cycloalkyl group.
The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
The (ZI-3) group is a group represented by the following general formula (ZI-3), which is a group having a phenacylsulfonium salt structure.

In general formula (ZI-3),
R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.
Any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom, a sulfur atom , An ester bond and an amide bond may be included. Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ^{− in} formula (ZI).
The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group. Examples of the cycloalkyl group include cyclohexane having 3 to 8 carbon atoms. An alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.
The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).
Preferably, any of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c. Is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.
_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c, and include a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxy group. A carbonylmethyl group is more preferred.
Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .
As for the alkoxy group in the alkoxycarbonylmethyl group, the same alkoxy groups as in R _{1c to} R _5c can be exemplified.
R _x and R _y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

In the general formula (ZII), R _{204 to} R ₂₀₅ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _205, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₅ represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of this heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like.
The alkyl group and cycloalkyl group in R _{204 to} R ₂₀₅ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₅ may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _205, the cycloalkyl group substituent which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms ), An aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
Z ⁻ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion, and examples thereof include the same as Z ⁻ in the general formula (ZI).

  Specific examples of the repeating unit (A) are illustrated below, but the present invention is not limited thereto.

The content of the repeating unit (A) in the resin (P) of the present invention is preferably in the range of 0.5 to 80 mol%, and in the range of 1 to 60 mol%, based on all repeating units. It is more preferable to contain, and it is especially preferable to contain in 3-40 mol%.
The method for synthesizing the monomer (a) corresponding to the repeating unit (A) is not particularly limited. For example, an acid anion having a polymerizable unsaturated bond corresponding to the repeating unit and a known onium salt halide are used. The method of synthesizing by exchanging is mentioned.
More specifically, a metal ion salt (for example, sodium ion, potassium ion, etc.) or an ammonium salt (ammonium, triethylammonium salt, etc.) of an acid having a polymerizable unsaturated bond corresponding to the repeating unit, and a halogen ion ( An onium salt having a chloride ion, bromide ion, iodide ion, etc.) is stirred in the presence of water or methanol to carry out an anion exchange reaction, such as dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone, tetrahydroxyfuran, etc. By performing a liquid separation / washing operation with an organic solvent and water, the monomer (a) corresponding to the target repeating unit (A) can be synthesized.
After anion exchange reaction by stirring in the presence of an organic solvent that can be separated from water, such as dichloromethane, chloroform, ethyl acetate, methyl isobutyl ketone, and tetrahydroxyfuran, and water separation, washing with water It can also be synthesized by operating.

Repeating unit (C)
In addition to the repeating unit (A), the resin (P) is decomposed by the action of an acid to generate an alkali-soluble group (C) (hereinafter referred to as “a repeating unit having an acid-decomposable group”). It is preferable to have
Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.
Preferred alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.

A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.
As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R _{01 to} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

  As the repeating unit (C), a repeating unit represented by the following general formula (V) is more preferable.

In the formula, R ₅₁ , R ₅₂ and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₅₂ represents an alkylene group and may be bonded to L ₅ to form a 5-membered or 6-membered ring. L ₅ represents a single bond or a divalent linking group (provided that it forms a 5-membered or 6-membered ring by binding to R ₅₂ ). R ₅₄ represents an alkyl group. R ₅₅ and R ₅₆ each independently represents an alkyl group, a cycloalkyl group or an aryl group. R ₅₅ and R ₅₆ may combine with each other to form a ring.

As the alkyl group for R _{51 to} R _53, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, or 2-ethylhexyl, which may have a substituent, is preferable. And an alkyl group having 20 or less carbon atoms such as a group, octyl group or dodecyl group, more preferably an alkyl group having 8 or less carbon atoms.
Examples of the cycloalkyl group include cycloalkyl groups that may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
A fluorine atom is more preferable.
The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in the above R _{51 to} R ₅₃ .

Examples of the divalent linking group represented by L _5, an alkylene group, an arylene group, aralkylene _{group, -COO-L 1 -, -} O-L 1 -, a group formed by combining two or more of these Is mentioned. Here, L ₁ represents an alkylene group, a cycloalkylene group, an arylene group, or an aralkylene group.
L ₅ is preferably a single bond, —COO-L ₁ — (L ₁ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene or propylene group) or an arylene group.

The alkyl group of R _{54 to} R ₅₆ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Particularly preferred are those having 1 to 4 carbon atoms such as a group, isobutyl group and t-butyl group.
The cycloalkyl group represented by R ₅₅ and R _56, preferably one having 1 to 20 carbon atoms, cyclopentyl, may be of monocyclic and cyclohexyl group, norbornyl group, tetracyclodecanyl deca A polycyclic group such as a nyl group or a tetracyclododecanyl group may be used, but a monocyclic group is more preferable from the viewpoint of solubility in a resist solvent.
The aryl group represented by R ₅₅ and _{R 56,} preferably has 6 to 20 carbon atoms, for example, a phenyl group, a naphthyl group, and the like. When either one of R ₅₅ and R ₅₆ is a hydrogen atom, the other is preferably aryl.
The ring formed by combining R ₅₅ and R ₅₆ with each other preferably has 1 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group. Polycyclic ones such as a tetracyclodecanyl group and a tetracyclododecanyl group may be used, but a monocyclic one is more preferable from the viewpoint of solubility in a resist solvent. When R ₅₅ and R ₅₆ are bonded to each other to form a ring, R ₅₄ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.

The content of the repeating unit (C) in the resin (P) is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, based on all repeating units. More preferably, it is the range of 20-70 mol%. One type of repeating unit (C) may be used, or two or more types may be used in combination.
As a method for synthesizing the monomer corresponding to the repeating unit (C), a general method for synthesizing a polymerizable group-containing ester can be applied, and is not particularly limited.

  Although the specific example of the repeating unit (C) in resin (P) is shown below, this invention is not limited to this.

  Moreover, as the repeating unit (C), a repeating unit represented by the following general formula (VI) is more preferable.

Here, R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ represents an alkylene group and may be bonded to Ar ₆ to form a 5-membered or 6-membered ring.
Ar ₆ represents an aromatic ring group.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4, preferably 1 to 2, and more preferably 1.

As the alkyl group of R _{61 to} R ₆₃ in the general formula (VI), a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may preferably have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, and more preferable examples include alkyl groups having 8 or less carbon atoms.
As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R _{61 to} R ₆₃ are preferable.
Examples of the cycloalkyl group include cycloalkyl groups that may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.
If R ₆₂ represents an alkylene group, the alkylene group, preferably methylene group, ethylene group, propylene group, butylene group, hexylene group include those having 1 to 8 carbon atoms such as octylene group.

The aromatic ring group of Ar ₆ preferably has 6 to 14 carbon atoms which may have a substituent, and specific examples thereof include a benzene ring, a toluene ring and a naphthalene ring.

n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of n represents a group capable of leaving by the action of an acid.
Examples of the group Y leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ). _{), - C (R 01)} (R 02) (OR 39), - C (R 01) (R 02) -C (= O) -O-C (R 36) (R 37) (R 38), —CH (R ₃₆ ) (Ar) and the like can be mentioned.

In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R _{01 to} R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
Ar represents an aryl group.
The alkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Group, octyl group and the like.
The cycloalkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group. Group, androstanyl group and the like. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
The aryl group of R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ and Ar is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
The aralkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
The alkenyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
The ring formed by combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkane structure having 3 to 8 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. As the polycyclic type, a cycloalkane structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. In addition, a part of carbon atoms in the cycloalkane structure may be substituted with a heteroatom such as an oxygen atom.
Each of the above groups as R ₆₁ , R ₆₂ , R ₆₃ , R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ , R _03, Ar and Ar ₆ may have a substituent. For example, alkyl group, cycloalkyl group, aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano Group, nitro group and the like, and a substituent having 8 or less carbon atoms is preferable.

  The group Y that is eliminated by the action of an acid is more preferably a structure represented by the following general formula (II).

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group, an alicyclic group which may contain a hetero atom, an aromatic ring group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. .
At least two of Q, M, and L ₁ may combine to form a 5-membered or 6-membered ring.

The alkyl group as L ₁ and L ₂ is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group. An octyl group can be preferably mentioned.
The cycloalkyl group as L ₁ and L ₂ is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and specifically, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group can be preferably exemplified.
The aryl group as L ₁ and L ₂ is, for example, an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group, and an anthryl group.
The aralkyl group as L ₁ and L ₂ has, for example, 6 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.

The divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.), cycloalkylene group (for example, cyclopentylene group, cyclohexylene group). Group), alkenylene group (for example, ethylene group, propenylene group, butenylene group, etc.), arylene group (for example, phenylene group, tolylene group, naphthylene group, etc.), -S-, -O-, -CO-, -SO _2- , -N (R ₀ )-, and a divalent linking group in which a plurality of these are combined. R ₀ represents a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group). Octyl group, etc.).
The alkyl group and cycloalkyl group as Q are the same as the above groups as L ₁ and L ₂ .
As the alicyclic group and the aromatic ring group in the alicyclic group which may contain a hetero atom as Q and the aromatic ring group which may contain a hetero atom, the cycloalkyl as L ₁ and L ₂ described above is used. Group, an aryl group, etc. are mentioned, Preferably it is C3-C15.
Examples of the alicyclic group containing a hetero atom and the aromatic ring group containing a hetero atom include, for example, thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole. And groups having a heterocyclic structure such as pyrrolidone, but are not limited to these as long as the structure is generally called a heterocyclic ring (a ring formed of carbon and a heteroatom, or a ring formed of a heteroatom). .

As a 5-membered or 6-membered ring that may be formed by combining at least two of Q, M, and L ₁ , at least two of Q, M, and L ₁ are combined to form, for example, a propylene group and a butylene group In this case, a 5-membered or 6-membered ring containing an oxygen atom is formed.
Each group represented by L ₁ , L ₂ , M, and Q in the general formula (II) may have a substituent. For example, R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ , _{Examples of the} substituent that may be possessed by R _03, Ar and Ar ₁ are mentioned, and the substituent preferably has 8 or less carbon atoms.

The group represented by -MQ is preferably a group composed of 1 to 30 carbon atoms, and has 5 carbon atoms.
A group composed of ˜20 is more preferred.

  Specific examples of the repeating unit represented by formula (VI) are shown below as preferred specific examples of the repeating unit (C), but the present invention is not limited thereto.

The content of the repeating unit (C) in the resin of the present invention is preferably 3 to 90 mol%, more preferably 5 to 80 mol%, based on all repeating units. Preferably, it is contained in the range of 7 to 70 mol%.
The ratio of the repeating unit (A) to the repeating unit (C) in the resin (number of moles of A / number of moles of C) is preferably 0.04 to 1.0, more preferably 0.05 to 0.9. 0.06-0.8 is particularly preferable.

Repeating unit (B)
The resin (P) preferably has a repeating unit (B) having an alkali-soluble group in addition to the repeating unit (A) or in addition to the repeating unit (A) / repeating unit (C).
As the repeating unit (B), any repeating unit having at least an alkali-soluble group can be used.
Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.
Preferred alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.

  As the repeating unit (B), an alkali-soluble group having an aromatic ring is preferable, and a structure represented by the following general formula (IV) is particularly preferable.

Here, R ₄₁ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
R ₄₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ represents an alkylene group and may be bonded to Ar ₄ to form a 5-membered or 6-membered ring.
Ar ₄ represents an aromatic ring group. n represents an integer of 1 to 4.

In the general formula (IV), the alkyl group of R ₄₁ , R ₄₂ and R ₄₃ is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec which may have a substituent. -Alkyl groups having 20 or less carbon atoms such as butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group are mentioned, more preferably alkyl groups having 8 or less carbon atoms, particularly preferably alkyl groups having 3 or less carbon atoms. Is mentioned.
As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R ₄₁ , R ₄₂ and R ₄₃ are preferable.
Examples of the cycloalkyl group include cycloalkyl groups that may be monocyclic or polycyclic. Preferable examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
Preferred substituents in the above groups include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, an alkyl group exemplified in R _{41 to} R ₄₃ , and a methoxy group. , Alkoxy groups such as ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, acyl groups such as formyl group, acetyl group and benzoyl group, acetoxy group , Acyloxy groups such as butyryloxy groups, and carboxy groups. In particular, a hydroxyl group and a halogen atom are preferable.
In the case where R ₄₂ represents an alkylene group, the alkylene group, preferably methylene group, ethylene group, propylene group, butylene group, hexylene group, and an alkylene group having 1 to 8 carbon atoms such as octylene group. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable.
R ₄₁ and R ₄₃ in the general formula (IV) are more preferably a hydrogen atom, an alkyl group, or a halogen atom. A hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group (— CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferred. R ₄₂ is more preferably a hydrogen atom, an alkyl group, a halogen atom, or an alkylene group (forming a ring with Ar ₄ ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group Particularly preferred are (—CH ₂ —OH), chloromethyl group (—CH ₂ —Cl), fluorine atom (—F), methylene group (forms a ring with Ar ₄ ), and ethylene group (forms a ring with Ar ₄ ). .

Ar ₄ represents a divalent aromatic ring group. The divalent aromatic ring group may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group, or, for example, thiophene, furan, Preferred examples include divalent aromatic ring groups containing heterocycles such as pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.
Preferred substituents in each of the above groups include alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups, etc., aryl groups such as phenyl groups, and the like mentioned for R _{41 to} R _43. Groups.
Ar ₄ is more preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, and particularly preferably a phenylene group, a naphthylene group, or a biphenylene group.

  Specific examples of the repeating unit represented by formula (IV) are shown below as preferred specific examples of the repeating unit (B), but the present invention is not limited thereto.

  The content of the repeating unit (B) in the resin of the present invention is preferably 3 to 90 mol%, more preferably 5 to 80 mol%, based on all repeating units. Preferably, it is contained in the range of 7 to 70 mol%.

Repeating unit (D)
The resin (P) preferably further has a repeating unit (D) having a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer.
As a group that decomposes by the action of an alkali developer and increases the dissolution rate in the alkali developer,
Examples include lactone structures and phenyl ester structures.
As the repeating unit (D), a repeating unit represented by the following general formula (AII) is more preferable.

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 4 carbon atoms).
Preferred substituents that the alkyl group represented by Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom and a methyl group are particularly preferred.
Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group obtained by combining these. Preferably a single bond, -Ab ₁ -CO ₂ - is a divalent linking group represented by.
Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
V represents a group that decomposes under the action of an alkali developer and increases the dissolution rate in the alkali developer. A group having an ester bond is preferable, and a group having a lactone structure is more preferable.

  As the group having a lactone structure, any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in the form to be formed are preferred. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring.

  The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.

  The content of the repeating unit (D) in the resin (P) is preferably contained in the range of 0.5 to 80 mol%, more preferably in the range of 1 to 60 mol%, based on all repeating units. Yes, more preferably in the range of 2-40 mol%. One type of repeating unit (D) may be used, or two or more types may be used in combination. By using a specific lactone structure, line edge roughness and development defects are improved.

Although the specific example of the repeating unit (D) in resin (P) is shown below, this invention is not limited to this. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The form of the resin (P) of the present invention may be any of random type, block type, comb type, and star type.
The resin (P) according to the present invention having the above-mentioned repeating units (A) to (C) or (A) to (D) can be obtained by, for example, radical, cation or anion polymerization of unsaturated monomers corresponding to each structure. Can be synthesized. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.
The resin (P) of the present invention uses, for example, an unsaturated monomer corresponding to each structure using radical polymerization initiators such as hydroperoxides, dialkyl peroxides, diacyl peroxides, and azo compounds. Accordingly, it can be produced by polymerization in an appropriate solvent in the presence of a chain transfer agent.
Examples of the solvent used for the polymerization include a solvent that can be used when preparing an actinic ray-sensitive or radiation-sensitive resin composition described below. These solvents can be used alone or in admixture of two or more.
The reaction temperature in the polymerization is usually 40 to 120 ° C., preferably 50 to 100 ° C., and the reaction time is usually 1 to 48 hours, preferably 1 to 24 hours. The concentration of the saturated monomer) is 5 to 70% by mass, preferably 10 to 50% by mass.

The molecular weight of the resin (P) according to the present invention is not particularly limited, but the weight average molecular weight is 100.
It is preferably in the range of 0 to 100,000, more preferably in the range of 1500 to 20000, and particularly preferably in the range of 2000 to 10,000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).
The dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.03 to 3.50, and still more preferably 1.05 to 2.50.

Further, for the purpose of improving the performance of the resin according to the present invention, it may further have repeating units derived from other polymerizable monomers as long as the dry etching resistance is not significantly impaired.
The content of repeating units derived from other polymerizable monomers in the resin is generally 50 mol% or less, preferably 30 mol% or less, based on all repeating units. Other polymerizable monomers that can be used include those shown below. For example, it is a compound having one addition polymerizable unsaturated bond selected from (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters and the like. .

Specifically, (meth) acrylic acid esters include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, t-butyl (meth) acrylate, (meth) Amyl acrylate, cyclohexyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid-t-octyl, (meth) acrylic acid 2-chloroethyl, (meth) acrylic acid 2 -Hydroxyethyl, glycidyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate and the like.
(Meth) acrylamides include, for example, (meth) acrylamide, N-alkyl (meth) acrylamide, (the alkyl group has 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl Group, t-butyl group, heptyl group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-aryl (meth) acrylamide (as aryl groups, for example, phenyl group, tolyl group , Nitrophenyl group, naphthyl group, cyanophenyl group, hydroxyphenyl group, carboxyphenyl group, etc.), N, N-dialkyl (meth) acrylamide (the alkyl group has 1 to 10 carbon atoms, for example, , Methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Hexyl group, etc.), N, N-aryl (meth) acrylamide (aryl groups include, for example, phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide. N-2-acetamidoethyl-N-acetylacrylamide and the like.

Examples of allyl compounds include allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyl Examples include oxyethanol.
Examples of vinyl ethers include alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2- Ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc., vinyl aryl ethers (eg vinyl phenyl ether, vinyl tolyl ether, vinyl chloride) Phenyl ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether) and the like.
Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, Examples thereof include vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.
Examples of the crotonic acid esters include alkyl crotonates (for example, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.).
Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
Examples of the dialkyl esters of maleic acid or fumaric acid include dimethyl maleate and dibutyl fumarate.
In addition, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilonitrile, and the like can be given. In general, any addition-polymerizable unsaturated compound copolymerizable with the repeating unit according to the present invention can be used without any particular limitation.

  Resin (P) of this invention can be used individually by 1 type or in combination of 2 or more types. The content of the resin (P) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. ˜100 mass% is particularly preferred.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further include a basic compound, a resin that decomposes by the action of an acid to increase the dissolution rate with respect to alkaline water solubility, and a conventional acid generation as necessary. An agent, a surfactant, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a dissolution promoting compound for a developer, a compound having a proton acceptor functional group, and the like can be contained.

[2] Basic compound The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound.
The basic compound is preferably a nitrogen-containing organic basic compound.

  Although the compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(4) is used preferably.

  (1) Compound represented by the following general formula (BS-1)

In general formula (BS-1),
Each R independently represents a hydrogen atom, an alkyl group (straight or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group, or an aralkyl group. However, not all three Rs are hydrogen atoms.
Although carbon number of the alkyl group as R is not specifically limited, Usually, 1-20, Preferably it is 1
~ 12.
Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, 3-20, Preferably it is 5-15.
Although carbon number of the aryl group as R is not specifically limited, Usually, 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, Usually, 7-20, Preferably it is 7-11. Specific examples include a benzyl group.
In the alkyl group, cycloalkyl group, aryl group or aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.
In the compound represented by the general formula (BS-1), it is preferable that only one of three Rs is a hydrogen atom, or all Rs are not hydrogen atoms.

Specific examples of the compound of the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine, Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N, N- Examples include dihexylaniline, 2,6-diisopropylaniline, 2,4,6-tri (t-butyl) aniline.
In addition, a compound in which at least one R in the general formula (BS-1) is an alkyl group substituted with a hydroxyl group can be mentioned as one of preferable embodiments. Specific examples of the compound include triethanolamine and N, N-dihydroxyethylaniline.

The alkyl group as R may have an oxygen atom in the alkyl chain, and an oxyalkylene chain may be formed. The oxyalkylene chain is preferably —CH ₂ CH ₂ O—. Specific examples include tris (methoxyethoxyethyl) amine and compounds exemplified in column 3, line 60 of US Pat. No. 6,040,112.

(2) Compound having a nitrogen-containing heterocyclic structure The heterocyclic structure may or may not have aromaticity. Moreover, you may have two or more nitrogen atoms, Furthermore, you may contain hetero atoms other than nitrogen. Specifically, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure (N-hydroxyethylpiperidine, bis (1,2,2,6) , 6-pentamethyl-4-piperidyl) sebacate), compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).
A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group has a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound. Examples of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. It may have a substituent.
More preferably, it is a compound having at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is preferable.
Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine and US Patent Application Publication No. 2007/0224539. The compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of the above.

(4) Ammonium salt An ammonium salt is also used as appropriate. Preferred is hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable.

  In addition, compounds synthesized in Examples of JP-A No. 2002-363146, compounds described in paragraph 0108 of JP-A No. 2007-298869, and the like can also be used.

A basic compound is used individually or in combination of 2 or more types.
The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of the total solid of actinic-ray-sensitive or radiation-sensitive resin composition, Preferably it is 0.01-5 mass%.

The molar ratio of acid generator / basic compound is preferably 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. This molar ratio is more preferably 5.0 to 200, and still more preferably 7.0 to 150.
The acid generator in the above molar ratio is the total amount of the repeating unit (a) contained in the resin (P) and the acid generator other than the resin (P) described later.

[3] Resin that is decomposed by the action of an acid to increase the dissolution rate for alkaline water solubility The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is decomposed by the action of an acid in addition to the resin (P). You may contain resin which the melt | dissolution rate with respect to alkali water solubility increases.

  Resins that decompose due to the action of an acid and increase the dissolution rate in an alkaline aqueous solution (hereinafter also referred to as “acid-decomposable resins”) are not included in the main chain or side chain of the resin, or both of the main chain and side chain. It is a resin having a group (acid-decomposable group) that decomposes by the action of and produces an alkali-soluble group. Among these, a resin having an acid-decomposable group in the side chain is more preferable.

The acid-decomposable resin is a precursor of a group that can be decomposed with an acid into an alkali-soluble resin as disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860, JP-A-4-251259, and the like. It can be obtained by copolymerizing an alkali-soluble resin monomer having a group which can be reacted with the body or capable of decomposing with an acid, with various monomers.
As the acid-decomposable group, for example, in a resin having an alkali-soluble group such as —COOH group and —OH group, a group in which the hydrogen atom of the alkali-soluble group shown on the left is substituted with a group capable of leaving by the action of an acid is preferable.
Specifically, the acid-decomposable group is preferably the same group as the acid-decomposable group described in the above-described resin of the present invention (for example, the acid-decomposable group described as the repeating unit (B) in the resin (P)). As an example.

The resin having an alkali-soluble group is not particularly limited. For example, poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene) and copolymers thereof, hydrogenated poly (Hydroxystyrene), poly (hydroxystyrene) s having a substituent represented by the following structure, and resins having phenolic hydroxyl groups, styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers, hydrogen An alkali-soluble resin having a hydroxystyrene structural unit such as a modified novolak resin, and an alkali-soluble resin containing a repeating unit having a carboxyl group such as (meth) acrylic acid or norbornenecarboxylic acid.

  The alkali dissolution rate of these alkali-soluble resins is preferably at least 170 kg / second as measured with 2.38 mass% tetramethylammonium hydroxide (TMAH) (23 ° C.). Particularly preferably, it is 330 Å / second or more.

  The content ratio of the group capable of decomposing with an acid is the number of repeating units (X) having a group capable of decomposing with an acid in the resin (X) and the number of repeating units having an alkali-soluble group not protected with a group capable of leaving with an acid. With (Y), it is expressed as X / (X + Y). The content is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and still more preferably 0.05 to 0.40.

The weight average molecular weight of the acid-decomposable resin is preferably 50,000 or less, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000 as a polystyrene conversion value by the GPC method.
The dispersity (Mw / Mn) of the acid-decomposable resin is preferably 1.0 to 3.0, more preferably 1.05 to 2.0, and still more preferably 1.1 to 1.7.
Two or more acid-decomposable resins may be used in combination.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the compounding amount in the composition of the acid-decomposable resin excluding the resin (P) is preferably 0 to 70% by mass in the total solid content of the composition, More preferably, it is 0-50 mass%, More preferably, it is 0-30 mass%.

[4] Acid generator The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (P) having a photoacid-generating structure, but in addition to the resin (P), actinic rays or A low-molecular compound that generates an acid upon irradiation with radiation (also referred to as an “acid generator”) may be contained.
Examples of such an acid generator include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or an actinic ray or radiation used for a microresist. A known compound that generates an acid by irradiation and a mixture thereof can be appropriately selected and used.

  Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates. Specific examples thereof include those described in [0164] to [0248] of US Patent Application Publication No. 2008 / 0241737A1.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, when an acid generator is used in addition to the resin (P) having a photoacid generating structure, the acid generator is used alone or in combination of two. The above can be used in combination. The content of the acid generator in the composition is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and further preferably 0 to 7% by mass based on the total solid content of the composition. The acid generator is not an essential component in the present invention, but is usually used in an amount of 0.01% by mass or more in order to obtain the effect of addition.

[5] Surfactant
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a surfactant. As the surfactant, fluorine-based and / or silicon-based surfactants are preferable.
Surfactants corresponding to these include Megafac F176, Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical, Sumitomo 3M Examples include Fluorad FC430 manufactured by Co., Ltd., polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include those described in [0273] et seq. Of US Patent Application Publication No. 2008/0248425.

Surfactants may be used alone or in combination of two or more.
The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.

[6] Acid-decomposable dissolution inhibiting compound The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is decomposed by the action of an acid to increase the dissolution rate in an alkali developer, and has a molecular weight of 3000 or less. A compound (hereinafter, also referred to as “dissolution inhibiting compound”) can be contained.
The dissolution inhibiting compound is preferably an alicyclic or aliphatic compound containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996). . Examples of the acid-decomposable group and alicyclic structure are the same as those described for the acid-decomposable resin.
When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is irradiated with an electron beam or EUV light, it preferably contains a structure in which the phenolic hydroxyl group of the phenol compound is substituted with an acid-decomposable group. The phenol compound preferably contains 1 to 9 phenol skeletons, more preferably 2 to 6 phenol skeletons.

  The molecular weight of the dissolution inhibiting compound in the present invention is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.

[7] Other components A dye may be contained. Suitable dyes include oily dyes and basic dyes.

  In order to improve the acid generation efficiency by exposure, a photosensitizer can be further added.

  The dissolution accelerating compound for the developer that can be used in the present invention is a low molecular weight compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. When it has a carboxy group, an alicyclic or aliphatic compound is preferable. Examples of such a phenol compound having a molecular weight of 1000 or less include those described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, and European Patent 219294.

  In addition, compounds having a proton acceptor functional group described in JP-A No. 2006-208781 and JP-A No. 2007-286574 can be suitably used for the composition of the present application.

[8] Solvent The actinic ray-sensitive or radiation-sensitive resin composition is prepared by dissolving the above components in a solvent. In addition, the range of the total solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition is generally 0.5 to 10.0% by mass, preferably 1.0 to 5.0% by mass.
Solvents that can be used when preparing the actinic ray-sensitive or radiation-sensitive resin composition by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate Esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may contain rings (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, etc. Mention may be made of organic solvents.

Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

  Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, -Penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methyl Cyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcyclo A preferred example is heptanone.

Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

Preferred solvents that can be used include 2-heptanone, cyclopentanone, γ-butyrolactone, cyclohexanone, butyl acetate, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-ethoxypropionic acid Examples include ethyl, ethyl pyruvate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, and propylene carbonate. Particularly preferred solvents include propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether.
In the present invention, the above solvents may be used alone or in combination of two or more.

[9] Pattern Formation Method The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is applied on a support such as a substrate to form a resist film. The thickness of the resist film is preferably 0.02 to 0.1 μm.
As a method of coating on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

For example, an actinic ray-sensitive or radiation-sensitive resin composition is applied to a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate application method such as a spinner or a coater. Dry to form a resist film. In addition, a known antireflection film can be applied in advance.
The resist film is usually irradiated with an electron beam (EB), X-rays or EUV light through a mask, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.

In the development step, an alkaline developer is used as follows. As an alkaline developer of the resist composition, inorganic hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline developer.
The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.

Synthesis example 1
9.33 parts by mass of 1-methoxy-2-propanol was heated to 80 ° C. under a nitrogen stream. While stirring this liquid, the monomer (a) described in the column of resin (P-1) in Table 1 below (synthesized with reference to JP-A-2008-163218) 4.23 parts by mass, 7.66 parts by mass of the monomer (c) described in the column of the resin (P-1), 8.11 parts by mass of the monomer (d) described in the column of the resin (P-1) in Table 1, A mixed solution of 37.33 parts by mass of -methoxy-2-propanol and 1.68 parts by mass of dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] was added dropwise over 2 hours. After completion of dropping, the mixture was further stirred at 80 ° C. for 4 hours. The reaction solution was allowed to cool to complete the polymerization.
Sephadex LH-20 (manufactured by GE Healthcare Biosciences) was used as a carrier, methanol / 1-methoxy-2-propanol (50/50 mass ratio) was used as a developing solvent, and the resulting resin was subjected to gel filtration with an open column ( Column thickness: diameter 70 mm, gel loading: 500 parts by mass).
Each of the obtained fractions was analyzed by HPLC, and after collecting the fractions in which the monomer (a) was below the detection limit (0.01% by mass or less), the fractions were concentrated under reduced pressure to give 1-methoxy of resin (P-1). 160 parts by mass of a 2-propanol solution was obtained. Further, the resin (P-1) of the present invention was prepared by reprecipitation with 3200 parts by mass of hexane / ethyl acetate (95/5 mass ratio), filtration, and vacuum drying (130 ° C., 2 hours). Obtained 2 parts by weight.
The weight average molecular weight (Mw: converted to polystyrene) obtained from GPC (carrier: N-methyl-2-pyrrolidone (NMP)) of the obtained resin (P-1) is Mw = 4900, and the dispersity is Mw / Mn = 1.67. Moreover, when the mass% of monomer (a) with respect to solid content of resin (P-1) (residual amount of monomer a (ii)) is measured by the following method, it is 0.01 mass% or less (detection) Below the limit).

<Measuring method of residual amount (ii) of monomer a>
Perform HPLC measurement of monomer (a) corresponding to repeating unit (A) at different concentrations (5 points), and create a calibration curve (“Relationship between HPLC area and monomer (a) concentration”) did.
100 mg of the resin (P-1) obtained in Synthesis Example 1 was precisely weighed into a measuring flask, and acetonitrile was added to make up to 5.0 mL. The prepared liquid was subjected to HPLC analysis under the following measurement conditions to calculate the mass% of monomer (a) relative to the solid content of resin (P) (residual amount of monomer a (ii)).
<HPLC measurement conditions>
Developing solvent: acetonitrile / buffer solution (90/10 volume ratio),
Buffer solution: triethylamine / phosphoric acid / ion exchange water (1/1/1000 volume ratio)
Column: Shim pack CLC-ODS, oven temperature: 40 ° C
Measurement wavelength: 254 nm, flow rate: 1 mL / min Note that the mixing ratio of the developing solvent for HPLC is appropriately between acetonitrile / buffer solution = 90 / 10-30 / 70 volume ratio, depending on the type of monomer a used. changed.

The abundance of monomer (a) relative to the mass of the actinic ray-sensitive or radiation-sensitive resin composition (residual amount (i) of monomer a) is determined as follows in accordance with the above. It was.
<Measuring method of residual amount (i) of monomer a>
The components shown in Table 2 to be described later are dissolved in the mixed solvent shown in Table 2 to prepare a solution having a total solid content concentration of 4.0% by mass. This solution is added to polytetrafluoro having a pore size of 0.1 μm. Filtration with an ethylene filter gave an actinic ray-sensitive or radiation-sensitive resin composition (positive resist composition). After 2.0 g of the obtained composition was precisely weighed into a measuring flask, acetonitrile was added to make up to 5.0 mL. By analyzing the prepared liquid under HPLC under the following conditions, the mass% of the monomer (a) corresponding to the repeating unit (A) in the composition (including the solvent) (residual amount of monomer a (i )) Was calculated.
The results are summarized in Table 1.

Synthesis Examples 2-6
Thereafter, resins (P-2) to (P-6) were synthesized in the same manner. Table 1 shows the monomer structure, composition ratio, weight average molecular weight, and degree of dispersion used for each synthesis.

Synthesis example 7
9.33 parts by mass of 1-methoxy-2-propanol was heated to 80 ° C. under a nitrogen stream. While stirring this liquid, 1.99 parts by mass of the monomer (a) described in the column of resin (P-7) in Table 1 and the monomer described in the column of resin (P-7) in Table 1 (C) 8.24 parts by mass, 9.77 parts by mass of monomer (d) described in the column of resin (P-7) in Table 1, 37.33 parts by mass of 1-methoxy-2-propanol and 2,2 A mixed solution of 1.61 parts by mass of dimethyl '-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] was dropped over 2 hours. After completion of dropping, the mixture was further stirred at 80 ° C. for 4 hours. The reaction solution was allowed to cool to complete the polymerization.
The obtained reaction liquid was poured into 1400 parts by mass of hexane / ethyl acetate (80/20 parts by mass) and reprecipitated, and then the obtained solid was dissolved in 50 parts by mass of acetone to obtain 1400 parts by mass of It was re-introduced into water / methanol (90/10 mass ratio) and re-precipitation was performed again (re-precipitation A). By filtration and vacuum drying (130 ° C., 2 hours), 8.5 parts by mass of the resin (P-7) of the present invention was obtained.
The weight average molecular weight (Mw: converted to polystyrene) obtained from GPC (carrier: N-methyl-2-pyrrolidone (NMP)) of the obtained resin (P-7) was Mw = 7400, and the dispersity was Mw / Mn = 1.71. Moreover, the residual amount of the monomer (a) calculated from HPLC was 0.41% by mass.

Synthesis Example 8
Resin (P-8) was synthesized in the same manner as described above.

Synthesis Example 9
9.33 parts by mass of 1-methoxy-2-propanol was heated to 80 ° C. under a nitrogen stream. While stirring this liquid, 1.99 parts by mass of the monomer (a) described in the column of resin (P-7) in Table 1 and the monomer described in the column of resin (P-7) in Table 1 (C) 8.24 parts by mass, 9.77 parts by mass of monomer (d) described in the column of resin (P-7) in Table 1, 37.33 parts by mass of 1-methoxy-2-propanol and 2,2 '-Azobisisobutyric acid dimethyl [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] 1.6
1 part by mass of the mixed solution was added dropwise over 2 hours. After completion of dropping, the mixture was further stirred at 80 ° C. for 4 hours. The reaction solution was allowed to cool to complete the polymerization.
The obtained reaction solution was poured into 1400 parts by mass of hexane / ethyl acetate (80/20 mass ratio) for reprecipitation (reprecipitation B), followed by filtration and vacuum drying (130 ° C., 2 hours). As a result, 14.1 parts by mass of Resin (P-9) was obtained.
The weight average molecular weight (Mw: converted to polystyrene) obtained from GPC (carrier: N-methyl-2-pyrrolidone (NMP)) of the obtained resin (P-9) was Mw = 7200, and the dispersity was Mw / Mn = 1.77. The residual amount of monomer (a) calculated from HPLC was 1.85% by mass.

Synthesis Example 10
Resin (P-10) was synthesized in the same manner as above.

Monomer a: Monomer derived from repeating unit (A) Monomer b: Monomer derived from repeating unit (B) Monomer c: Monomer derived from repeating unit (C) Monomer Body d: Monomer derived from repeating unit (D) Residual amount of monomer a (i): Mass (percentage) of monomer (a) with respect to the mass of the actinic ray-sensitive or radiation-sensitive resin composition
Residual amount of monomer a (ii): mass (percentage) of monomer (a) with respect to solid content of resin (P)
Residual amount of monomer other than monomer a: Total mass (percentage) of monomer other than monomer (a) with respect to solid content of resin (P)

  Hereinafter, the structures of the resins (P-1) to (P-10) are shown.

[Examples 1-15 and Comparative Examples 1-2]
<Resist evaluation (EB)>
The components shown in Table 2 below were dissolved in the mixed solvent shown in Table 2 to prepare a solution having a total solid content concentration of 4.0% by mass. In addition, the density | concentration in a table | surface represents the mass% with respect to the total solid. This solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain a positive resist solution. The prepared positive resist solution is uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 110 ° C. for 90 seconds to form a resist having a film thickness of 100 nm. A film was formed.
This resist film was irradiated with an electron beam using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage: 50 keV). Immediately after irradiation, it was heated on a hot plate at 130 ° C. for 90 seconds. Furthermore, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried to form a line and space pattern. Was evaluated by the following method.

〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a 100 nm line (line: space = 1: 1).
[Resolution]
The resolving power was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the irradiation dose showing the above sensitivity.
[Line edge roughness (LER)]
The distance from the reference line where there should be an edge, using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.) for any 30 points in the length direction 50 μm of the 100 nm line pattern at the irradiation amount showing the sensitivity described above. Was measured, the standard deviation was obtained, and 3σ was calculated.
[Pattern shape]
The cross-sectional shape of the 100 nm line pattern at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), and three-step evaluation was performed: rectangular, slightly tapered, and tapered.

  From Table 2, it is clear that the actinic ray-sensitive or radiation-sensitive resin composition of the present invention satisfies high sensitivity, high resolution, good pattern shape, and good line edge roughness at the same time.

The basic compounds used in the examples are shown below.
TOA: Tri-n-octylamine

Surfactants and solvents used in Examples and Comparative Examples are shown below.
W-1: Megafac F176 (Dainippon Ink Chemical Co., Ltd., fluorine-based)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd., fluorine and silicon)
W-3: Polysiloxane polymer (Shin-Etsu Chemical Co., Ltd., silicon-based)
S1: Propylene glycol monomethyl ether acetate (PGMEA)
S2: Propylene glycol monomethyl ether (PGME)
S3: Methyl lactate

[Examples 16 to 20]
<Resist evaluation (EUV light)>
The components shown in Table 3 below were dissolved in the mixed solvent shown in Table 3 to prepare a solution having a solid content concentration of 4.0% by mass. This solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain a positive resist solution. The symbols of the compounds described in Table 3 are the same as those in Table 2. Moreover, the density | concentration in a table | surface represents the mass% with respect to the total solid.
The prepared positive resist solution is uniformly coated on a silicon substrate that has been subjected to hexamethyldisilazane treatment using a spin coater, and is heated and dried on a hot plate at 120 ° C. for 90 seconds to form a resist having a film thickness of 100 nm. A film was formed.
The resist film was irradiated with an EUV exposure apparatus (wavelength 13 nm), and immediately after the irradiation, it was heated on a hot plate at 130 ° C. for 90 seconds. Further, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, dried, and a line and space pattern (line: space = 1: 1). ) And the obtained pattern was evaluated by the following method.
〔sensitivity〕
The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.). Sensitivity was defined as the minimum irradiation energy when resolving a 100 nm line (line: space = 1: 1).
[Pattern shape]
The cross-sectional shape of the 100 nm line pattern at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.), and three-step evaluation was performed: rectangular, slightly tapered, and tapered.

From the results in Table 3, it can be seen that the actinic ray-sensitive or radiation-sensitive resin composition of the present invention exhibits good sensitivity and can form a pattern having a good shape even by EUV exposure.

Claims (17)

An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (P) having a repeating unit (A) having a structural site (X) that decomposes upon irradiation with actinic rays or radiation to generate an acid, The abundance of the monomer (a) constituting the repeating unit (A) contained in the resin (P) in the composition is based on the mass of the actinic ray-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition (however, the repeating unit (1) represented by the following general formula (1) and the following general formula (2) ), A repeating unit (2) represented by the following general formula (3), and a repeating unit (4) represented by the following general formula (4). A polymer containing at least one repeating unit and a solvent Excluding radiation-sensitive resin composition comprising a.).

(In the general formula (1), R ¹ represents a hydrogen atom, a methyl group, or a trifluoromethyl group, and Z represents a monovalent group having a function of generating an acid upon irradiation).

(In the above general formulas (2), (3), and (4), R ² independently represents a hydrogen atom, a methyl group, or a trifluoromethyl group. The above general formulas (2) and (4) In the formula, each A independently represents a methylene group, a linear or branched alkylene group having 2 to 10 carbon atoms, or an arylene group having 3 to 10 carbon atoms. represents a group having the structure represented by the following general formula (i), a is 0 or 1. in formula (3), R ³ is a linear or branched alkyl having 1 to 10 carbon atoms (In the general formula (4), b represents an integer of 2 to 4, and c represents 0 or 1).

(In the above general formula (i), R ⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, p represents 1 or 2, and q represents 1 or 2. , P = 2, the two R ⁴ may be the same or different.)   Actinic ray-sensitive containing resin (P) having a repeating unit (A) having a structural site (X) that decomposes upon irradiation with actinic rays or radiation to generate an acid, and purified by gel filtration chromatography Or it is a radiation sensitive resin composition, Comprising: The abundance of the monomer (a) which comprises the repeating unit (A) contained in the said resin (P) in the said composition is said actinic-ray-sensitive Or the actinic-ray-sensitive or radiation-sensitive resin composition characterized by being 0.05 mass% or less with respect to the mass of a radiation-sensitive resin composition. An activity containing a repeating unit (A) having a structural site (X) that decomposes upon irradiation with actinic rays or radiation to generate an acid and a resin (P) having a repeating unit represented by the following general formula (VI) A light-sensitive or radiation-sensitive resin composition, wherein the abundance of the monomer (a) constituting the repeating unit (A) contained in the resin (P) in the composition is the activity-sensitive An actinic ray-sensitive or radiation-sensitive resin composition, which is 0.05% by mass or less based on the mass of the light-sensitive or radiation-sensitive resin composition.

Here, R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ represents an alkylene group and may be bonded to Ar ₆ to form a 5-membered or 6-membered ring.
Ar ₆ represents an aromatic ring group.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4. An activity containing a repeating unit (A) having a structural site (X) that decomposes upon irradiation with actinic rays or radiation to generate an acid and a resin (P) having a repeating unit represented by the following general formula (IV) A light-sensitive or radiation-sensitive resin composition, wherein the abundance of the monomer (a) constituting the repeating unit (A) contained in the resin (P) in the composition is the activity-sensitive An actinic ray-sensitive or radiation-sensitive resin composition, which is 0.05% by mass or less based on the mass of the light-sensitive or radiation-sensitive resin composition.

Here, R ₄₁ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
R ₄₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ represents an alkylene group and may be bonded to Ar ₄ to form a 5-membered or 6-membered ring.
Ar ₄ represents an aromatic ring group. n represents an integer of 1 to 4. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4 , wherein the resin (P) further has a repeating unit (B) having an alkali-soluble group. . The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , 3 or 4 , wherein the resin (P) is purified by a gel filtration chromatography method. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 , 2, and 4 , wherein the resin (P) further has a repeating unit represented by the following general formula (VI).

Here, R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ represents an alkylene group and may be bonded to Ar ₆ to form a 5-membered or 6-membered ring.
Ar ₆ represents an aromatic ring group.
n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3 , wherein the resin (P) further has a repeating unit represented by the following general formula (IV).

Here, R ₄₁ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
R ₄₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ represents an alkylene group and may be bonded to Ar ₄ to form a 5-membered or 6-membered ring.
Ar ₄ represents an aromatic ring group. n represents an integer of 1 to 4. The actinic ray-sensitive or radiation-sensitive resin according to any one of claims 1 to 8 , wherein the structural part (X) is a structural part that generates an acid anion in a side chain of the resin by irradiation with actinic rays or radiation. Composition. The monomer (a) constituting the repeating unit (A) contained in the resin (P) is 1.0% by mass or less based on the solid content of the resin (P). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of 1 to 9 . The resin (P) is further decomposed by the action of an acid, according to any one of claims 1 to 1 0, characterized by having a repeating unit (C) having a group which produce an alkali-soluble group An actinic ray-sensitive or radiation-sensitive resin composition. The resin (P) further, according to claim 1 to 1 1, characterized by having a repeating unit (D) having a group which dissolution rate is increased to decompose by the action of an alkali developer alkali developer The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above. As an exposure light source, electron beam, X-ray or actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 1 2, characterized by using the EUV light. Resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 1 3. Pattern formation method using the claim 1-1 ray- according to any one of the three or radiation-sensitive resin composition to form a resist film, exposure, and having a step of developing. The resin (P) is a resin purified by gel filtration chromatography, and an actinic ray-sensitive or radiation-sensitive resin composition is prepared using the resin (P), and a resist film is formed from the composition. The pattern forming method according to claim 15 , further comprising a step of exposing and developing. Purification method of the resin (P) contained in the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 1 3, a resin which is a gel-filtration chromatography Purification method.