JP7191981B2 - Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and electronic device manufacturing method - Google Patents

Description

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and an electronic device manufacturing method.

Conventionally, in the manufacturing process of semiconductor devices such as IC (Integrated Circuit) and LSI (Large Scale Integrated Circuit), microfabrication by lithography using a chemically amplified resist composition has been performed. there is

For example, Patent Document 1 describes a negative resist composition containing an alkali-soluble resin containing a repeating unit containing a hydroxyl group, a photoacid generator, and a cross-linking agent.

JP 2006-215067 A

In recent years, there is a demand for even finer patterns obtained by lithography, and along with this, the pattern size represented by the line width and hole diameter of the pattern is, for example, 45 nm or less. , LWR (Line Width Roughness) and LER (Line Edge Roughness) are small, and a pattern excellent in CDU (Critical Dimension Uniformity) is required. There is also a demand for improved exposure latitude (EL) and sensitivity.

The present invention provides excellent sensitivity and EL, small LWR and LER, and excellent CDU when forming an ultrafine pattern (for example, a line-and-space pattern with a line width of 45 nm or a hole pattern with a hole size of 45 nm or less). An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.

一般式（Ｐ１）中、
Ｒ^ｐは、水素原子、ハロゲン原子、又は１価の有機基を表す。
Ｌ^ｐは、単結合、又は多価の連結基を表す。
Ｒ^ｐとＬ^ｐは結合して環構造を形成していてもよい。
Ｘ^ｐは、Ｏ、Ｓ、又はＮＲ^Ｎ１を表す。Ｒ^Ｎ１は、水素原子又は１価の有機基を表す。
Ｙ^ｐは、Ｏ、Ｓ、又はＮＲ^Ｎ２を表す。Ｒ^Ｎ２は、水素原子又は１価の有機基を表す。
Ｚ^ｐは、水素原子を表す。
Ｒ^ｐ１及びＲ^ｐ２は、各々独立に、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基、シクロアルキニル基、又はアリール基を表し、上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記シクロアルケニル基、上記アルキニル基、及び上記シクロアルキニル基は、炭素－炭素結合の間にヘテロ原子を有してもよい。ただし、Ｒ^ｐ１はパーフルオロアルキル基又はパーフルオロシクロアルキル基を表すことはない。Ｒ^ｐ２はパーフルオロアルキル基又はパーフルオロシクロアルキル基を表すことはない。
Ｒ^ｐ３及びＲ^ｐ４は、各々独立に、水素原子、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基、シクロアルキニル基、又はアリール基を表し、上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記シクロアルケニル基、上記アルキニル基、及び上記シクロアルキニル基は、炭素－炭素結合の間にヘテロ原子を有してもよい。ただし、Ｒ^ｐ３がパーフルオロアルキル基又はパーフルオロシクロアルキル基を表し、かつＲ^ｐ４がパーフルオロアルキル基又はパーフルオロシクロアルキル基を表すことはない。
Ｒ^ｐ１～Ｒ^ｐ４のいずれか２つが結合して環構造を形成していてもよい。
［２］
上記一般式（Ｐ１）で表される繰り返し単位が、下記一般式（Ｐ２）で表される繰り返し単位である、［１］に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（Ｐ２）中、
Ｒ^ｐは、水素原子、ハロゲン原子、又は１価の有機基を表す。
Ｌ^ｐは、単結合、又は多価の連結基を表す。
Ｒ^ｐとＬ^ｐは結合して環構造を形成していてもよい。
Ｙ^ｐは、Ｏ、Ｓ、又はＮＲ^Ｎ２を表す。Ｒ^Ｎ２は、水素原子又は１価の有機基を表す。
Ｒ^ｐ１及びＲ^ｐ２は、各々独立に、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基、シクロアルキニル基、又はアリール基を表し、上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記シクロアルケニル基、上記アルキニル基、及び上記シクロアルキニル基は、炭素－炭素結合の間にヘテロ原子を有してもよい。ただし、Ｒ^ｐ１はパーフルオロアルキル基又はパーフルオロシクロアルキル基を表すことはない。Ｒ^ｐ２はパーフルオロアルキル基又はパーフルオロシクロアルキル基を表すことはない。
Ｒ^ｐ３及びＲ^ｐ４は、各々独立に、水素原子、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基、シクロアルキニル基、又はアリール基を表し、上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記シクロアルケニル基、上記アルキニル基、及び上記シクロアルキニル基は、炭素－炭素結合の間にヘテロ原子を有してもよい。ただし、Ｒ^ｐ３がパーフルオロアルキル基又はパーフルオロシクロアルキル基を表し、かつＲ^ｐ４がパーフルオロアルキル基又はパーフルオロシクロアルキル基を表すことはない。
Ｒ^ｐ１～Ｒ^ｐ４のいずれか２つが結合して環構造を形成していてもよい。
［３］
上記一般式（Ｐ１）で表される繰り返し単位が、下記一般式（Ｐ３）で表される繰り返し単位である、［１］又は［２］に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（Ｐ３）中、
Ｒ^ｐは、水素原子、ハロゲン原子、又は１価の有機基を表す。
Ｒ^ｐ１及びＲ^ｐ２は、各々独立に、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基、シクロアルキニル基、又はアリール基を表し、上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記シクロアルケニル基、上記アルキニル基、及び上記シクロアルキニル基は、炭素－炭素結合の間にヘテロ原子を有してもよい。ただし、Ｒ^ｐ１はパーフルオロアルキル基又はパーフルオロシクロアルキル基を表すことはない。Ｒ^ｐ２はパーフルオロアルキル基又はパーフルオロシクロアルキル基を表すことはない。
Ｒ^ｐ３及びＲ^ｐ４は、各々独立に、水素原子、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基、シクロアルキニル基、又はアリール基を表し、上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記シクロアルケニル基、上記アルキニル基、及び上記シクロアルキニル基は、炭素－炭素結合の間にヘテロ原子を有してもよい。ただし、Ｒ^ｐ３がパーフルオロアルキル基又はパーフルオロシクロアルキル基を表し、かつＲ^ｐ４がパーフルオロアルキル基又はパーフルオロシクロアルキル基を表すことはない。
Ｒ^ｐ１～Ｒ^ｐ４のいずれか２つが結合して環構造を形成していてもよい。
［４］
上記樹脂Ｐが、酸分解性基を有する繰り返し単位Ｋ１を更に含み、上記繰り返し単位Ｋ１は、上記一般式（Ｐ１）で表される繰り返し単位とは異なる繰り返し単位である、［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。
［５］
上記一般式（Ｐ１）において、下記一般式（Ｐ１－Ｄ）で表される部位の原子量の総和が３００以下である［１］に記載の感活性光線性又は感放射線性樹脂組成物。

一般式（Ｐ１－Ｄ）中、
Ｘ^ｐは、Ｏ、Ｓ、又はＮＲ^Ｎ１を表す。Ｒ^Ｎ１は、水素原子又は１価の有機基を表す。
Ｚ^ｐは、水素原子を表す。
Ｒ^ｐ１及びＲ^ｐ２は、各々独立に、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基、シクロアルキニル基、又はアリール基を表し、上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記シクロアルケニル基、上記アルキニル基、及び上記シクロアルキニル基は、炭素－炭素結合の間にヘテロ原子を有してもよい。ただし、Ｒ^ｐ１はパーフルオロアルキル基又はパーフルオロシクロアルキル基を表すことはない。Ｒ^ｐ２はパーフルオロアルキル基又はパーフルオロシクロアルキル基を表すことはない。
Ｒ^ｐ３及びＲ^ｐ４は、各々独立に、水素原子、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基、シクロアルキニル基、又はアリール基を表し、上記アルキル基、上記シクロアルキル基、上記アルケニル基、上記シクロアルケニル基、上記アルキニル基、及び上記シクロアルキニル基は、炭素－炭素結合の間にヘテロ原子を有してもよい。ただし、Ｒ^ｐ３がパーフルオロアルキル基又はパーフルオロシクロアルキル基を表し、かつＲ^ｐ４がパーフルオロアルキル基又はパーフルオロシクロアルキル基を表すことはない。
Ｒ^ｐ１～Ｒ^ｐ４のいずれか２つが結合して環構造を形成していてもよい。
＊はＹ^ｐとの結合位置を示す。
［６］
上記樹脂Ｐに含まれる繰り返し単位は、（メタ）アクリレート系繰り返し単位又はフェノール性水酸基を含む繰り返し単位である、［１］～［５］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。
［７］
［１］～［６］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。
［８］
［１］～［６］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たパターン形成方法。
［９］
［８］に記載のパターン形成方法を含む、電子デバイスの製造方法。
本発明は、上記［１］～［９］に関するものであるが、本明細書には参考のためその他の事項についても記載した。
As a result of intensive studies aimed at solving the above problems, the inventors of the present invention have found that the above problems can be solved by the following configuration, and completed the present invention. That is, the present invention is as follows. [1]
A sensitizer containing a resin P having a repeating unit represented by the following general formula (P1) in an amount of 30% by mass or more based on the total solid content and a crosslinking agent of 10% by mass or less based on the total solid content. A light-sensitive or radiation-sensitive resin composition,
The resin P further includes a repeating unit K2 having a polar group, and the repeating unit K2 is a repeating unit different from the repeating unit represented by the general formula (P1),
the polar group contained in the repeating unit K2 is at least one group selected from the group consisting of a lactone group, a sultone group, a sultam group, a carboxylic acid group, and a cyclic carbonate group;
further comprising a photoacid generator A,
The photoacid generator A is a photoacid generator Aw in which the pKa of the generated acid is -1.40 or more,
The content of the photoacid generator Aw is 16 to 35% by mass with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition,
A basic compound (DA), a basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation, and generates an acid having a pKa greater than that of the acid generated from the photoacid generator Aw by 1.00 or more. a compound (DC), a compound (DD) having a nitrogen atom and having a group that leaves under the action of an acid, and an onium salt compound (DE) having a nitrogen atom in the cation moiety. Actinic ray or radiation sensitive resin composition.

In general formula (P1),
R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
L ^p represents a single bond or a polyvalent linking group.
R ^p and L ^p may combine to form a ring structure.
X ^p represents O, S, or NR ^N1 . ^RN1 represents a hydrogen atom or a monovalent organic group.
Y ^p represents O, S, or NR ^N2 . ^RN2 represents a hydrogen atom or a monovalent organic group.
Z ^p represents a hydrogen atom.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl group, the cycloalkenyl group, the alkynyl group and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, ^Rp3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and ^Rp4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.
[2]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit represented by the general formula (P1) is a repeating unit represented by the following general formula (P2).

In the general formula (P2),
R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
L ^p represents a single bond or a polyvalent linking group.
R ^p and L ^p may combine to form a ring structure.
Y ^p represents O, S, or NR ^N2 . ^RN2 represents a hydrogen atom or a monovalent organic group.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl group, the cycloalkenyl group, the alkynyl group and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, ^Rp3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and ^Rp4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.
[3]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the repeating unit represented by the general formula (P1) is a repeating unit represented by the following general formula (P3). .

In general formula (P3),
R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl group, the cycloalkenyl group, the alkynyl group and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, ^Rp3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and ^Rp4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.
[4]
[1] to [3], wherein the resin P further includes a repeating unit K1 having an acid-decomposable group, and the repeating unit K1 is a repeating unit different from the repeating unit represented by the general formula (P1). ] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of .
[5]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the total atomic weight of the sites represented by the following general formula (P1-D) in the general formula (P1) is 300 or less.

In the general formula (P1-D),
X ^p represents O, S, or NR ^N1 . ^RN1 represents a hydrogen atom or a monovalent organic group.
Z ^p represents a hydrogen atom.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl group, the cycloalkenyl group, the alkynyl group and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, ^Rp3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and ^Rp4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.
* indicates the binding position with ^Yp .
[6]
Actinic ray-sensitive or radiation-sensitive according to any one of [1] to [5], wherein the repeating unit contained in the resin P is a (meth)acrylate repeating unit or a repeating unit containing a phenolic hydroxyl group. elastic resin composition.
[7]
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6].
[8]
A pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6].
[9]
A method for manufacturing an electronic device, including the pattern forming method according to [8].
Although the present invention relates to the above [1] to [9], other matters are also described in this specification for reference.

<1>
A sensitizer containing a resin P having a repeating unit represented by the following general formula (P1) in an amount of 30% by mass or more relative to the total solid content and a crosslinking agent of 10% by mass or less relative to the total solid content. Light sensitive or radiation sensitive resin composition.

In general formula (P1),
R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
L ^p represents a single bond or a polyvalent linking group.
R ^p and L ^p may combine to form a ring structure.
X ^p represents O, S, or NR ^N1 . ^RN1 represents a hydrogen atom or a monovalent organic group.
Y ^p represents O, S, or NR ^N2 . ^RN2 represents a hydrogen atom or a monovalent organic group.
Z ^p represents a hydrogen atom or a monovalent organic group.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl group, the cycloalkenyl group, the alkynyl group and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, ^Rp3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and ^Rp4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.
<2>
The actinic ray-sensitive or radiation-sensitive resin composition according to <1>, wherein the repeating unit represented by the general formula (P1) is a repeating unit represented by the following general formula (P2).

In general formula (P2),
R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
L ^p represents a single bond or a polyvalent linking group.
R ^p and L ^p may combine to form a ring structure.
Y ^p represents O, S, or NR ^N2 . ^RN2 represents a hydrogen atom or a monovalent organic group.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl group, the cycloalkenyl group, the alkynyl group and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, ^Rp3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and ^Rp4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.
<3>
The actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <2>, wherein the repeating unit represented by the general formula (P1) is a repeating unit represented by the following general formula (P3). .

In general formula (P3),
R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl group, the cycloalkenyl group, the alkynyl group and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, ^Rp3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and ^Rp4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.
<4>
<1> to <3, wherein the resin P further includes a repeating unit K1 having an acid-decomposable group, and the repeating unit K1 is a repeating unit different from the repeating unit represented by the general formula (P1). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of >.
<5>
<1> to <4>, wherein the resin P further includes a repeating unit K2 having a polar group, and the repeating unit K2 is a repeating unit different from the repeating unit represented by the general formula (P1). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3.
<6>
The polar group contained in the repeating unit K2 is an ester group, a sulfonate group, a sulfonamide group, a carboxylic acid group, a sulfonic acid group, a carbonate group, a carbamate group, an alcoholic hydroxyl group, a sulfoxide group, a sulfonyl group, a ketone group, and an imide group. , an amide group, a sulfonimide group, a cyano group, a nitro group, and an ether group, the actinic ray-sensitive or radiation-sensitive resin composition according to <5>.
<7>
<5> or The actinic ray-sensitive or radiation-sensitive resin composition according to <6>.
<8>
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <7>, further comprising a photoacid generator A.
<9>
The actinic ray-sensitive or radiation-sensitive resin composition according to <8>, wherein the photoacid generator A is a photoacid generator Aw whose generated acid has a pKa of -1.40 or more.
<10>
A basic compound (DA), a basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation, and generates an acid having a pKa greater than that of the acid generated from the photoacid generator Aw by 1.00 or more. compound (DC), a compound (DD) having a nitrogen atom and having a group that leaves under the action of an acid, and at least one of an onium salt compound (DE) having a nitrogen atom in the cation moiety, < The actinic ray-sensitive or radiation-sensitive resin composition according to 9>.
<11>
Actinic ray-sensitive or according to any one of <1> to <10>, wherein the sum of atomic weights of the sites represented by the following general formula (P1-D) in the general formula (P1) is 300 or less A radiation-sensitive resin composition.

In the general formula (P1-D),
X ^p represents O, S, or NR ^N1 . ^RN1 represents a hydrogen atom or a monovalent organic group.
Z ^p represents a hydrogen atom or a monovalent organic group.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl group, the cycloalkenyl group, the alkynyl group and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and R ^p4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.
* indicates the binding position with ^Yp .
<12>
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <11>.
<13>
A pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <11>.
<14>
A method for manufacturing an electronic device, including the pattern forming method according to <13>.

In the repeating unit represented by the general formula (P1), the polar group represented by Y ^p (or Y ^p and L ^p ) is protected by a group (leaving group) that decomposes and leaves under the action of an acid. structure. That is, the repeating unit represented by general formula (P1) is a repeating unit containing a group that is decomposed by the action of an acid to increase its polarity (hereinafter also referred to as "acid-decomposable group").
Therefore, in the pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, typically, when an alkaline developer is employed as the developer, a positive pattern is suitably formed and developed. When an organic developer is used as the liquid, a negative pattern is preferably formed.
By having the polar group represented by -X ^p -Z ^p in the general formula (P1), it is possible to moderately suppress the diffusion of the acid generated from the photoacid generator, thereby improving the EL performance. The inventors speculate.
In addition, the group represented by -X ^p -Z ^p interacts with an anionic group in the photoacid generator typically contained in the resist composition, thereby forming the resin P and the photoacid generator. This improves the compatibility with the photoacid generator, which improves the uniformity of the distribution of the photoacid generator in the resist film. .
Furthermore, the repeating unit represented by the general formula (P1) has a structure in which Y ^p and X ^p are bonded via two carbon atoms, and a rearrangement reaction easily occurs, resulting in high reactivity ( high sensitivity). This rearrangement reaction is specific to structures in which Y ^p and X ^p are bonded via two carbon atoms, and structures in which Y ^p and X ^p are bonded via three or four carbon atoms. It usually doesn't happen.
In addition, since the leaving group has a polar group represented by -X ^p -Z ^p , in the formation of a negative pattern, the solubility of the unexposed portion of the resist film in an organic solvent developer is moderately lowered. In the formation of the mold pattern, it is considered that the solubility of the unexposed area in an alkaline developer is moderately improved, thereby improving the sensitivity.

According to the present invention, when forming an ultrafine pattern (for example, a line and space pattern with a line width of 45 nm or a hole pattern with a hole size of 45 nm or less), the sensitivity and EL are excellent, the LWR and LER are small, and the CDU is excellent. It is possible to provide an excellent actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and an electronic device manufacturing method using the actinic ray- or radiation-sensitive resin composition.

The present invention will be described in detail below.
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
The term "actinic ray" or "radiation" as used herein means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam) and the like. As used herein, "light" means actinic rays or radiation.
The term "exposure" as used herein means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also electron beams and ion beams. It also includes drawing with particle beams such as beams.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.

As used herein, (meth)acrylate stands for acrylate and methacrylate.
In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw/Mn) of the resin are measured using a GPC (Gel Permeation Chromatography) device (HLC manufactured by Tosoh Corporation). -8120 GPC) by GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential It is defined as a polystyrene conversion value by a refractive index detector (Refractive Index Detector).

As used herein, pKa (acid dissociation constant pKa) represents the acid dissociation constant pKa in an aqueous solution. Defined. The lower the value of the acid dissociation constant pKa, the higher the acid strength. The value of pKa is obtained by calculation using the following software package 1 and based on Hammett's substituent constant and a database of known literature values. All pKa values described herein are calculated using this software package.

Software Package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

Regarding the notation of groups (atomic groups) in this specification, the notations that do not describe substitution and unsubstituted include not only groups having no substituents but also groups having substituents. For example, an "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). Also, the term "organic group" as used herein refers to a group containing at least one carbon atom.

In addition, in the present specification, the type of substituent, the position of the substituent, and the number of substituents are not particularly limited when it is said that it may have a substituent. The number of substituents can be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from the following substituents T, for example.

(substituent T)
The substituent T includes halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group, etc. Alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; Arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; Alkyl groups; Cycloalkyl groups; carboxy groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; mentioned.

[Actinic ray-sensitive or radiation-sensitive resin composition]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as the "composition of the present invention") contains a resin having a repeating unit represented by the general formula (P1) in the total solid content of It is an actinic ray-sensitive or radiation-sensitive resin composition containing 30% by mass or more of the total solid content of the cross-linking agent and 10% by mass or less of the cross-linking agent.

The composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. Moreover, it may be a resist composition for alkali development or a resist composition for organic solvent development.
The composition of the present invention is typically a chemically amplified resist composition.
The components contained in the composition of the present invention are described in detail below.

[Resin (Resin P) Having a Repeating Unit Represented by Formula (P1)]
The composition of the present invention contains a resin having a repeating unit represented by the following general formula (P1) (hereinafter also referred to as "resin P"). A repeating unit represented by the following general formula (P1) is a repeating unit containing an acid-decomposable group, and the resin P is an acid-decomposable resin.

In general formula (P1),
R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
L ^p represents a single bond or a polyvalent linking group.
R ^p and L ^p may combine to form a ring structure.
X ^p represents O, S, or NR ^N1 . ^RN1 represents a hydrogen atom or a monovalent organic group.
Y ^p represents O, S, or NR ^N2 . ^RN2 represents a hydrogen atom or a monovalent organic group.
Z ^p represents a hydrogen atom or a monovalent organic group.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl group, the cycloalkenyl group, the alkynyl group and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and R ^p4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.

In general formula (P1), R ^p1 and R ^p2 are not each a perfluoroalkyl group or a perfluorocycloalkyl group, and both R ^p3 and R ^p4 are a perfluoroalkyl group or a perfluorocycloalkyl group. The resin P expresses sufficient acid decomposition reactivity by not representing

In general formula (P1), R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
Halogen atoms represented by R ^p include, for example, fluorine, chlorine, bromine and iodine atoms.
Although the monovalent organic group represented by R ^p is not particularly limited, an alkyl group is preferable.
When R ^p represents an alkyl group, the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl and propyl. The alkyl group may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
R ^p is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, even more preferably a methyl group.

In general formula (P1), L ^p represents a single bond or a polyvalent linking group.
The polyvalent linking group represented by L ^p is not particularly limited, but examples include -C(=O)-, -O-, -S(=O) ₂ -, an alkylene group (preferably having 1 to 10 carbon atoms alkylene group), a cycloalkylene group (preferably a cycloalkylene group having 3 to 20 carbon atoms), a divalent heterocyclic group, and a linking group formed by combining these.
L ^p is preferably a divalent or trivalent linking group, more preferably a divalent linking group, -C(=O)-, -O-, -S(=O) ₂ - , an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms), and a divalent linking group formed by combining these are more preferably -C(=O)- or -S(=O) ₂ - is more preferred, and -C(=O)- is particularly preferred.
Note that R ^p and L ^p may combine to form a ring structure.

In general formula (P1), X ^p represents O, S, or NR ^N1 . ^RN1 represents a hydrogen atom or a monovalent organic group.
When R ^N1 represents a monovalent organic group, the monovalent organic group includes an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), a cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms). ), an aryl group (preferably an aryl group having 6 to 20 carbon atoms), and the like. R ^N1 is preferably a hydrogen atom.
X ^p preferably represents O.

In general formula (P1), Y ^p represents O, S, or NR ^N2 . ^RN2 represents a hydrogen atom or a monovalent organic group.
Examples of monovalent organic groups in which ^RN2 represents a monovalent organic group include monovalent organic groups in which ^RN1 represents a monovalent organic group. R ^N2 is preferably a hydrogen atom.
^Yp preferably represents O or NH, more preferably O.

In general formula (P1), Z ^p represents a hydrogen atom or a monovalent organic group.
When Z ^p represents a monovalent organic group, the monovalent organic group includes an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 6 carbon atoms) and the like. These groups may have a substituent, and examples of the substituent include halogen atoms (preferably fluorine atoms).
When X ^p is O or S, Z ^p is preferably a hydrogen atom.
When X ^p is NR ^N1 , Z ^p is preferably an alkylsulfonyl group.

In general formula (P1), R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group. The cycloalkyl groups, the alkenyl groups, the cycloalkenyl groups, the alkynyl groups, and the cycloalkynyl groups may have heteroatoms between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.

The alkyl group represented by R ^p1 and R ^p2 is not particularly limited, but an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and specifically, a methyl group and an ethyl group. , propyl group, n-butyl group, sec-butyl group, hexyl group, octyl group and the like, more preferably methyl group and ethyl group, particularly preferably methyl group. The alkyl groups represented by R ^p1 and R ^p2 may have a substituent.

The cycloalkyl group represented by R ^p1 and R ^p2 is not particularly limited, and may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl groups. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, such as adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinene group, tricyclodecanyl group, A tetracyclododecyl group, androstanyl group, and the like can be mentioned.
As the cycloalkyl group, a cycloalkyl group having 4 to 10 carbon atoms is more preferred, and a cyclohexyl group is even more preferred. The cycloalkyl groups represented by R ^p1 and R ^p2 may have a substituent.

The alkenyl group represented by R ^p1 and R ^p2 is not particularly limited, but is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, such as vinyl group, allyl group, butenyl group. etc. The alkenyl groups represented by R ^p1 and R ^p2 may have a substituent.

The cycloalkenyl group represented by R ^p1 and R ^p2 is not particularly limited, and may be a monocyclic cycloalkenyl group or a polycyclic cycloalkenyl group. The monocyclic cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms, and the polycyclic cycloalkenyl group is preferably a cycloalkenyl group having 6 to 20 carbon atoms.
As the cycloalkenyl group, a cycloalkenyl group having 4 to 10 carbon atoms is more preferable. The cycloalkenyl groups represented by R ^p1 and R ^p2 may have a substituent.

The alkynyl group represented by R ^p1 and R ^p2 is not particularly limited, but an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 6 carbon atoms is more preferable. The alkynyl groups represented by R ^p1 and R ^p2 may have a substituent.

The cycloalkynyl group represented by R ^p1 and R ^p2 is not particularly limited, and may be a monocyclic cycloalkynyl group or a polycyclic cycloalkynyl group. The monocyclic cycloalkynyl group is preferably a cycloalkynyl group having 3 to 20 carbon atoms, and the polycyclic cycloalkynyl group is preferably a cycloalkynyl group having 6 to 20 carbon atoms.
As the cycloalkynyl group, a cycloalkynyl group having 4 to 10 carbon atoms is more preferable. The cycloalkynyl groups represented by R ^p1 and R ^p2 may have a substituent.

The aryl group represented by R ^p1 and R ^p2 is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 15 carbon atoms is more preferable, and specifically, a phenyl group and a naphthyl group. , and anthryl groups, etc., more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group represented by R ^p1 and R ^p2 may have a substituent.

The alkyl group, the cycloalkyl group, the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. Heteroatoms include, for example, oxygen atoms, sulfur atoms, and nitrogen atoms.

R ^p1 and R ^p2 may combine with each other to form a ring structure. The ring structure to be formed is preferably a ring structure having 3 to 20 carbon atoms, more preferably a ring structure having 4 to 10 carbon atoms, and further preferably a ring structure having 4 to 8 carbon atoms. preferable.

R ^p1 and R ^p2 each independently represent a methyl group or an ethyl group, or R ^p1 and R ^p2 preferably combine to form a ring structure having 4 to 8 carbon atoms, and a methyl group or an ethyl group. is more preferred, and a methyl group is even more preferred.

In general formula (P1), R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl The groups, the cycloalkyl groups, the alkenyl groups, the cycloalkenyl groups, the alkynyl groups, and the cycloalkynyl groups may have heteroatoms between the carbon-carbon bonds. However, R ^p3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and R ^p4 represents a perfluoroalkyl group or perfluorocycloalkyl group.

The alkyl group represented by R ^p3 and R ^p4 is not particularly limited, but an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and specifically, a methyl group and an ethyl group. , propyl group, n-butyl group, sec-butyl group, hexyl group, octyl group and the like, more preferably methyl group and ethyl group, particularly preferably methyl group. The alkyl groups represented by R ^p3 and R ^p4 may have a substituent.

The cycloalkyl group represented by R ^p3 and R ^p4 is not particularly limited, and may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl groups. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, such as adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinene group, tricyclodecanyl group, A tetracyclododecyl group, androstanyl group, and the like can be mentioned.
As the cycloalkyl group, a cycloalkyl group having 4 to 10 carbon atoms is more preferred, and a cyclohexyl group is even more preferred. The cycloalkyl groups represented by R ^p3 and R ^p4 may have a substituent.

The alkenyl group represented by R ^p3 and R ^p4 is not particularly limited, but is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, such as vinyl group, allyl group and butenyl group. etc. The alkenyl group represented by R ^p3 and R ^p4 may have a substituent.

The cycloalkenyl group represented by R ^p3 and R ^p4 is not particularly limited, and may be a monocyclic cycloalkenyl group or a polycyclic cycloalkenyl group. The monocyclic cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms, and the polycyclic cycloalkenyl group is preferably a cycloalkenyl group having 6 to 20 carbon atoms.
As the cycloalkenyl group, a cycloalkenyl group having 4 to 10 carbon atoms is more preferable. The cycloalkenyl groups represented by R ^p3 and R ^p4 may have a substituent.

The alkynyl group represented by R ^p3 and R ^p4 is not particularly limited, but an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 6 carbon atoms is more preferable. The alkynyl group represented by R ^p3 and R ^p4 may have a substituent.

The cycloalkynyl group represented by R ^p3 and R ^p4 is not particularly limited, and may be a monocyclic cycloalkynyl group or a polycyclic cycloalkynyl group. The monocyclic cycloalkynyl group is preferably a cycloalkynyl group having 3 to 20 carbon atoms, and the polycyclic cycloalkynyl group is preferably a cycloalkynyl group having 6 to 20 carbon atoms.
As the cycloalkynyl group, a cycloalkynyl group having 4 to 10 carbon atoms is more preferable. The cycloalkynyl groups represented by R ^p3 and R ^p4 may have a substituent.

The aryl group represented by R ^p3 and R ^p4 is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 15 carbon atoms is more preferable, and specifically, a phenyl group and a naphthyl group. , and anthryl groups, etc., more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group represented by R ^p3 and R ^p4 may have a substituent.

The alkyl group, the cycloalkyl group, the alkenyl group, the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. Heteroatoms include, for example, oxygen atoms, sulfur atoms, and nitrogen atoms.

R ^p3 and R ^p4 may combine with each other to form a ring structure. The ring structure to be formed is preferably a ring structure having 3 to 20 carbon atoms, more preferably a ring structure having 4 to 10 carbon atoms, and further preferably a ring structure having 4 to 8 carbon atoms. preferable.

R ^p3 and R ^p4 each independently represent a methyl group or an ethyl group, or R ^p3 and R ^p4 preferably combine to form a ring structure having 4 to 8 carbon atoms, and a methyl group or an ethyl group. is more preferred, and a methyl group is even more preferred.

The smaller the size of the decomposition product produced when the repeating unit represented by the general formula (P1) is decomposed by the action of an acid, the lower the persistence of the decomposition product in the resist film and the less development variation. can be done. Therefore, the smaller the size of the decomposition product, the better from the viewpoint of LWR, LER, and CDU. It is considered that the size of the decomposed product has a correlation with the sum of the atomic weights of the sites (decomposition sites) eliminated by the acid decomposition reaction. In the present invention, the formula weight (sum of atomic weights) of the site (group) represented by the following general formula (P1-D), which corresponds to the decomposition site in general formula (P1), is preferably 300 or less, and 250 It is more preferably 200 or less, still more preferably 150 or less, particularly preferably 120 or less, and most preferably 110 or less.

In the general formula (P1-D),
X ^p represents O, S, or NR ^N1 . ^RN1 represents a hydrogen atom or a monovalent organic group.
Z ^p represents a hydrogen atom or a monovalent organic group.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl group, the cycloalkenyl group, the alkynyl group and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and R ^p4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.
* indicates the binding position with ^Yp .

In general formula (P1-D), X ^p , Z ^p , and R ^p1 to R ^p4 have the same meanings as X ^p , Z ^p , and R ^p1 to R ^p4 in general formula (P1), and preferred examples are also the same. be.

In the repeating unit represented by formula (P1), the polar group represented by —X ^p —Z ^p is preferably a hydroxy group. That is, the repeating unit represented by general formula (P1) is preferably a repeating unit represented by general formula (P2) below.

In general formula (P2),
R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
L ^p represents a single bond or a polyvalent linking group.
R ^p and L ^p may combine to form a ring structure.
Y ^p represents O, S, or NR ^N2 . ^RN2 represents a hydrogen atom or a monovalent organic group.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl group, the cycloalkenyl group, the alkynyl group and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, ^Rp3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and ^Rp4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.

In general formula (P2), R ^p , L ^p , Y ^p , and R ^p1 to R ^p4 are synonymous with R ^p , L ^p , Y ^p , and R ^p1 to R ^p4 in general formula (P1). , and preferred examples are also the same.

Further, the repeating unit represented by the general formula (P1) is a repeating unit represented by the following general formula (P3) from the viewpoint of having moderate solubility in a developing solution and easy raw material availability. It is more preferable to have

In general formula (P3),
R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl group, the cycloalkenyl group, the alkynyl group and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and R ^p4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.

In general formula (P3), R ^p and R ^p1 to R ^p4 have the same definitions as R ^p and R ^p1 to R ^p4 in general formula (P1), and preferred examples are also the same.

Specific examples of the repeating unit represented by formula (P1) are shown below.

The resin P may contain the repeating unit represented by the general formula (P1) singly or in combination of two or more.

The content of the repeating unit represented by the general formula (P1) contained in the resin P (the total content when there are a plurality of repeating units represented by the general formula (P1)) is the total number of repeating units of the resin P. It is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, and even more preferably 15 to 60 mol %, relative to the unit.

<Repeating unit K1 having an acid-decomposable group>
In addition to the repeating unit represented by the general formula (P1), the resin P includes a repeating unit (also referred to as “repeating unit K1”) having an acid-decomposable group different from the repeating unit represented by the general formula (P1). ) is further included.
The acid-decomposable group preferably includes a structure in which a polar group is protected by a group that decomposes and leaves by the action of an acid (leaving group).
Polar groups include carboxy groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, and (alkylsulfonyl)(alkylcarbonyl)imide groups. , bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, and tris(alkylsulfonyl)methylene group, etc. (a group that dissociates in a 2.38% by mass tetramethylammonium hydroxide aqueous solution), an alcoholic hydroxyl group, and the like.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group). It excludes aliphatic alcohol groups substituted with functional groups (eg, hexafluoroisopropanol groups, etc.). As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20 is preferable.

The polar group is preferably a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

Groups preferred as acid-decomposable groups are groups in which the hydrogen atoms of these groups are substituted with groups that leave by the action of acid (leaving groups).
Examples of groups that leave by the action of an acid (leaving groups) include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and - C(R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) and the like.
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may combine with each other to form a ring.
R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

The alkyl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl. groups, and octyl groups.
The cycloalkyl groups of R ₃₆ -R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic ring is preferably a cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. The polycyclic ring is preferably a cycloalkyl group having 6 to 20 carbon atoms, such as adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinene group, tricyclodecanyl group, tetracyclododecyl group. , and androstanyl group. One or more carbon atoms in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
The aryl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl, naphthyl and anthryl groups.
Aralkyl groups represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably aralkyl groups having 7 to 12 carbon atoms, such as benzyl, phenethyl and naphthylmethyl groups.
Alkenyl groups represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably alkenyl groups having 2 to 8 carbon atoms, such as vinyl, allyl, butenyl and cyclohexenyl groups.
The ring formed by combining R ₃₆ and R ₃₇ is preferably a cycloalkyl group (monocyclic or polycyclic). The monocyclic cycloalkyl group is preferably a cyclopentyl group, cyclohexyl group, or the like, and the polycyclic cycloalkyl group is preferably a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like.

The acid-decomposable group is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or an acetal ester group, more preferably an acetal group or a tertiary alkyl ester group.

The resin P preferably contains a repeating unit represented by the following general formula (AI) as the repeating unit K1.

In general formula (AI), T represents a single bond or a divalent linking group.
Examples of the divalent linking group for T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an arylene group.
T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably -CH ₂ -, -(CH ₂ ) ₂ -, or -(CH ₂ ) ₃ -.
More preferably T is a single bond.

In general formula (AI), Xa ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group.
Xa ₁ is preferably a hydrogen atom or an alkyl group.
The alkyl group of Xa ₁ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
The alkyl group of Xa ₁ preferably has 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, hydroxymethyl and trifluoromethyl groups. The alkyl group of Xa ₁ is preferably a methyl group.

In general formula (AI), Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group.
Any two of Rx ₁ to Rx ₃ may or may not combine to form a ring structure.
The alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and include methyl, ethyl, n-propyl, isopropyl and n-butyl groups. , isobutyl group, t-butyl group and the like are preferred. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, and even more preferably 1-3. Some of the carbon-carbon bonds in the alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be double bonds.
The cycloalkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be monocyclic or polycyclic. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic cycloalkyl group. Polycyclic cycloalkyl groups include norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.

The ring formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ may be monocyclic or polycyclic. Examples of monocyclic rings include monocyclic cycloalkane rings such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, and cyclooctane ring. Examples of polycyclic rings include polycyclic cycloalkyl rings such as norbornane, tetracyclodecane, tetracyclododecane, and adamantane rings. Among them, a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is preferable.
As the ring formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ , the rings shown below are also preferable.

Specific examples of the monomer corresponding to the repeating unit represented by formula (AI) are given below.
The following specific examples correspond to the case where Xa ₁ in general formula (AI) is a methyl group, but Xa ₁ can optionally be substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

Resin P also preferably has, as repeating unit K1, a repeating unit described in paragraphs <0336> to <0369> of US Patent Application Publication No. 2016/0070167A1.

In addition, the resin P contains, as the repeating unit K1, a group that is decomposed by the action of an acid to produce an alcoholic hydroxyl group described in paragraphs <0363> to <0364> of US Patent Application Publication No. 2016/0070167A1. May have units.

When the resin P contains the repeating unit K1, the type of the repeating unit K1 contained in the resin P may be one or two or more.

The content of the repeating unit K1 contained in the resin P (the total content of the repeating units K1 when a plurality of repeating units K1 are present) is preferably 10 to 90 mol%, preferably 20 to 80 mol%, based on the total repeating units of the resin P. mol % is more preferred, and 30 to 70 mol % is even more preferred.

<Repeating unit K2 having a polar group>
The resin P includes, in addition to the repeating unit represented by the general formula (P1), a repeating unit (also referred to as “repeating unit K2”) having a polar group different from the repeating unit represented by the general formula (P1).
) is further included.

The polar group possessed by the repeating unit K2 includes an ester group, a sulfonate group, a sulfonamide group, a carboxylic acid group, a sulfonic acid group, a carbonate group, a carbamate group, an alcoholic hydroxyl group, a sulfoxide group, a sulfonyl group, a ketone group, an imide group, It is preferably at least one group selected from the group consisting of an amide group, a sulfonimide group, a cyano group, a nitro group, and an ether group, a lactone group, a sultone group, a sultam group, a carboxylic acid group, an alcoholic hydroxyl group, and a cyclic carbonate group, more preferably a lactone group or a sultone group, and particularly preferably a lactone group.
That is, the repeating unit K2 preferably has a lactone structure or a sultone structure, and particularly preferably has a lactone structure.

The lactone structure or sultone structure may have a lactone ring or a sultone ring, and a lactone structure having a 5- to 7-membered lactone ring or a sultone structure having a 5- to 7-membered sultone ring is preferred.
A lactone structure in which a 5- to 7-membered lactone ring is condensed with another ring to form a bicyclo structure or a spiro structure is also preferred. A sultone structure in which a 5- to 7-membered sultone ring is condensed with another ring to form a bicyclo structure or a spiro structure is also preferred.

Among them, the resin P has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-22), or any of the following general formulas (SL1-1) to (SL1-3). It preferably contains a repeating unit having the represented sultone structure. Also, the lactone structure or sultone structure may be directly bonded to the main chain.
Among them, general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), general formula (LC1-21) Alternatively, a lactone structure represented by general formula (LC1-22) or a sultone structure represented by general formula (SL1-1) is preferred.

The lactone structure or sultone structure may or may not have a substituent (Rb ₂ ). The substituent (Rb ₂ ) includes 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 2 to 8 carbon atoms, a carboxy group, A halogen atom, a hydroxyl group, a cyano group, or the like is preferable, and an alkyl group having 1 to 4 carbon atoms or a cyano group is more preferable. _n2 represents an integer of 0-4. When n ₂ is 2 or more, the multiple substituents (Rb ₂ ) may be the same or different. Moreover, multiple substituents (Rb ₂ ) may be bonded to each other to form a ring.

As the repeating unit having a lactone structure or sultone structure, a repeating unit represented by the following general formula (LS1) is preferable.

In the above general formula (LS1),
A ^LS represents an ester bond (group represented by --COO--) or an amide bond (group represented by --CONH--).

t is the number of repetitions of the structure represented by -R ^LS2 -R ^LS3 - and represents an integer of 0 to 5, preferably 0 or 1, more preferably 0. When t is 0, (-R ^LS2 -R ^LS3 -)t becomes a single bond.

R ^LS2 represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are multiple R ^LS2s , the multiple R ^LS2s may be the same or different.
The alkylene group or cycloalkylene group of R ^LS2 may have a substituent.

^RLS3 represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond. When a plurality of R ^LS3 are present, the plurality of R ^LS3 may be the same or different.
Among them, ^RLS3 is preferably an ether bond or an ester bond, more preferably an ester bond.

^RLS4 represents a monovalent organic group having a lactone structure or a sultone structure.
Among them, in any one of the structures represented by the general formulas (LC1-1) to (LC1-22) and the structures represented by the general formulas (SL1-1) to (SL1-3), a lactone structure Alternatively, it is preferably a group obtained by removing one hydrogen atom from one carbon atom constituting the sultone structure. The carbon atoms from which one hydrogen atom is removed are preferably not carbon atoms constituting the substituent (Rb ₂ ).

^RLS1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).

Examples of monomers corresponding to repeating units having at least one selected from the group consisting of lactone structures and sultone structures are shown below.
In the examples below, the methyl group attached to the vinyl group may be replaced with a hydrogen atom, a halogen atom, or a monovalent organic group.

Resin P may have a repeating unit having a carbonate structure. As the carbonate structure, a cyclic carbonate (cyclic carbonate) structure is preferable.
As the repeating unit having a cyclic carbonate structure, a repeating unit represented by the following general formula (A-1) is preferable.

In general formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
n represents an integer of 0 or more.
_RA2 ^represents a substituent. When n is 2 or more, a plurality of R _A ² may be the same or different.
A represents a single bond or a divalent linking group.
Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

The resin P may have repeating units having polar groups such as hydroxyl groups, cyano groups, carboxy groups, and fluorinated alcohol groups (eg, hexafluoroisopropanol groups). As the repeating unit having a polar group, a repeating unit having an alicyclic hydrocarbon structure substituted with the polar group is preferable. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably a cyclohexyl group, an adamantyl group, or a norbornane group.

Specific examples of the monomer corresponding to the repeating unit having the polar group are shown below, but the present invention is not limited to these specific examples.

Resin P also preferably has, as repeating unit K2, a repeating unit described in paragraphs <0370> to <0433> of US Patent Application Publication No. 2016/0070167A1.

When the resin P contains the repeating unit K2, the type of the repeating unit K2 contained in the resin P may be one or two or more.

When the resin P contains the repeating unit K2, the content of the repeating unit K2 contained in the resin P (the total content when there are a plurality of repeating units K2) is 5 to 70 mol % is preferred, 10 to 65 mol % is more preferred, and 20 to 60 mol % is even more preferred.

<Repeating unit K3 having neither an acid-decomposable group nor a polar group>
Resin P may further contain a repeating unit having neither an acid-decomposable group nor a polar group (also referred to as “repeating unit K3”).
The repeating unit K3 preferably has an alicyclic hydrocarbon structure. Examples of the repeating unit K3 include repeating units described in paragraphs [0236] to <0237> of US Patent Application Publication No. 2016/0026083A1.
Preferred examples of the monomer corresponding to repeating unit K3 are shown below.

In addition, specific examples of the repeating unit K3 include repeating units disclosed in paragraph <0433> of US Patent Application Publication No. 2016/0070167A1.
When the resin P contains the repeating unit K3, the type of the repeating unit K3 contained in the resin P may be one, or two or more.
When the resin P contains the repeating unit K3, the content of the repeating unit K3 (the total content when there are a plurality of repeating units K3) is 5 to 40 mol% with respect to all repeating units in the resin P. is preferred, 5 to 30 mol% is more preferred, and 5 to 25 mol% is even more preferred.

In addition to the above repeating structural units, the resin P may include other repeating units such as dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, which are generally required characteristics of resists. It may have various repeating units for the purpose of adjusting heat resistance, sensitivity and the like.
Such repeating units include, but are not limited to, repeating units corresponding to a given monomer.

The predetermined monomer has one addition-polymerizable unsaturated bond selected from, for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. compounds and the like.
In addition, addition-polymerizable unsaturated compounds that are copolymerizable with the monomers corresponding to the above-mentioned various repeating structural units may be used.
In the resin P, the molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.

When the composition of the present invention is used for ArF exposure, it is preferable that the repeating unit having an aromatic group accounts for 15 mol % or less of all the repeating units in the resin P, from the viewpoint of ArF light transmittance. , 10 mol % or less.

When the composition of the present invention is for ArF exposure, the resin P contains (meta)
It is preferably composed of acrylate repeating units. In this case, all repeating units may be methacrylate repeating units, all repeating units may be acrylate repeating units, or all repeating units may be methacrylate repeating units and acrylate repeating units. Although it can be used, it is preferable that the acrylate-based repeating unit is 50 mol % or less with respect to the total repeating units of the resin P.

When the composition of the present invention is for KrF exposure, EB exposure, or EUV exposure, the resin P preferably has a repeating unit having an aromatic hydrocarbon ring group, and the phenolic hydroxyl group is decomposed by the action of acid. It is more preferable to contain a repeating unit having a structure (acid-decomposable group) protected by a leaving group that leaves as a group. Repeating units containing a phenolic hydroxyl group include hydroxystyrene repeating units and hydroxystyrene (meth)acrylate repeating units.
When the composition of the present invention is for KrF exposure, EB exposure, or EUV exposure, the content of the repeating unit having an aromatic hydrocarbon ring group contained in the resin P is On the other hand, 30 mol % or more is preferable. Although the upper limit is not particularly limited, it is, for example, 100 mol % or less. Among them, 30 to 100 mol % is preferable, 40 to 100 mol % is more preferable, and 50 to 100 mol % is even more preferable.

The weight average molecular weight (Mw) of the resin P is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, even more preferably 3,000 to 20,000. The dispersity (Mw/Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, further preferably 1.1 to 2.0. preferable.

In the composition of the present invention, the resin P may be used singly or in combination of two or more.
The content of the resin P in the composition of the present invention is 30% by mass or more based on the total solid content.
The content of the resin P is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, relative to the total solid content. Although the upper limit of the content of the resin P in the composition of the present invention is not particularly limited, it is preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 92% by mass or less.
In addition, solid content intends the component except the solvent in a composition, and if it is a component other than a solvent, even if it is a liquid component, it will be considered as solid content.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains 10% by mass or less of a cross-linking agent based on the total solid content of the composition. The content of the cross-linking agent is preferably 5% by mass or less, more preferably 1% by mass or less.

[Photoacid generator A]
The composition of the present invention typically preferably contains a photoacid generator (also referred to as "photoacid generator A").
The photoacid generator A is a compound that generates an acid upon exposure to actinic rays or radiation.
As the photoacid generator A, a compound that generates an organic acid upon exposure to actinic rays or radiation is preferred. Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oximesulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzylsulfonate compounds.

As the photoacid generator A, a known compound that generates an acid upon exposure to actinic rays or radiation can be appropriately selected and used either singly or as a mixture thereof. As the photoacid generator A, a photoacid generator commonly used for causing a deprotection reaction of an acid-decomposable resin can be used. ＞～
<0319>, paragraphs [0086] to <0094> of US Patent Application Publication No. 2015/0004544A1, and paragraphs <0323> to <0402> of US Patent Application Publication No. 2016/0237190A1 can be preferably used.

As the photoacid generator A, for example, compounds represented by the following general formula (ZI), general formula (ZII), or general formula (ZIII) are preferable.

In the above general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The number of carbon atoms in the organic groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Also, two of R ₂₀₁ to R ₂₀₃ may combine 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. Groups formed by combining two of R ₂₀₁ to R ₂₀₃ include alkylene groups (eg, butylene group and pentylene group) and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —.
Z ⁻ represents an anion (preferably a non-nucleophilic anion).

Preferred embodiments of the cation in general formula (ZI) include compound (ZI-1), compound (ZI-2), and compounds represented by general formula (ZI-3) (compound (ZI-3)), which will be described later. and corresponding groups in the compound represented by general formula (ZI-4) (compound (ZI-4)).
The photoacid generator A may be a compound having a plurality of structures represented by general formula (ZI). For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by general formula (ZI) and at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by general formula (ZI) are single bonds. Alternatively, it may be a compound having a structure bonded via a linking group.

First, compound (ZI-1) will be described.
Compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ in general formula (ZI) is an aryl group, that is, a compound having an arylsulfonium cation.
In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be aryl groups, or part of R ₂₀₁ to R ₂₀₃ may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
In addition, one of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the remaining two of R ₂₀₁ to R ₂₀₃ may combine to form a ring structure, in which an oxygen atom, a sulfur atom, It may contain an ester group, an amide group, or a carbonyl group. The group formed by bonding two of R ₂₀₁ to R ₂₀₃ includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group and/or a carbonyl group. alkylene groups (eg, butylene group, pentylene group, or —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —).
Arylsulfonium compounds include, for example, triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

The aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, 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. Heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group optionally possessed by the arylsulfonium compound is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. is preferred, and examples thereof include methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, cyclopropyl, cyclobutyl and cyclohexyl groups.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are each independently an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 15 carbon atoms), an aryl group (eg, carbon 6 to 14), an alkoxy group (eg, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.

Next, compound (ZI-2) will be described.
Compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.
The organic group having no 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-oxocyclo It is an alkyl group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, 1-5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, compound (ZI-3) will be described.

In general formula (ZI-3), M represents an alkyl group, a cycloalkyl group, or an aryl group, and when it has a ring structure, the ring structure is an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon - may contain at least one carbon double bond. _{R6c and R7c each} independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. R _6c and R _7c may combine to form a ring. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, or an alkenyl group. R _x and R _y may combine to form a ring. In addition, at least two selected from M, R _6c and R _7c may combine to form a ring structure, and the ring structure may contain a carbon-carbon double bond. Z ⁻ represents an anion.

In general formula (ZI-3), the alkyl group and cycloalkyl group represented by M include linear alkyl groups having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), 3 to 15 carbon atoms ( A branched alkyl group preferably having 3 to 10 carbon atoms) or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms) is preferable, and specifically, a methyl group, an ethyl group and a propyl group. , n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group, norbornyl group and the like.
The aryl group represented by M is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a sulfur atom, or the like. Heterocyclic structures include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, and the like.

M above may further have a substituent (for example, substituent T). As this embodiment, for example, M may be a benzyl group.
When M has a ring structure, the ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond.

Examples of the alkyl group, cycloalkyl group, and aryl group represented by R _6c and R _7c are the same as those for M described above, and preferred embodiments thereof are also the same. Also, R _6c and R _7c may combine to form a ring.
Halogen atoms represented by R _6c and R _7c include, for example, fluorine, chlorine, bromine and iodine atoms.

Examples of the alkyl group and cycloalkyl group represented by R _x and R _y include the same groups as those for M described above, and preferred embodiments thereof are also the same.
The alkenyl group represented by R _x and R _y is preferably an allyl group or a vinyl group.
R _x and R _y may further have a substituent (for example, substituent T). Examples of this embodiment include 2-oxoalkyl groups and alkoxycarbonylalkyl groups as R _x and R _y .
Examples of the 2-oxoalkyl group represented by R _x and R _y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), specifically 2-oxopropyl group, and 2-oxobutyl group.
Alkoxycarbonylalkyl groups represented by R _x and R _y include, for example, those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Also, R _x and R _y may combine to form a ring.
The ring structure formed by combining R _x and R _y may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.

In general formula (ZI-3), M and R _6c may combine to form a ring structure, and the formed ring structure may contain a carbon-carbon double bond.

Compound (ZI-3) above is preferably compound (ZI-3A).
Compound (ZI-3A) is a compound represented by the following general formula (ZI-3A) and having a phenacylsulfonium salt structure.

In general formula (ZI-3A),
R _1c to R _5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, or a hydroxyl group , represents a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c have the same definitions as R _6c and R _7c in general formula (ZI-3) described above, and preferred embodiments thereof are also the same.
R _x and R _y have the same meanings as R _x and R _y in general formula (ZI-3) described above, and preferred embodiments thereof are also the same.

Any two or more of R _1c to R _5c and R _x and R _y may each be combined to form a ring structure, which ring structure is each independently an oxygen atom, a sulfur atom, an ester bond, It may contain an amide bond or a carbon-carbon double bond. In addition, R _5c and R _6c , R _5c and R _x may each combine to form a ring structure, and this ring structure may each independently contain a carbon-carbon double bond. Also, R _6c and R _7c may be combined to form a ring structure.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings in which two or more of these rings are combined. The ring structure includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

Examples of groups formed by bonding 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.
The groups formed by combining R _5c and R _6c and R _5c and R _x are preferably single bonds or alkylene groups. The alkylene group includes a methylene group, an ethylene group, and the like.
^Zc- represents an anion.

Next, compound (ZI-4) will be described.
Compound (ZI-4) is represented by the following general formula (ZI-4).

In general formula (ZI-4),
l represents an integer of 0 to 2; It is particularly preferred that l is 0.
r represents an integer of 0 to 8;
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent.
When multiple R ₁₄ are present, they are each independently an alkyl group, cycloalkyl group, alkoxy group, alkylsulfonyl group, cycloalkylsulfonyl group, alkylcarbonyl group, alkoxycarbonyl group, or monocyclic or polycyclic cycloalkyl represents an alkoxy group having a skeleton. These groups may have a substituent.
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be joined together to form a ring. When two R ₁₅ are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, two R ₁₅ are alkylene groups, preferably joined together to form a ring structure.
Z ⁻ represents an anion.

In general formula (ZI-4), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ are linear or branched. The number of carbon atoms in the alkyl group is preferably 1-10. As the alkyl group, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like is more preferable. Two R ₁₅ 's may combine with each other to form a ring, and when forming a ring, the number of ring members is preferably 5-6.
When two R ₁₅ 's combine to form a ring, the ring may have a substituent. Examples of the substituent include, but are not particularly limited to, a hydroxyl group, a halogen atom, an alkyl group, or an alkoxy group. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom. The above alkyl groups may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-6. Examples of the alkyl group include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group. The above alkyl group may have a substituent, and the substituent is not particularly limited, but examples thereof include a halogen atom. The alkoxy group may be linear or branched. The alkoxy group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Examples of the alkoxy group include methoxy group, ethoxy group and tert-butoxy group. The alkoxy group may have a substituent, and the substituent is not particularly limited. cycloalkyl group).

Next, general formulas (ZII) and (ZIII) will be described.
In general formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
The aryl group represented by R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Skeletons of aryl groups having a heterocyclic structure include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl group and pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group and norbornyl group) are preferred.

Each of the aryl groups, alkyl groups and cycloalkyl groups of R ₂₀₄ to R ₂₀₇ may independently have a substituent. Examples of substituents that the aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (eg, 1 to 15 carbon atoms) and a cycloalkyl group (eg, 3 to 3 carbon atoms). 15), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.
Z ⁻ represents an anion.

Preferred examples of the sulfonium cation in general formula (ZI) and the iodonium cation in general formula (ZII) are shown below.

Z - in general formula (ZI), Z ^- in general formula (ZII), Z ^- in general formula (ZI-3), Zc ^- in general formula (ZI ^- 3A), and Z in general formula (ZI-4) A preferred embodiment of ^- is an anion represented by the following general formula (3).

In general formula (3), o represents an integer of 1-3. p represents an integer from 0 to 10; q represents an integer from 0 to 10;

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4. A perfluoroalkyl group is preferable as the alkyl group substituted with at least one fluorine atom.
Xf is preferably a fluorine atom or a C 1-4 perfluoroalkyl group, more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that both Xf are fluorine atoms.

_R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at _least one fluorine atom. When multiple R ₄ and R ₅ are present, each of R ₄ and R ₅ may be the same or different.
The alkyl groups represented by R ₄ and R ₅ may have substituents and preferably have 1 to 4 carbon atoms. R ₄ and R ₅ are preferably hydrogen atoms.
Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in general formula (3).

L represents a divalent linking group. When there are multiple L's, each L may be the same or different.
Examples of divalent linking groups include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, - SO—, —SO ₂ —, alkylene group (preferably having 1 to 6 carbon atoms), cycloalkylene group (preferably having 3 to 15 carbon atoms)
, an alkenylene group (preferably having 2 to 6 carbon atoms) and a divalent linking group combining a plurality of these groups. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene group-, -OCO-alkylene group-, -CONH- Alkylene group- or -NHCO-alkylene group- is preferred, and -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene group- or -OCO-alkylene group- is more preferred.

W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferable.
Cyclic organic groups include, for example, alicyclic groups, aryl groups, and heterocyclic groups.
Alicyclic groups may be monocyclic or polycyclic. Monocyclic alicyclic groups include, for example, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

Aryl groups may be monocyclic or polycyclic. The aryl group includes, for example, phenyl group, naphthyl group, phenanthryl group and anthryl group.
A heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further suppress acid diffusion. Moreover, the heterocyclic group may or may not have aromaticity. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Non-aromatic heterocycles include, for example, tetrahydropyran, lactone, sultone and decahydroisoquinoline rings. Examples of the lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the resins described above. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

The cyclic organic group may have a substituent. Examples of this substituent include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic, and spirocyclic). any group, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide groups, and sulfonate ester groups. In addition, carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic|annular organic group.

Examples of anions represented by the general formula (3) include SO ₃ ⁻ —CF ₂ —CH ₂ —OCO-(L)q′-W, SO ₃ ^— —CF ₂ —CHF—CH ₂ —OCO-(L) q′-W, SO ₃ ⁻ —CF ₂ —COO-(L)q′-W, SO ₃ ⁻ —CF ₂ —CF ₂ —CH ₂ —CH ₂ —(L)qW, SO ₃ ^— —CF ₂ -CH(CF ₃ )-OCO-(L)q'-W is preferred. Here, L, q and W are the same as in general formula (3). q' represents an integer from 0 to 10;

In one embodiment, Z - in general formula (ZI), Z ^- in general formula (ZII), Z ^- in general formula (ZI-3), Zc ^- in general formula (ZI ^- 3A), and general formula (ZI- Z ⁻ in 4) is also preferably an anion represented by the following general formula (4).

In general formula (4),
X ^B1 and X ^B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom. X ^B1 and X ^B2 are preferably hydrogen atoms.
X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. At least one of X ^B3 and X ^B4 is preferably a fluorine atom or a monovalent organic group having a fluorine atom, and both of X ^B3 and X ^B4 are a fluorine atom or a monovalent organic group having a fluorine atom is more preferred. More preferably, both X ^B3 and X ^B4 are fluorine-substituted alkyl groups.
L, q and W are the same as in general formula (3).

Z - in general formula (ZI), Z ^- in general formula (ZII), Z ^- in general formula (ZI-3), Zc ^- in general formula (ZI ^- 3A), and Z in general formula (ZI-4) ^- may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted by a branched alkyl group or a cycloalkyl group.

Z - in general formula (ZI), Z ^- in general formula (ZII), Z ^- in general formula (ZI-3), Zc ^- in general formula (ZI ^- 3A), and Z in general formula (ZI-4) ^- is also preferably an aromatic sulfonate anion represented by the following general formula (SA1).

In formula (SA1),
Ar represents an aryl group and may further have a substituent other than the sulfonate anion and -(D-B) group. Substituents which may be further included include a fluorine atom and a hydroxyl group.

n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and still more preferably 3.

D represents a single bond or a divalent linking group. Examples of divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate ester groups, ester groups, and groups consisting of combinations of two or more thereof.

B represents a hydrocarbon group.

Preferably D is a single bond and B is an aliphatic hydrocarbon structure. B is more preferably an isopropyl group or a cyclohexyl group.

Z - in general formula (ZI), anion Z ^- in general formula (ZII), Z ^- in general formula (ZI-3), Zc ^- in general formula (ZI ^- 3A), and general formula (ZI-4) Preferred examples of Z ⁻ are shown below, but are not limited thereto.

In the present invention, any combination of the above cations and anions can be used as the photoacid generator A.

<Photoacid generator Aw>
In the present invention, the strength of the acid generated by the photoacid generator A is not particularly limited, but a pKa of -1.40 or more is particularly preferable from the viewpoint of improving EL performance. That is, in the composition of the present invention, it is preferable to use, as the photoacid generator A, a photoacid generator whose generated acid has a pKa of -1.40 or higher (also referred to as "photoacid generator Aw"). . The upper limit of the pKa of the acid generated from the photoacid generator Aw is not particularly limited, and is, for example, 5.00 or less.
The pKa of the acid generated from the photo-acid generator Aw is −1.38 or higher in that the LWR, LER, and CDU of the pattern to be formed are superior, and/or the uniformity of the film surface is superior. preferable. Moreover, the upper limit is preferably 2.00 or less, more preferably 1.30 or less, in terms of the LWR, LER, and CDU of the formed pattern.
The acid generated from the photoacid generator Aw is not particularly limited as long as it satisfies the above pKa, but sulfonic acid is preferred.

The photoacid generator Aw includes Z ⁻ in general formula (ZI), Z ⁻ in general formula (ZII), Z ⁻ in general formula (ZI-3), Zc in general formula (ZI ^- 3A), And Z 1 ^- in general formula (ZI-4) is preferably represented by general formula (1-1) or (1-2) below.
That is, Z in the aforementioned general formula (ZI) ^, Z in general formula (ZII), Z in general formula (ZI ^- 3), Zc in general formula (ZI ^- 3A), ^and general formula (ZI- A particularly preferred embodiment of Z 1 ^- in 4) is an anion represented by the following general formula (1-1) or (1-2).

In general formula (1-1), R ₁₁ represents a hydrogen atom or a monovalent organic group, R ₁₂ represents a monovalent organic group, Rf ₁₁ represents a hydrogen atom, a fluorine atom, or a monovalent represents an organic group.
In general formula (1-2), R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom, a fluorine atom or a monovalent organic group, and R ₂₄ represents a monovalent organic group. , Rf ₂₁ represent a fluorine atom or a monovalent organic group containing a fluorine atom.

In general formula (1-1), R ₁₁ represents a hydrogen atom or a monovalent organic group.
The monovalent organic group represented by R ₁₁ is not particularly limited, and is preferably a monovalent organic group having 1 to 20 carbon atoms, such as an alkyl group or a cycloalkyl group. may be linear or branched. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 6 to 20 carbon atoms. In addition, the said alkyl group or cycloalkyl group may further have a substituent. The monovalent organic group represented by R ₁₁ preferably has no fluorine atom.
R ₁₁ is preferably a hydrogen atom.

R ₁₂ represents a monovalent organic group. The monovalent organic group represented by R ₁₂ is not particularly limited, and is preferably a monovalent organic group having 1 to 20 carbon atoms. For example, the group represented by *-L ₁₁ -W ₁₁ mentioned. Here, L ₁₁ represents a divalent linking group, W ₁₁ represents an organic group containing a cyclic structure, and * represents a bonding position.

Examples of the divalent linking group represented by L ₁₁ include -COO-(-C(=O)-O-)
, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, linear or branched alkylene group (preferably 1 carbon atom to 6), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group combining a plurality of these. Specifically, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -AL-, -COO-AL-, -OCO-AL-, -CONH-AL-, -NHCO-AL-, -AL-OCO-, -AL-COO-, -CO-AL-, -AL-CO-, -O-AL-, -AL-O-, and, -AL-O-CO-O-AL- and the like. AL above represents a linear or branched alkylene group (preferably having 1 to 6 carbon atoms).

_W11 represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferable.
Cyclic organic groups include, for example, alicyclic groups, aryl groups, and heterocyclic groups.
Alicyclic groups may be monocyclic or polycyclic. Monocyclic alicyclic groups include, for example, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

Aryl groups may be monocyclic or polycyclic. The aryl group includes, for example, phenyl group, naphthyl group, phenanthryl group, and anthryl group.
A heterocyclic group may be monocyclic or polycyclic. Moreover, the heterocyclic group may or may not have aromaticity. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Non-aromatic heterocycles include, for example, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the resins described above. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

The cyclic organic group may have a substituent. Examples of such substituents include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic, and spirocyclic). It may be any, preferably having 3 to 20 carbon atoms.), an aryl group (preferably having 6 to 14 carbon atoms.), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, Sulfonamide groups and sulfonate ester groups are included. In addition, carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic|annular organic group.

Rf ₁₁ represents a hydrogen atom, a fluorine atom, or a monovalent organic group.
The monovalent organic group represented by Rf ₁₁ is not particularly limited, but is preferably a monovalent organic group containing a fluorine atom. ) or a cycloalkyl group. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-4. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. A perfluoroalkyl group is preferable as the alkyl group substituted with at least one fluorine atom. A perfluorocycloalkyl group is preferred as the cycloalkyl group substituted with at least one fluorine atom.
Rf ₁₁ is preferably a fluorine atom or a monovalent organic group containing a fluorine atom, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and still more preferably a fluorine atom or CF ₃ .

Preferred specific examples of the generated acid (acid having a pKa of −1.40 or more) when the anion of the photoacid generator Aw is an anion represented by the general formula (1-1) are shown below. It is not limited to these.

In general formula (1-2) above, R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom, a fluorine atom or a monovalent organic group. The monovalent organic group represented by R ₂₁ , R ₂₂ and R ₂₃ is not particularly limited, and examples thereof include the groups exemplified for the substituent T described above. It may be chain or branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 6), or a cycloalkyl group (having 3 to 20 carbon atoms). preferably 6 to 15) is preferred. The alkyl group or cycloalkyl group represented by R ₂₁ , R ₂₂ and R ₂₃ may further have a substituent, for example, may be substituted with a fluorine atom.
R ₂₁ , R ₂₂ and R ₂₃ are preferably hydrogen atoms or fluorine atoms.
At least one of R ₂₁ and R ₂₂ preferably represents a group other than a fluorine atom, and more preferably both represent a hydrogen atom.

_R24 represents a monovalent organic group.
The monovalent organic group represented by R ₂₄ is preferably a monovalent organic group having 1 to 20 carbon atoms, such as a monovalent organic group having 1 to 20 carbon atoms and having no fluorine atom. Specific examples include the same monovalent organic groups as those represented by R ₁₂ in general formula (1-1).

Rf ₂₁ represents a fluorine atom or a monovalent organic group containing a fluorine atom.
Examples of the fluorine atom-containing monovalent organic group represented by Rf ₂₁ include those exemplified for the fluorine atom-containing monovalent organic group represented by Rf ₁₁ in the general formula (1-1).

Preferable specific examples of the generated acid (acid having a pKa of −1.40 or more) when the anion of the photoacid generator Aw is an anion represented by the general formula (1-2) are shown below. It is not limited to these.

Specific examples of the photoacid generator Aw are shown below, but are not limited thereto.

The photoacid generator A may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of a polymer. Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer may be used in combination.
The photoacid generator A is preferably in the form of a low molecular weight compound.
When the photoacid generator A is in the form of a low-molecular-weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less.
When the photoacid generator A is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the resin P described above, or may be incorporated in a resin different from the resin P.
The photo-acid generator A may be used individually by 1 type, and may use 2 or more types together.
In the composition of the present invention, the content of the photoacid generator A (the total content when multiple types are present) is 0.1 to 35% by mass with respect to the total solid content of the composition of the present invention. is preferred, 0.5 to 25 mass % is more preferred, and 1 to 20 mass % is even more preferred.

<Acid diffusion control agent>
The composition of the present invention preferably contains an acid diffusion control agent. The acid diffusion control agent traps the acid generated from the photoacid generator A and the like during exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation
(Also referred to as “compound (DB)”), a compound (DC) that generates an acid that is relatively weak with respect to photoacid generator A (also referred to as “compound (DC)”), a nitrogen atom However, a compound (DD) (also referred to as "compound (DD)") having a group that leaves by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation moiety (also referred to as "compound (DE)") ) etc. can be used as an acid diffusion control agent. Known acid diffusion control agents can be used as appropriate in the composition of the present invention. For example, paragraphs <0627>-<0664> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0095>-<0187> of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1 Known compounds disclosed in paragraphs <0403> to <0423> of the specification and paragraphs <0259> to <0328> of US Patent Application Publication No. 2016/0274458A1 can be suitably used as acid diffusion control agents. .

(Basic compound (DA))
As the basic compound (DA), compounds having structures represented by the following formulas (A) to (E) are preferred.

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl represents a group (6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each independently represent an alkyl group having 1 to 20 carbon atoms.

The alkyl groups in general formulas (A) and (E) may be substituted or unsubstituted.
Regarding the above alkyl group, the substituted alkyl group is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
The alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.

As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, or piperidine are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, A compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, or an aniline derivative having a hydroxyl group and/or an ether bond is more preferred.

The difference between the pKa of the conjugate acid of the basic compound (DA) and the pKa of the acid generated from the photoacid generator A (preferably the photoacid generator Aw) (the pKa of the conjugate acid of the basic compound (DA) to the photoacid The value obtained by subtracting the pKa of the acid generated from the acid generator A (preferably the photoacid generator Aw) is preferably 1.00 or more, more preferably 1.00 to 14.00, and 2.00 to 13.0. 00 is more preferred.
In addition, the pKa of the conjugate acid of the basic compound (DA) varies depending on the type of photoacid generator A (preferably photoacid generator Aw) used, but is preferably 0.00 to 14.00, for example. 3.00 to 13.00 is more preferred, and 3.50 to 12.50 is even more preferred.

(Basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation)
The basic compound (DB) has a proton acceptor functional group and is decomposed by exposure to actinic rays or radiation to reduce or eliminate the proton acceptor, or change the proton acceptor to acidic. is a compound.

The proton-accepting functional group is a functional group having electrons or a group capable of electrostatically interacting with protons, for example, a functional group having a macrocyclic structure such as cyclic polyether, or a π-conjugated means a functional group having a nitrogen atom with a lone pair of electrons that does not contribute to A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

Preferred partial structures of proton acceptor functional groups include, for example, crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures.

The compound (DB) is decomposed by exposure to actinic rays or radiation to reduce or eliminate its proton acceptor property, or to generate a compound whose proton acceptor property is changed to an acidic one. Here, the reduction or disappearance of proton acceptor property, or the change from proton acceptor property to acidity is a change in proton acceptor property due to the addition of protons to the proton acceptor functional group. means that when a proton adduct is produced from a compound (DB) having a proton-accepting functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.
Proton acceptor properties can be confirmed by measuring pH.

The pKa of the compound generated by decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa<-1, more preferably satisfies -13<pKa<-1, and -13<pKa. It is more preferable to satisfy <−3.

Compound (DB) is preferably a compound represented by general formula (bd-1).
General formula (bd-1):
R _b1 -B _b1 -X _b1 -A _b1 -W ₁ -N ^- -W ₂ -Rf _b1 [C _b1 ⁺ ]

In the general formula (bd-1),
W ₁ and W ₂ each independently represent -SO ₂ - or -CO-.
Rf _b1 represents an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted aryl group.
A _b1 represents a single bond or a divalent linking group.
X _b1 represents a single bond, —SO ₂ —, or —CO—.
B _b1 represents a single bond, an oxygen atom, or —N(R _b1x )R _b1y —.
R _b1x represents a hydrogen atom or an organic group.
R _b1y represents a single bond or a divalent organic group.
R _b1 represents a monovalent organic group having a proton acceptor functional group.
R _b1x may combine with R _b1y to form a ring, or may combine with R _b1 to form a ring.
[C _b1 ⁺ ] represents a counter cation.

At least one of W ₁ and W ₂ is preferably —SO ₂ —, more preferably both are —SO ₂ —.

Rf _b1 is preferably an optionally fluorine-containing alkyl group having 1 to 6 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and a perfluoroalkyl group having 1 to 3 carbon atoms. A fluoroalkyl group is more preferred.

The divalent linking group for A _b1 is preferably a divalent linking group having 2 to 12 carbon atoms, such as an alkylene group and a phenylene group. Among them, an alkylene group having at least one fluorine atom is preferable, and the number of carbon atoms is preferably 2-6, more preferably 2-4. A linking group such as an oxygen atom or a sulfur atom may be present in the alkylene chain. The alkylene group is preferably an alkylene group in which 30 to 100% of the hydrogen atoms are substituted with fluorine atoms, and more preferably the carbon atoms bonded to X _b1 or W ₁ have fluorine atoms. Among them, the divalent linking group in _Ab1 is preferably a perfluoroalkylene group, more preferably a perfluoroethylene group, a perfluoropropylene group, or a perfluorobutylene group.

The monovalent organic group for R _b1x preferably has 2 to 30 carbon atoms, such as an alkyl group, a cycloalkyl group optionally having an oxygen atom in the ring, an aryl group, an aralkyl group, and an alkenyl group. is mentioned.
The alkyl group for R _b1x may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom and/or a nitrogen atom in the alkyl chain. may have
As the alkyl group having a substituent, a group in which a linear or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue, etc.). mentioned.
The cycloalkyl group for R _b1x may have a substituent, and is preferably a cycloalkyl group having 3 to 20 carbon atoms. Moreover, the cycloalkyl group may have an oxygen atom in the ring.
The aryl group for R _b1x may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.
The aralkyl group for R _b1x may have a substituent, and is preferably an aralkyl group having 7 to 20 carbon atoms.
The alkenyl group for R _b1x may have a substituent, and examples thereof include groups having a double bond at any position of the alkyl group exemplified for R _b1x .

When B _b1 represents —N(R _b1x )R _b1y —, the divalent organic group for R _b1y is preferably an alkylene group. In this case, the ring that can be formed by combining R _b1x and R _b1y includes, for example, a 5- to 8-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring. The nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X _b1 in -N(R _b1x )R _b1y -.

When B _b1 represents —N(R _b1x )R _b1y —, it is preferred that R _b1 and R _b1x combine with each other to form a ring. The formation of a ring improves the stability and the storage stability of the composition using it. The ring preferably has 4 to 20 carbon atoms, may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom and/or a nitrogen atom in the ring. The nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X _b1 in -N(R _b1x )R _b1y -.

Monocyclic rings include 4-, 5-, 6-, 7-, and 8-membered rings containing a nitrogen atom. Such ring structures include, for example, a piperazine ring and a piperidine ring. Polycyclic rings include structures consisting of combinations of two or more monocyclic structures.
Each of the monocyclic and polycyclic rings may have a substituent, such as a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group. (Preferably 6 to 14 carbon atoms), alkoxy groups (preferably 1 to 10 carbon atoms), acyl groups (preferably 2 to 15 carbon atoms), acyloxy groups (preferably 2 to 15 carbon atoms), alkoxycarbonyl groups ( preferably 2 to 15 carbon atoms), or an aminoacyl group (preferably 2 to 20 carbon atoms). These substituents may have further substituents if possible. Examples of aryl groups and cycloalkyl groups further having substituents include alkyl groups (preferably having 1 to 15 carbon atoms). Examples of substituents further possessed by the aminoacyl group include alkyl groups (preferably having 1 to 15 carbon atoms).

The proton-accepting functional group in R _b1 is as described above, and examples of the partial structure include structures of crown ethers, primary to tertiary amines, and nitrogen-containing heterocycles (pyridine, imidazole, pyrazine, etc.). It is preferable to have
As the proton acceptor functional group, a functional group having a nitrogen atom is preferable, and a group having a primary to tertiary amino group or a nitrogen-containing heterocyclic group is more preferable. In these structures, all atoms adjacent to nitrogen atoms contained in the structures are preferably carbon atoms or hydrogen atoms. Further, it is preferable that an electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly connected to the nitrogen atom.
The monovalent organic group in such a monovalent organic group (group R _b1 ) containing a proton acceptor functional group preferably has 2 to 30 carbon atoms, and is an alkyl group, a cycloalkyl group, an aryl group, Aralkyl groups, alkenyl groups, and the like can be mentioned, and each group may have a substituent.

The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group in the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group containing a proton acceptor functional group in R _b1 are, respectively, The same groups as the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group exemplified as R _b1x can be mentioned.

Examples of substituents that each of the above groups may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a cycloalkyl group (preferably having 3 to 10 carbon atoms. may be substituted with a group having (such as an ester group)), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 20), acyloxy groups (preferably having 2 to 10 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 20 carbon atoms), and aminoacyl groups (preferably having 2 to 20 carbon atoms). Examples of substituents possessed by cyclic groups such as aryl groups and cycloalkyl groups include alkyl groups (preferably having 1 to 20 carbon atoms). Substituents possessed by the aminoacyl group include, for example, 1 or 2 alkyl groups (preferably having 1 to 20 carbon atoms).

[C _b1 ⁺ ] is preferably a sulfonium cation or an iodonium cation as a counter cation. Examples of sulfonium cations and iodonium cations include sulfonium cations and iodonium cations in the cations that the photoacid generator A may have (more specifically, cations in compounds represented by general formula (ZI), and general cations in compounds represented by formula (ZII)) can be used as well.

The difference between the pKa of the conjugate acid of the basic compound (DB) and the pKa of the acid generated from the photoacid generator A (preferably the photoacid generator Aw) (the pKa of the conjugate acid of the basic compound (DB) to the light The value obtained by subtracting the pKa of the acid generated from the acid generator A (preferably the photoacid generator Aw) is preferably 1.00 or more, more preferably 1.00 to 14.00, and 2.00 to 13.0. 00 is more preferred.
In addition, the pKa of the conjugate acid of the basic compound (DB) varies depending on the type of photoacid generator A (preferably photoacid generator Aw) used, but is preferably 0.00 to 14.00, for example. 3.00 to 13.00 is more preferred, and 3.50 to 12.50 is even more preferred.

(Compound (DC) that generates an acid that is relatively weak to the photoacid generator A)
The compound (DC) is preferably a compound that generates an acid upon exposure to actinic rays or radiation. Hereinafter, among compounds (DC), a compound that generates an acid upon exposure to actinic rays or radiation is also referred to as "photoacid generator B".
The photoacid generator B is preferably a compound that generates an acid having a pKa greater than that of the acid generated from the photoacid generator A (preferably the photoacid generator Aw) by 1.00 or more.
The difference between the pKa of the acid generated from the photo-acid generator B and the pKa of the acid generated from the photo-acid generator A (preferably the photo-acid generator Aw) (from the pKa of the acid generated from the photo-acid generator B to the light The value obtained by subtracting the pKa of the acid generated from the acid generator A (preferably the photoacid generator Aw) is 1.00 or more, preferably 1.00 to 10.00, and 1.00 to 5.00. is more preferred, and 1.00 to 3.00 is even more preferred.
Further, the pKa of the acid generated from the photoacid generator B varies depending on the type of the photoacid generator A (preferably the photoacid generator Aw) used, but is preferably 0.00 to 10.00, for example. 0.50 to 5.00 is more preferred, and 1.00 to 5.00 is even more preferred.

The photoacid generator B is preferably an onium salt compound consisting of an anion and a cation. As such onium salt compounds, compounds represented by general formulas (d1-1) to (d1-3) are preferable.

In the formula, R ⁵¹ represents a hydrocarbon group (eg, an aryl group such as a phenyl group) optionally having a substituent (eg, hydroxyl group).
Z ^2c represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms (provided that the carbon atom adjacent to S is not substituted with a fluorine atom).
The above hydrocarbon group for Z ^2c may be linear or branched, and may have a cyclic structure. In addition, the carbon atoms in the hydrocarbon group (preferably the carbon atoms forming a cyclic structure when the hydrocarbon group has a cyclic structure) may be carbonyl carbon (--CO--). Examples of the hydrocarbon group include a group having an optionally substituted norbornyl group. A carbon atom forming the norbornyl group may be a carbonyl carbon.
^R52 represents an organic group ^, Y3 represents a linear or branched alkylene group, cycloalkylene group or arylene group, and Rf represents a hydrocarbon group containing a fluorine atom.
Further, “Z ^2c —SO ₃ ⁻ ” in general formula (d1-2) is an anion (preferably in general formula (1-1) described above) in photoacid generator A (preferably photoacid generator Aw). or the group represented by the general formula (1-2) described above).
Each M ⁺ is independently an ammonium cation, a sulfonium cation, or an iodonium cation.
Examples of sulfonium cations and iodonium cations include sulfonium cations and iodonium cations in the cations that the photoacid generator A may have (more specifically, compounds represented by general formula (ZI), and general formula ( ZII) cations in compounds represented by ZII) can likewise be used.

The photoacid generator B may be a compound having a cation site and an anion site in the same molecule, and the cation site and the anion site are linked by a covalent bond.
As the compound, a compound represented by general formula (C-1) or a compound represented by general formula (C-2) is preferable.

In general formulas (C-1) to (C-3),
R ₁ , R ₂ and R ₃ each independently represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond that links a cationic group (S ⁺ , I ⁺ , or N ⁺ ) ^and -X-.
—X ^— represents —COO ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , or —N ⁻ —R ₄ .
R ₄ has at least one of a carbonyl group (--CO--), a sulfonyl group (--SO ₂ --), and a sulfinyl group (--S(=O)--) at the linking site with the adjacent N atom represents a monovalent substituent.
R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may combine with each other to form a ring.
In general formula (C-3), two of R ₁ to R ₃ together represent one divalent substituent, which may be bonded to the N atom via a double bond.

Examples of substituents having 1 or more carbon atoms for R ₁ to R ₃ include alkyl groups, cycloalkyl groups, aryl groups (preferably having 6 to 15 carbon atoms), alkyloxycarbonyl groups, cycloalkyloxycarbonyl groups, and aryloxycarbonyl groups. , an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, and the like. Among them, an alkyl group, a cycloalkyl group, or an aryl group is preferable.

L ₁ as a divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group (preferably having 6 to 15 carbon atoms), carbonyl group, ether bond, ester bond, amide bond, urethane A bond, a urea bond, a group formed by combining two or more of these, and the like. Among them, an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these is preferable.

The photoacid generator B is a compound that generates an acid with a pKa greater than that of the acid generated from the photoacid generator A (preferably the photoacid generator Aw) by 1.00 or more, and has a nitrogen atom in the cation portion. Onium salt compounds may also be used. The onium salt compound having a nitrogen atom in the cation portion preferably has a basic site containing a nitrogen atom in the cation portion.
The basic moiety is preferably an amino group, more preferably an aliphatic amino group. Also, all atoms adjacent to the nitrogen atom in the basic moiety are preferably hydrogen atoms or carbon atoms. Moreover, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom, etc.) is not directly connected to the nitrogen atom.

The photoacid generator B may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of a polymer. Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer may be used in combination.
The photoacid generator B is preferably in the form of a low molecular weight compound.
When the photoacid generator B is in the form of a low-molecular-weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less.

(Compound (DD) having a group having a nitrogen atom and leaving by the action of an acid)
The compound (DD) is preferably an amine derivative having a group on the nitrogen atom that leaves under the action of an acid.
The group that leaves by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, more preferably a carbamate group or a hemiaminal ether group. .
Compound (DD) is preferably a low-molecular-weight compound.
The molecular weight of the compound (DD) is preferably 100-1000, more preferably 100-700, even more preferably 100-500.
Compound (DD) may have a carbamate group with a protecting group on the nitrogen atom. A protecting group constituting a carbamate group is represented by the following general formula (d-1).

In general formula (d-1),
Rb each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group ( preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb's may combine with each other to form a ring.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are each independently a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, a functional group such as an oxo group, an alkoxy group, or It may be substituted with a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

Rb is preferably a linear or branched alkyl group, cycloalkyl group or aryl group, more preferably a linear or branched alkyl group or cycloalkyl group.
Examples of the ring formed by connecting two Rb's to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
Specific structures of the group represented by formula (d-1) include, but are not limited to, structures disclosed in paragraph <0466> of US Patent Publication No. US2012/0135348A1.

Compound (DD) preferably has a structure represented by the following general formula (6).

In general formula (6),
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l+m=3.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two Ra's may be the same or different, and the two Ra's may be linked together to form a heterocyclic ring together with the nitrogen atom in the formula. This heterocyclic ring may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same definition as Rb in formula (d-1) above, and preferred examples are also the same.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra are each independently substituted with an alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb. It may be substituted with the same groups as the groups described above as good groups.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above groups) for Ra include the same groups as the specific examples described above for Rb. be done.
Specific examples of particularly preferred compounds (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012/0135348A1.

Difference between pKa of conjugate acid of compound (DD) and pKa of acid generated from photoacid generator A (preferably photoacid generator Aw) (pKa of conjugate acid of compound (DD) to photoacid generator A (Preferably the value obtained by subtracting the pKa of the acid generated from the photoacid generator Aw) is preferably 1.00 or more, more preferably 1.00 to 14.00, and still more preferably 2.00 to 13.00. .
The pKa of the conjugate acid of the compound (DD) varies depending on the type of the photoacid generator A (preferably the photoacid generator Aw) used, but is preferably 0.00 to 14.00. 00 to 13.00 is more preferred, and 3.50 to 12.50 is even more preferred.

(Onium salt compound (DE) having a nitrogen atom in the cation moiety)
Compound (DE) is preferably a compound having a basic moiety containing a nitrogen atom in the cation portion. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. More preferably all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Moreover, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom, etc.) is not directly connected to the nitrogen atom.
Preferred specific examples of the compound (DE) include, but are not limited to, the compounds disclosed in paragraph <0203> of US Patent Application Publication No. 2015/0309408A1.

Difference between pKa of conjugate acid of compound (DE) and pKa of acid generated from photoacid generator A (preferably photoacid generator Aw) (pKa of conjugate acid of compound (DE) to photoacid generator A (Preferably the value obtained by subtracting the pKa of the acid generated from the photoacid generator Aw) is preferably 1.00 or more, more preferably 1.00 to 14.00, and still more preferably 2.00 to 13.00. .
The pKa of the conjugate acid of the compound (DE) varies depending on the type of photoacid generator A (preferably photoacid generator Aw) used, but is preferably 0.00 to 14.00. 00 to 13.00 is more preferred, and 3.50 to 12.50 is even more preferred.

The composition of the present invention comprises the photoacid generator Aw described above, a basic compound (DA), a basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation, and a photoacid generator Aw. A compound (DC) that generates an acid with a pKa greater than that of the generated acid by 1.00 or more, a compound (DD) that has a nitrogen atom and has a group that leaves under the action of an acid, and a cation portion that has a nitrogen atom It preferably contains at least one onium salt compound (DE).

Preferred examples of acid diffusion control agents are shown below, but are not limited thereto.

In the composition of the present invention, one type of acid diffusion control agent may be used alone, or two or more types may be used in combination.
The content of the acid diffusion control agent in the composition of the present invention (the total when multiple types are present) is preferably 0.05 to 10% by mass, preferably 0.05 to 10% by mass, based on the total solid content of the composition. 5% by mass is more preferred.

[Hydrophobic resin]
The composition of the invention may contain a hydrophobic resin. In addition, the hydrophobic resin is a resin different from the resin P, and in that it is superior in film thickness uniformity, a repeating unit having a group (acid-decomposable group) that is decomposed by the action of an acid to increase the polarity is used. It is preferably substantially free. The expression "substantially free of repeating units having an acid-decomposable group" means that the content of repeating units containing the acid-decomposable group in the hydrophobic resin is less than the total repeating units of the hydrophobic resin. , 0 mol % or more and 5 mol % or less are intended, and the upper limit is preferably 3 mol % or less, more preferably 1 mol % or less.
By including a hydrophobic resin in the composition of the present invention, it is easy to control the static and/or dynamic contact angle on the surface of the resist film (actinic ray-sensitive or radiation-sensitive film). This makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid followability in immersion exposure, reduce immersion defects, and the like.
Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film. It does not have to contribute to mixing.

From the viewpoint of uneven distribution on the film surface layer, the hydrophobic resin includes a fluorine atom, a fluorine atom-containing group, a silicon atom-containing group, a linear or branched alkyl group or a cycloalkyl group having 6 or more carbon atoms, an aryl group having 9 or more carbon atoms, an aralkyl group having 10 or more carbon atoms, an aryl group substituted with at least one linear or branched alkyl group having 3 or more carbon atoms, and at least one carbon The resin preferably has one or more groups (hereinafter also referred to as “hydrophobic groups”) selected from the group consisting of aryl groups substituted with cycloalkyl groups of number 5 or more.
Moreover, the hydrophobic resin preferably contains a repeating unit containing the hydrophobic group.
When the hydrophobic resin contains fluorine atoms and/or silicon atoms, the fluorine atoms and/or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin, or may be contained in the side chain. It may be

As the fluorine atom-containing group, a fluorine atom-containing linear or branched alkyl group, a cycloalkyl group, or a fluorine atom-containing aryl group is preferred.
As the linear or branched alkyl group having a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms is preferable, and CF ₃ is more preferable.
As the cycloalkyl group having a fluorine atom, a perfluorocycloalkyl group having 3 to 20 carbon atoms is preferable.
An aryl group having a fluorine atom includes, for example, a phenyl group substituted with a fluorine atom.

Examples of the silicon atom-containing groups include alkylsilyl groups.
Examples of the alkylsilyl group include trimethylsilyl group, triethylsilyl group, and tert-butyldimethylsilyl group.

Examples of the linear or branched alkyl group or cycloalkyl group having 6 or more carbon atoms include a linear or branched alkyl group or cycloalkyl group having 6 to 20 carbon atoms. Examples include 2-ethylhexyl group, norbornyl group, and adamantyl group.

Examples of the aryl group having 9 or more carbon atoms include polycyclic aryl groups formed by combining two or more 5- or 6-membered monocyclic aromatic hydrocarbon rings.

As the aralkyl group having 10 or more carbon atoms, for example, an aralkyl group having 10 to 20 carbon atoms is preferable, and specifically, 1-naphthylmethyl group, 1-(1-naphthyl)ethyl group, triphenylmethyl group. , and pyrenylmethyl groups.

The aryl group substituted with at least one linear or branched alkyl group having 3 or more carbon atoms is, for example, a linear or branched aryl group having 3 to 20 carbon atoms (preferably 3 to 10 carbon atoms) or A phenyl group substituted with a branched alkyl group can be mentioned.

Examples of the aryl group substituted with at least one cycloalkyl group having 5 or more carbon atoms include a phenyl group substituted with a cycloalkyl group having 5 to 20 carbon atoms (preferably 5 to 10 carbon atoms). be done.

Among others, the hydrophobic resin preferably contains a repeating unit containing a fluorine atom or a group having a fluorine atom. Moreover, the number of fluorine atoms contained in the hydrophobic resin is preferably larger than the number of fluorine atoms contained in the photoacid generator A from the viewpoint of better film thickness uniformity.
Here, the number of fluorine atoms contained in the hydrophobic resin is determined by the following formula (1) when the hydrophobic resin contains only one type of repeating unit containing fluorine atoms. When the hydrophobic resin contains two or more kinds of repeating units containing fluorine atoms, it is obtained as the sum of the values obtained by the following formula (1) for each repeating unit containing fluorine atoms.
Formula (1): _YA = a x b/100
_YA : Number of fluorine atoms contained in the hydrophobic resin a: Number of fluorine atoms in the repeating units containing fluorine atoms b: Content of repeating units containing fluorine atoms with respect to all repeating units in the hydrophobic resin (mol %)

The hydrophobic resin preferably contains at least one group selected from (x) and (y) shown below, and more preferably contains a repeating unit containing a group selected from (y).
Moreover, (x) and (y) shown below may contain the above-described hydrophobic group.
(x) an acid group (y) a group that decomposes under the action of an alkaline developer to increase its solubility in the alkaline developer (hereinafter also referred to as a polarity conversion group)

The acid group (x) includes a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl ) imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, and tris(alkylsulfonyl) A methylene group etc. are mentioned.
As the acid group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group)
, a sulfonimide group, or a bis(alkylcarbonyl)methylene group are preferred.

The group (y) that decomposes under the action of an alkaline developer to increase the solubility in the alkaline developer includes, for example, a lactone group, a carboxyester group (-COO- or -OCO-), an acid anhydride group (-CO -O-CO-), acid imide group (-NHCONH-), carboxythioester group (-COS- or -SCO-), carbonate group (-O-CO-O-)
, a sulfate ester group (--OSO ₂ O--), a sulfonate ester group (--SO ₂ O-- or --OSO _2-- ) and the like, and a lactone group or a carboxy ester group (--COO-- or --OCO-- ) is preferred, and a carboxyester group (-COO- or -OCO-) is more preferred.

Examples of the repeating unit containing the group selected from (y) include (1) a repeating unit in which the group selected from (y) is directly bonded to the main chain of the resin (e.g., acrylic acid ester and methacrylic acid and (2) a repeating unit in which the group selected from (y) above is bonded to the main chain of the resin via a linking group.
As the repeating unit having a lactone group, for example, the same repeating unit as the repeating unit having a lactone structure described in the section of the resin P can be mentioned.

The repeating unit containing a group selected from (y) above is preferably in the form of (2) described above, and more preferably a repeating unit represented by the following general formula (7).

In general formula (7), Z ₁ represents a halogen atom, a hydrogen atom, an alkyl group, or a cycloalkyl group.
The halogen atom represented by Z ₁ includes, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
The alkyl group represented by Z ₁ includes alkyl groups having 1 to 12 carbon atoms. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1-6, more preferably 1-3. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 5 to 15 carbon atoms.

L ₁ represents an (n+1)-valent linking group.
The (n+1)-valent linking group represented by L ₁ is not particularly limited, and examples thereof include a divalent or higher aliphatic hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom.
Examples of the heteroatoms include nitrogen atoms, oxygen atoms, and sulfur atoms.
A heteroatom may be included in the form of a linking group such as —O—, —S—, —SO ₂ —, —NR ^A —, —CO—, or a combination of two or more of these. R ^A represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
As the divalent or higher aliphatic hydrocarbon group having 1 to 20 carbon atoms which may contain a heteroatom, for example, a linear or branched chain having 1 to 20 carbon atoms which may contain a heteroatom An alkylene group and a cycloalkylene group can be mentioned, and a linear or branched alkylene group having 1 to 10 carbon atoms is preferred.

X ₁ represents a group represented by *-Y ₁ -R ₁ . Y ₁ above represents -CO-O- or -O-CO-. The above * represents a binding position.

R ₁ above represents an electron-withdrawing group.
The electron-withdrawing group is not particularly limited, for example, an alkyl group having 1 to 10 carbon atoms substituted with at least one fluorine atom (either linear or branched) or cyclo Examples include alkyl groups, and specific examples include -CF ₃ , -CF ₂ CF ₃ , -CH ₂ CF ₃ , -CHFCF ₃ and -CH(CF ₃ ) ₂ . Among them, —CH(CF ₃ ) ₂ is preferable as the electron-withdrawing group in terms of better film thickness uniformity.

n represents a positive integer.
n is not particularly limited as long as it is 1 or more, and its upper limit is 10, for example.
In addition, when n is 2 or more, _a plurality of X1's may be the same or different.

When the hydrophobic resin contains a repeating unit containing a group selected from (y) above, the content thereof is preferably 1 to 100 mol%, preferably 3 to 98 mol%, based on the total repeating units in the hydrophobic resin. is more preferred, and 5 to 95 mol % is even more preferred.

When the hydrophobic resin contains a repeating unit containing a fluorine atom, the content thereof is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, more preferably 30 to 100 mol%, based on the total repeating units in the hydrophobic resin. 95 mol % is more preferred.
Further, when the hydrophobic resin contains repeating units containing silicon atoms, the content thereof is preferably 10 to 100 mol %, more preferably 20 to 100 mol %, based on the total repeating units in the hydrophobic resin.

The hydrophobic resin contains the repeating unit represented by the above-described general formula (7) and a repeating unit other than the repeating unit represented by the general formula (7) in terms of superior film surface uniformity. is preferred.
Repeating units other than the repeating unit represented by the general formula (7) include a repeating unit containing a group selected from the above (y) and containing the above-described hydrophobic group (in other words, the above-described alkali A repeating unit having a group that is decomposed by the action of a developer to increase the solubility in an alkaline developer and containing the above-mentioned hydrophobic group) is preferable, and contains a group selected from the above (y) and a linear or branched alkyl group or cycloalkyl group having 6 or more carbon atoms, an aryl group having 9 or more carbon atoms, an aralkyl group having 10 or more carbon atoms, and at least one carbon atom of 3 or more One or more groups selected from the group consisting of an aryl group substituted with a linear or branched alkyl group and an aryl group substituted with at least one cycloalkyl group having 5 or more carbon atoms It is preferably a repeating unit containing
In addition, it is preferable that repeating units other than the repeating unit represented by the general formula (7) do not contain a fluorine atom.
When the hydrophobic resin contains a repeating unit represented by the general formula (7) and other repeating units other than the repeating unit represented by the general formula (7), the repeating unit represented by the general formula (7) The unit content is preferably 95 mol % or less, more preferably 90 mol % or less, and even more preferably 85 mol % or less, relative to all repeating units in the hydrophobic resin. The lower limit is not particularly limited, and is, for example, 10 mol % or more, more preferably 30 mol % or more.

The weight average molecular weight of the hydrophobic resin in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.

The total content of residual monomers and/or oligomer components contained in the hydrophobic resin is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. Further, the dispersity (Mw/Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

As the hydrophobic resin, known resins can be appropriately selected and used either singly or as a mixture thereof. For example, known resins disclosed in paragraphs [0451] to <0704> of US Patent Application Publication No. 2015/0168830A1 and paragraphs <0340> to <0356> of US Patent Application Publication No. 2016/0274458A1 are used. It can be suitably used as a hydrophobic resin. Further, the repeating units disclosed in paragraphs [0177] to <0258> of US Patent Application Publication No. 2016/0237190A1 are also preferable as repeating units constituting the hydrophobic resin.

Preferred examples of monomers corresponding to repeating units constituting the hydrophobic resin are shown below.

Hydrophobic resin may be used individually by 1 type, and may use 2 or more types.
It is also preferable to use a mixture of two or more hydrophobic resins having different surface energies from the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure.
When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin in the composition of the present invention (if it contains more than one, the total content) is the total solid content in the composition of the present invention 0.1 to 12.0% by mass is preferable, 0.2 to 10.0% by mass is more preferable, and 0.3 to 10.0% by mass is more preferable.

〔solvent〕
The composition of the invention may contain a solvent.
A known resist solvent can be appropriately used in the composition of the present invention. For example, paragraphs <0665>-<0670> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0210>-<0235> of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1 Known solvents disclosed in paragraphs <0424> to [0426] of the specification and paragraphs [0357] to <0366> of US Patent Application Publication No. 2016/0274458A1 can be suitably used.
Solvents that can be used in preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), Organic solvents such as monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates can be mentioned.

As the organic solvent, a mixed solvent in which a solvent having a hydroxyl group in its structure and a solvent having no hydroxyl group are mixed may be used.
As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the above-described exemplary compounds can be appropriately selected. ), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate are more preferred. As the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may have a ring, cyclic lactone, or alkyl acetate are preferable. Glycol monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate are more preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate , cyclohexanone, cyclopentanone, or 2-heptanone are more preferred. Propylene carbonate is also preferred as the solvent having no hydroxyl group.
The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and 20/80 to 60/40. More preferred. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable from the viewpoint of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate. In this case, the solvent may be a single solvent of propylene glycol monomethyl ether acetate, or a mixed solvent of two or more kinds including propylene glycol monomethyl ether acetate.

The solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, even more preferably 2.0 to 5.3% by mass. In other words, when the composition contains a solvent, the content of the solvent in the composition is preferably adjusted so as to satisfy the preferred range of solid content concentration. The solid content concentration is the mass percentage of the mass of other resist components excluding the solvent relative to the total mass of the composition.
By setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity, coating property or film forming property is improved, resist film (actinic ray sensitive or radiation sensitive) made of the composition of the present invention film) can be adjusted.

[Surfactant]
The composition of the invention may also contain a surfactant.
The surfactant is preferably a fluorine-based and/or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both fluorine atoms and silicon atoms). .

When the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, it is easy to obtain a pattern with good sensitivity and resolution, good adhesion, and few development defects.
Fluorinated and/or silicon-based surfactants include surfactants described in paragraph <0276> of US Patent Application Publication No. 2008/0248425.
Also, surfactants other than the fluorine-based and/or silicon-based surfactants described in paragraph <0280> of US Patent Application Publication No. 2008/0248425 may be used.

One type of surfactant may be used alone, or two or more types may be used.
When the composition of the present invention contains a surfactant, the content of the surfactant (if more than one is included, the total content) is 0.0001 to 2% by mass with respect to the total solid content of the composition. is preferred, and 0.0005 to 1% by mass is more preferred.
On the other hand, if the content of the surfactant is 10 ppm by mass (parts per million) or more relative to the total solid content of the composition, the uneven surface distribution of the hydrophobic resin increases. As a result, the surface of the resist film can be made more hydrophobic, and the followability to water during immersion exposure is improved.

[Other additives]
The composition of the present invention further contains resins other than those mentioned above, acid multipliers, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, dissolution accelerators, and the like. good too.

<Preparation method>
The composition of the present invention is preferably used by dissolving the above components in a given organic solvent (preferably the above mixed solvent), filtering the mixture, and coating it on a given support (substrate).
The pore size of the filter used for filtration is preferably 0.1 µm or less, more preferably 0.05 µm or less, and even more preferably 0.03 µm or less. When the composition has a high solid content concentration (for example, 25% by mass or more), the pore size of the filter used for filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. The filter is preferably a polytetrafluoroethylene, polyethylene, or nylon filter. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (JP 2002-62667), cyclic filtration may be performed, and multiple types of filters are connected in series or in parallel. Filtration may be performed by connecting to Also, the composition may be filtered multiple times. Furthermore, before and after filtering, the composition may be subjected to a degassing treatment or the like.

<Application>
The composition of the present invention relates to an actinic ray- or radiation-sensitive resin composition that reacts with irradiation of actinic rays or radiation to change its properties. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as IC (Integrated Circuit), circuit board manufacturing such as liquid crystals or thermal heads, manufacturing of imprint mold structures, other photofabrication processes, or The present invention relates to an actinic ray- or radiation-sensitive resin composition used for producing a lithographic printing plate or an acid-curable composition. The pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode forming process, a rewiring forming process, MEMS (Micro Electro Mechanical Systems), and the like.

[Pattern formation method, resist film]
The present invention also relates to a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition. The pattern forming method of the present invention will be described below. The resist film (actinic ray-sensitive or radiation-sensitive film) of the present invention will also be explained together with the explanation of the pattern forming method.

The pattern forming method of the present invention comprises
(i) A step of forming a resist film (actinic ray-sensitive or radiation-sensitive film) on a support using the actinic ray-sensitive or radiation-sensitive resin composition described above (resist film forming step (film-forming step) )
,
(ii) a step of exposing the resist film (irradiating actinic rays or radiation) (exposure step), and
(iii) A step of developing the exposed resist film using a developer (developing step).

The pattern forming method of the present invention is not particularly limited as long as it includes the above steps (i) to (iii), and may further include the following steps.
In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may be liquid immersion exposure.
The pattern forming method of the present invention preferably includes (iv) a pre-heating (PB: PreBake) step before the (ii) exposure step.
The pattern forming method of the present invention preferably includes (v) a post exposure bake (PEB) step after (ii) the exposure step and (iii) before the development step.
The pattern forming method of the present invention may include (ii) the exposure step multiple times.
The pattern forming method of the present invention may include (iv) the preheating step multiple times.
The pattern forming method of the present invention may include (v) the post-exposure heating step multiple times.

In the pattern forming method of the present invention, the above-described (i) resist film forming step (film forming step)
, (ii) the exposure step, and (iii) the development step can be performed by a generally known method.

From the viewpoint of improving resolution, the thickness of the resist film is preferably 110 nm or less, more preferably 95 nm or less.
If necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film) may be formed between the resist film and the support. As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used.
A protective film (top coat) may be formed on the resist film. A known material can be appropriately used as the protective film. For example, US2007/0178407, US2008/0085466, US2007/0275326, US2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016/157988A can be preferably used. The protective film-forming composition preferably contains the acid diffusion control agent described above.
A protective film may be formed on the resist film containing the hydrophobic resin described above.

The support is not particularly limited, and a substrate generally used in the manufacturing process of semiconductors such as ICs, the manufacturing process of circuit boards such as liquid crystals or thermal heads, and the lithography process of other photofabrication is used. can. Specific examples of the support include inorganic substrates such as silicon, SiO ₂ , and SiN.

The heating temperature is preferably 70 to 130° C., more preferably 80 to 120° C. in both the (iv) pre-heating step and (v) post-exposure heating step.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds in both (iv) the preheating step and (v) the post-exposure heating step.
Heating can be performed by means provided in the exposure device and the development device, and may be performed using a hot plate or the like.

The wavelength of the light source used in the exposure process is not limited, but examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Among these, far ultraviolet light is preferred, and its wavelength is preferably 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser ₍ 157 nm), X-ray, EUV (13 nm), electron beam, etc. are preferable, and KrF excimer laser, ArF excimer laser, EUV or electron beam is more preferred.

(iii) In the developing step, an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer) may be used.

As the alkaline developer, quaternary ammonium salts such as tetramethylammonium hydroxide are usually used, but in addition to this, alkaline aqueous solutions such as inorganic alkalis, primary to tertiary amines, alcohol amines, and cyclic amines are also used. Available.
Further, the alkaline developer may contain appropriate amounts of alcohols and/or surfactants. The alkali concentration of the alkali developer is usually 0.1 to 20 mass %. The pH of the alkaline developer is usually 10-15.
The time for developing with an alkaline developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.

The organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. is preferred.

Ketone solvents include, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl. ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butane butyl acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, butyl propionate and the like.

As alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents, the solvents disclosed in paragraphs <0715> to <0718> of US Patent Application Publication No. 2016/0070167A1 can be used.

A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass, relative to the total amount of the developer. % is particularly preferred.

The developer may contain an appropriate amount of a known surfactant as required.

The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, relative to the total amount of the developer.

The organic developer may contain an acid diffusion control agent.

As the development method, for example, a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), a method of raising the developer on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle method), There is a method of spraying the developer onto the surface of the substrate (spray method), and a method of continuously ejecting the developer while scanning the developer ejection nozzle onto the substrate rotating at a constant speed (dynamic dispensing method). mentioned.

A step of developing using an alkaline aqueous solution (alkali developing step) and a step of developing using a developer containing an organic solvent (organic solvent developing step) may be combined. As a result, the pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern can be formed.

(iii) It is preferable to include a step of washing with a rinse solution (rinse step) after the development step.

Pure water, for example, can be used as the rinsing solution used in the rinsing step after the developing step using the alkaline developer. The pure water may contain an appropriate amount of surfactant. Moreover, after the developing process or the rinsing process, a process of removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid may be added. Further, after rinsing or supercritical fluid treatment, heat treatment may be performed to remove moisture remaining in the pattern.

The rinsing solution used in the rinsing step after the developing step using the developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a common solution containing an organic solvent can be used. As the rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. is preferred.
Specific examples of the hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, and ether-based solvent include the same solvents as those described for the developer containing an organic solvent.
As the rinse solution used in the rinse step in this case, a rinse solution containing a monohydric alcohol is more preferable.

Monohydric alcohols used in the rinse step include linear, branched, or cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1 -heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methylisobutylcarbinol.
It is also preferred that the monohydric alcohol has 5 or more carbon atoms, examples of which are 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol. , and methyl isobutyl carbinol.

A plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.
The water content in the rinse solution used in the rinse step after the development step using the developer containing an organic solvent is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. If the water content is 10% by mass or less, good developing properties can be obtained.
A rinse solution after a development step using a developer containing an organic solvent may contain an appropriate amount of a surfactant.

In the rinsing step, the developed substrate is washed with a rinsing liquid. The method of the cleaning treatment is not particularly limited, but for example, a method of continuously discharging the rinse solution onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a bath filled with the rinse solution for a certain period of time. method (dip method), or a method of spraying a rinse liquid onto the substrate surface (spray method). Among them, a method of performing cleaning treatment by a spin coating method, rotating the substrate at a rotation speed of 2,000 to 4,000 rpm after cleaning, and removing the rinsing liquid from the substrate is preferable. It is also preferable to include a heating step (Post Bake) after the rinsing step. This heating process removes the developer and rinse remaining between the patterns and inside the patterns. In the heating step after the rinsing step, the heating temperature is usually 40 to 160°C, preferably 70 to 95°C, and the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

Various materials used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the pattern forming method of the present invention (e.g., resist solvent, developer, rinse, composition for forming an antireflection film, or top The coat-forming composition, etc.) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the various materials described above is preferably 1 mass ppm or less, more preferably 100 mass ppt (parts per trillion) or less, even more preferably 10 mass ppt or less, and substantially free of them. (below the detection limit of the measuring device) is particularly preferred.

As a method for removing impurities such as metals from the above various materials, for example, filtration using a filter can be mentioned. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. A filter pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel and used. When multiple types of filters are used, filters with different pore sizes and/or materials may be used in combination. Further, various materials may be filtered multiple times, and the process of filtering multiple times may be a circulation filtration process. As the filter, a filter with reduced extractables as disclosed in Japanese Patent Application Publication No. 2016-201426 (JP 2016-201426) is preferable.
In addition to filter filtration, an adsorbent may be used to remove impurities, or filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of metal adsorbents include materials disclosed in Japanese Patent Application Publication No. 2016-206500 (JP 2016-206500).
In addition, as a method for reducing impurities such as metals contained in the various materials, selecting raw materials with a low metal content as raw materials constituting various materials, performing filter filtration on raw materials constituting various materials, Alternatively, distillation may be performed under conditions in which contamination is suppressed as much as possible by, for example, lining the inside of the apparatus with Teflon (registered trademark). It is also preferable to apply glass lining to all processes of manufacturing equipment for synthesizing various materials (binders, photo-acid generators, etc.) for resist components in order to reduce metals to the ppt order. Preferred conditions for filtering the raw materials constituting various materials are the same as those described above.

In order to prevent contamination of impurities, the above various materials are described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (JP 2015-123351), and Japan. It is preferably stored in a container described in Patent Application Publication No. 2017-13804 (Japanese Patent Application Laid-Open No. 2017-13804).

A method for improving surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention. As a method for improving the surface roughness of the pattern, for example, there is a method of treating the pattern with hydrogen-containing gas plasma disclosed in US Patent Application Publication No. 2015/0104957. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Application Publication No. 2004-235468), US Patent Application Publication No. 2010/0020297, and Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.
In addition, the pattern formed by the above method is, for example, Japanese Patent Application Publication No. 1991-270227 (JP-A-3-270227), and US Patent Application Publication No. 2013/0209941. It can be used as the core of the process.

[Method for manufacturing electronic device]
The present invention also relates to a method of manufacturing an electronic device, including the pattern forming method described above. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted in electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.). be done.

The present invention will be described in more detail based on examples below. Materials, usage amounts, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the examples shown below.
In Examples 1, 2, 4, 8, 10 to 12, 14, 16, 19, 22 to 26, 28 and 29, "Example" should be read as "Reference Example".

<Synthesis Example: Monomer Synthesis)>

Pinacol (37.8 g) and tetrahydrofuran (400 mL) were stirred at room temperature, and after the pinacol was completely dissolved, the mixture was cooled to 0°C and stirred. To this, n-butyllithium (nBuLi) (1.6 mol/L hexane solution) was added dropwise while maintaining the internal temperature at 15°C, and after the dropwise addition, the mixture was further stirred at 0°C for 30 minutes to prepare a pinacol-tetrahydrofuran solution. .
Separately, methacrylic acid chloride (36.8 g) and tetrahydrofuran (400 mL) were stirred at 0°C, and the pinacol-tetrahydrofuran solution was added dropwise so as to maintain the internal temperature at 15°C or lower. After completion of dropping, the reaction solution was warmed to room temperature and stirred for 30 minutes.
After that, the reaction solution was poured into 400 mL of saturated sodium bicarbonate aqueous solution, and tetrahydrofuran was distilled off under reduced pressure. The resulting aqueous solution was extracted three times with 250 mL of ethyl acetate and dried over sodium sulfate. After drying, the ethyl acetate solution was filtered, and the filtrate was concentrated under reduced pressure to obtain 40.2 g of a crude product.
This crude product was column-purified with 600 g of silica gel and a developing solution of hexane/ethyl acetate=6/1 (vol) to obtain 33.3 g (56% yield) of the desired monomer. ¹ H-NMR, 400 MHz, δ ((CDCl ₃ ) ppm: 1.24 (6H, s), 1.54 (6H, s), 1.92-1.95 (3H, m), 3.44 ( 1H, bs), 5.52-5.58 (1H, m), 6.02-6.07 (1H, m).

<Synthesis Example: Synthesis of Resin)>
80.78 parts by mass of cyclohexanone was heated to 80° C. under a nitrogen stream. While stirring this liquid, 17.78 parts by mass of a monomer represented by the following structural formula D-1, 11.18 parts by mass of a monomer represented by the following structural formula D-2, and the following structural formula E-1 A mixed solution of 11.78 parts by weight of the represented monomer, 150.03 parts by weight of cyclohexanone, and 2.76 parts by weight of dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] It dripped over time. After the dropwise addition was completed, the mixture was further stirred at 80° C. for 2 hours. After allowing the reaction solution to cool, it was reprecipitated with a large amount of methanol/water (mass ratio of 9:1) and filtered. Parts by mass were obtained.

The weight average molecular weight (Mw: in terms of polystyrene) obtained from GPC (developing solvent: tetrahydrofuran) of the obtained resin A-1 was Mw=8000, and the degree of dispersion was Mw/Mn=1.67. The composition ratio (molar ratio; correspondence from left to right) measured by ¹³ C-NMR (nuclear magnetic resonance) was 40/30/30 (mol %).

Resins A-2 to A-22 described later, which are acid-decomposable resins, were synthesized by performing the same operations as in the above synthesis examples.

<Acid-decomposable resin>
The structures of the acid-decomposable resins (A-1 to A-22, B-1 and B-2) used are shown below.
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (in terms of polystyrene). Also, the resin composition ratio (mol% ratio) was measured by ¹³ C-NMR (nuclear magnetic resonance).

In addition, the unit of the content ratio of each repeating unit of the resin is mol%.

A-1 to A-22 above have a repeating unit represented by general formula (P1). Regarding the repeating unit represented by the general formula (P1) in A-1 to A-22 above, the site (degradation site (site represented by the above general formula (P1-D)) that is eliminated by an acid decomposition reaction) is shown in Table 1 below.

<Photoacid generator>
The structures of the photoacid generators (PAG-1 to PAG-12) used are shown below.

<Acid diffusion control agent>
The structures of the acid diffusion control agents (N-1 to N-6) used are shown below.

PAG-1 to PAG-12, N-5 and N-6 are shown below with the pKa of the acid generated from them (generated acid).

The pKa values of the conjugate acids of N-1 to N-4 are shown below.

<Hydrophobic resin>
The structures of the hydrophobic resins (1b, 2b) used are shown below.
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (in terms of polystyrene). Also, the composition ratio (mol% ratio) of the resin was measured by ¹³ C-NMR.

In addition, the unit of the content ratio of each repeating unit of the resin is mol %.

<Surfactant>
The surfactants used are shown below.
W-1: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

<Solvent>
The solvents used are shown below.
SL-1: propylene glycol monomethyl ether acetate (PGMEA)
SL-2: propylene glycol monomethyl ether (PGME)
SL-3: cyclohexanone SL-4: γ-butyrolactone

[Preparation of resist composition]
Each component shown in Tables 4 and 5 was mixed so that the solid content concentration was 3% by mass. Then, the resulting mixture was filtered through a polyethylene filter with a pore size of 0.03 μm to prepare an actinic ray-sensitive or radiation-sensitive resin composition (resist composition). In addition, solid content means all the components other than a solvent.

[Pattern formation and evaluation]
-ArF immersion exposure: formation of positive pattern-
An organic antireflection film forming composition ARC29SR (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. A resist composition shown in Table 4 was coated on the obtained antireflection film and baked (PB: Prebake) at 100° C. for 60 seconds to form a resist film having a thickness of 85 nm.
Using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection), the resulting wafer was scanned with a 1:1 line width of 44 nm. It was exposed through a 6% halftone mask with a 1 line and space pattern. Ultrapure water was used as the immersion liquid. Then, it was heated at 100° C. for 60 seconds (PEB: Post Exposure Bake). Next, development was performed by puddle with a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds, and the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds to obtain a 1:1 line and space with a line width of 44 nm. formed a pattern.

<Evaluation of sensitivity>
The optimum exposure dose for reproducing a 1:1 line-and-space mask pattern with a line width of 44 nm was defined as sensitivity (E _opt ) (mJ/cm ² ).

<Evaluation of exposure latitude (EL)>
Based on the determined optimum exposure (E _opt ), the exposure was then determined so that the line width was within ±10% of the target value of 44 nm (ie, 39.6 nm and 48.4 nm).
The exposure latitude (EL) defined by the following equation was calculated using the obtained exposure value.
EL (%) = [[(exposure amount at which the line width is 48.4 nm) - (exposure amount at which the line width is 39.6 nm)]/E _opt ] × 100
The larger the EL value, the smaller the change in line width due to the change in the exposure amount, indicating that the EL performance of the resist film is good.

<Evaluation of Roughness Performance (Line Width Roughness; LWR)>
The resulting 1:1 line-and-space pattern with a line width of 44 nm was observed from above the pattern with a length-measuring scanning electron microscope (SEM, Hitachi Ltd. S-9380II). For the range, the line width was measured at 50 points, the standard deviation of the measurement variation was determined, and 3σ was calculated. A smaller value indicates better performance.

-ArF immersion exposure: formation of negative pattern-
An organic antireflection film ARC29SR (manufactured by Brewer Science) was coated on a silicon wafer and baked at 205° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. was applied and baked at 100° C. for 60 seconds to form a resist film with a thickness of 90 nm.
Using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, C-Quad, outer sigma 0.98, inner sigma 0.89, XY deflection), the X direction is a mask size of 45 nm, the pitch is 90 nm, and the Y Exposure was performed through a mask pattern (6% halftone) for pattern formation with a mask size of 60 nm and a pitch of 120 nm in the direction. Ultrapure water was used as the immersion liquid. After heating at 100° C. for 60 seconds, the film was developed with butyl acetate, which is an organic developer, for 30 seconds and spin-dried to obtain a resist pattern (hole pattern).

<Evaluation of sensitivity>
The hole size is observed with a length-measuring scanning electron microscope (SEM, Hitachi Ltd. S-9380II), and the optimum exposure amount when resolving a hole pattern with an average hole size of 45 nm in the X direction is measured as sensitivity (E _opt ). (mJ/cm ² ).

<Evaluation of exposure latitude (EL)>
Based on the determined optimum exposure dose (E _opt ), the exposure dose at which the hole size was ±10% of the target value of 45 nm (that is, 40.5 nm and 49.5 nm) was determined. Then, an exposure latitude (EL) defined by the following equation was calculated. The larger the EL value, the smaller the change in performance due to the change in exposure amount, which is good.
[EL (%)]=[(exposure amount at which hole size is 40.5 nm)−(exposure amount at which hole size is 49.5 nm)]/E _opt ×100

<Evaluation of Pattern Dimension Uniformity (CDU)>
In one shot exposed with the optimum exposure dose, the hole size in the X direction of 25 arbitrary holes (that is, a total of 500 holes) was measured in each of 20 regions with an interval of 1 μm from each other. , and 3σ was calculated. A smaller value indicates less dimensional variation and better performance.

[Preparation of resist composition]
Each component shown in Table 6 was dissolved in a solvent to prepare a solution with a solid concentration of 1.6% by mass. Then, the obtained solution was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare an actinic ray-sensitive or radiation-sensitive resin composition (resist composition).

[Method of forming a resist pattern]
-EUV exposure: formation of negative pattern or positive pattern-
A resist composition shown in Table 6 is applied on a silicon wafer having AL412 (manufactured by Brewer Science) as a lower layer film, and baked at 100 ° C. for 60 seconds (PB: Prebake) to obtain a resist with a film thickness of 30 nm. A film was formed.
Using an EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), pattern irradiation was performed on the silicon wafer having the obtained resist film. rice field. As the reticle, a mask having a line size of 20 nm and a line:space ratio of 1:1 was used.
Then, it was heated at 105° C. for 60 seconds (PEB: Post Exposure Bake). Next, development is performed by paddle for 30 seconds with a negative developer (butyl acetate) or a positive developer (2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution), followed by development with a negative rinse (FIRM Extreme 10 (AZEM product)) or a positive rinse solution (pure water). After that, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds to form a 1:1 line-and-space pattern with a line width of 20 nm.

<Evaluation of sensitivity>
Using a scanning electron microscope (SEM: CG-4100 manufactured by Hitachi High-Technologies Corporation), the exposure dose for reproducing a 1:1 line and space mask pattern with a line width of 20 nm was obtained, and this was used as the optimum exposure. The quantity E _opt .

<Evaluation of exposure latitude (EL)>
Next, the exposure amount was determined so that the line width was within ±10% of the target value of 20 nm (that is, 18 nm and 22 nm).
The exposure latitude (EL) defined by the following equation was calculated using the obtained exposure value.
The larger the EL value, the smaller the change in line width due to the change in the exposure amount, indicating that the EL performance of the resist film is good.
EL (%) = [[(exposure amount at which the line width is 22 nm) - (exposure amount at which the line width is 18 nm)]/E _opt ] × 100

<Evaluation of Line Edge Roughness (LER)>
When observing the line-and-space resist pattern resolved at the optimum exposure dose in sensitivity evaluation, observe from the top of the pattern with a scanning electron microscope (SEM: Scanning Electron Microscope (CG-4100 manufactured by Hitachi High-Technologies Corporation)). At that time, the distance from the center of the pattern to the edge was observed at an arbitrary point, and the measurement variation was evaluated by 3σ. A smaller value indicates better performance.

As can be seen from the results in Tables 4 to 6, the compositions of the present invention were excellent in sensitivity and EL when forming ultrafine patterns, small in LWR and LER, and excellent in CDU.

Claims (9)

A sensitizer containing a resin P having a repeating unit represented by the following general formula (P1) in an amount of 30% by mass or more based on the total solid content and a crosslinking agent of 10% by mass or less based on the total solid content. A light-sensitive or radiation-sensitive resin composition,
The resin P further includes a repeating unit K2 having a polar group, and the repeating unit K2 is a repeating unit different from the repeating unit represented by the general formula (P1),
the polar group contained in the repeating unit K2 is at least one group selected from the group consisting of a lactone group, a sultone group, a sultam group, a carboxylic acid group, and a cyclic carbonate group;
further comprising a photoacid generator A,
The photoacid generator A is a photoacid generator Aw in which the pKa of the generated acid is -1.40 or more,
The content of the photoacid generator Aw is 16 to 35% by mass with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition,
A basic compound (DA), a basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation, and generates an acid having a pKa greater than that of the acid generated from the photoacid generator Aw by 1.00 or more. a compound (DC), a compound (DD) having a nitrogen atom and having a group that leaves under the action of an acid, and an onium salt compound (DE) having a nitrogen atom in the cation moiety. Actinic ray or radiation sensitive resin composition.

In general formula (P1),
R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
L ^p represents a single bond or a polyvalent linking group.
R ^p and L ^p may combine to form a ring structure.
X ^p represents O, S, or NR ^N1 . ^RN1 represents a hydrogen atom or a monovalent organic group.
Y ^p represents O, S, or NR ^N2 . ^RN2 represents a hydrogen atom or a monovalent organic group.
Z ^p represents a hydrogen atom.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl groups, the cycloalkenyl groups, the alkynyl groups and the cycloalkynyl groups may have heteroatoms between the carbon-carbon bonds. However, ^Rp3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and ^Rp4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit represented by the general formula (P1) is a repeating unit represented by the following general formula (P2).

In the general formula (P2),
R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
L ^p represents a single bond or a polyvalent linking group.
R ^p and L ^p may combine to form a ring structure.
Y ^p represents O, S, or NR ^N2 . ^RN2 represents a hydrogen atom or a monovalent organic group.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl groups, the cycloalkenyl groups, the alkynyl groups and the cycloalkynyl groups may have heteroatoms between the carbon-carbon bonds. However, ^Rp3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and ^Rp4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure. 3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit represented by the general formula (P1) is a repeating unit represented by the following general formula (P3).

In general formula (P3),
R ^p represents a hydrogen atom, a halogen atom, or a monovalent organic group.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl groups, the cycloalkenyl groups, the alkynyl groups and the cycloalkynyl groups may have heteroatoms between the carbon-carbon bonds. However, ^Rp3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and ^Rp4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure. Claims 1 to 3, wherein the resin P further comprises a repeating unit K1 having an acid-decomposable group, and the repeating unit K1 is a repeating unit different from the repeating unit represented by the general formula (P1). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the total atomic weight of the sites represented by the following general formula (P1-D) in the general formula (P1) is 300 or less.

In the general formula (P1-D),
X ^p represents O, S, or NR ^N1 . ^RN1 represents a hydrogen atom or a monovalent organic group.
Z ^p represents a hydrogen atom.
R ^p1 and R ^p2 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group, and the alkyl group, the cycloalkyl group, the alkenyl group , the cycloalkenyl group, the alkynyl group, and the cycloalkynyl group may have a heteroatom between the carbon-carbon bonds. However, R ^p1 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group. R ^p2 does not represent a perfluoroalkyl group or a perfluorocycloalkyl group.
R ^p3 and R ^p4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, or an aryl group; The alkenyl groups, the cycloalkenyl groups, the alkynyl groups and the cycloalkynyl groups may have heteroatoms between the carbon-carbon bonds. However, ^Rp3 does not represent a perfluoroalkyl group or perfluorocycloalkyl group and ^Rp4 represents a perfluoroalkyl group or perfluorocycloalkyl group.
Any two of R ^p1 to R ^p4 may combine to form a ring structure.
* indicates the binding position with ^Yp . The actinic ray-sensitive or radiation-sensitive resin according to any one of claims 1 to 5, wherein the repeating unit contained in the resin P is a (meth)acrylate repeating unit or a repeating unit containing a phenolic hydroxyl group. Composition. A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6. A pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 8 .