JP6715375B2 - Positive resist composition and method for forming resist pattern - Google Patents

Description

The present invention relates to a positive resist composition, a resist pattern forming method, a photoreactive quencher and a polymer compound.

In the lithographic technique, for example, a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed to radiation such as light or an electron beam through a mask on which a predetermined pattern is formed. Then, a development process is performed to form a resist pattern having a predetermined shape on the resist film.
A resist material in which the exposed portion changes to a characteristic that dissolves in a developing solution is called a positive type, and a resist material in which the exposed portion changes to a characteristic that does not dissolve in a developing solution is called a negative type.
2. Description of the Related Art In recent years, in the manufacture of semiconductor devices and liquid crystal display devices, pattern miniaturization is rapidly progressing due to advances in lithography technology.

As a resist material capable of forming a pattern with a fine dimension, a chemically amplified resist composition conventionally containing a base material component whose solubility in a developing solution is changed by the action of an acid and an acid generator component which generates an acid upon exposure. Things are used. When a resist film formed using such a resist composition is selectively exposed at the time of forming a resist pattern, an acid is generated from the acid generator component in the exposed portion. In the case of using a resist material in which the exposed portion is changed to have a property of dissolving in a developing solution, the polarity of the exposed portion is changed by the action of the acid, and the solubility in the developing solution is changed. Is formed.

A resist pattern having a fine dimension is required to have various lithographic characteristics such as reduced linewise roughness (LWR) and good sensitivity and resolution. Various studies have been conducted on the acid generator component in order to improve the lithographic properties.
For example, Patent Document 1 describes a resist composition that can reduce LWR and probe defects by employing an acid generator component containing a predetermined amount of fluorine atoms.
Further, Patent Document 2 describes a resist composition capable of improving lithographic properties such as line edge roughness by employing an acid generator component having a triphenylsulfonium skeleton containing a predetermined amount of fluorine atoms. ..

JP, 2011-253017, A JP 2005-91976 A

With further advances in lithography technology and further miniaturization of resist patterns in the future, resist materials are required to have various improvements in lithography characteristics.
When the conventional acid generators described in Patent Documents 1 and 2 are used, various lithographic properties still have room for improvement.
The present invention has been made in view of the above circumstances, and provides a resist composition capable of forming a resist pattern having excellent lithographic properties, and a resist pattern forming method using the resist composition. It is an issue.

A first aspect of the present invention is a positive resist composition that generates an acid upon exposure to light and has increased solubility in an alkali developing solution due to the action of an acid. And a compound (m) represented by the following general formula (m0) are contained in the positive resist composition.

［一般式（ｍ０）中、
Ｚ^０１〜Ｚ^０４は、それぞれ独立に電子吸引性の置換基であり、
Ｒｂ^２１及びＲｂ^２２は、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基であり（但し、Ｒｂ^２１及びＲｂ^２２が有していてもよい置換基に電子吸引性の置換基は含まないものとする。）、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数であり、
Ｘ０^-は有機アニオンである。］

[In the general formula (m0),
Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing substituent,
Rb ²¹ and Rb ²² are each independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² may have a substituent Does not include electron-withdrawing substituents.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3,
X0 ^- is an organic anion. ]

A second aspect of the present invention is a positive resist composition which generates an acid upon exposure and whose solubility in a developing solution is increased by the action of an acid, wherein the solubility in a developing solution is increased by the action of an acid. A base material component (A), the base material component (A) contains a resin component (A2), and the resin component (A2) is represented by the following general formula (a6-1): A positive resist composition containing a polymer compound having a structural unit (a6) derived from

［一般式（ａ６−１）中、
Ｚ^０１〜Ｚ^０４は、それぞれ独立に電子吸引性の置換基であり、
Ｒｂ^２１及びＲｂ^２２は、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基であり（但し、Ｒｂ^２１及びＲｂ^２２が有していてもよい置換基に電子吸引性の置換基は含まないものとする。）、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数である。
Ｘ１１−１⁻は、一般式（ａ６−１−１）〜（ａ６−１−３）のいずれかで表される有機アニオンである。一般式（ａ６−１−１）〜（ａ６−１−３）中、Ｒｂ^２０１は、置換基を有していてもよい鎖状のアルケニル基であり、
Ｒｂ^２０４は、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基または置換基を有していてもよい鎖状のアルケニル基であり、
Ｒｂ^２０５は、置換基を有していてもよい鎖状のアルケニル基である。
Ｒｂ^２０６〜Ｒｂ^２０８は、それぞれ独立に、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基である（但し、Ｒｂ^２０６〜Ｒｂ^２０８の少なくとも１つは、置換基を有していてもよい鎖状のアルケニル基である）。
Ｒｂ^１０２は、フッ素原子または炭素数１〜５のフッ素化アルキル基である。Ｙｂ^１０１は、単結合または酸素原子を含む２価の連結基である。Ｖｂ^１０１〜Ｖｂ^１０３は、それぞれ独立に、単結合、アルキレン基、フッ素化アルキレン基、アリーレン基またはフッ素化アリーレン基である。Ｌｂ^１０１〜Ｌｂ^１０２は、それぞれ独立に、単結合または酸素原子である。Ｌｂ^１０３〜Ｌｂ^１０５は、それぞれ独立に、単結合、−ＣＯ−又は−ＳＯ_２−である。ｎ_１０１は０又は１である。］

[In general formula (a6-1),
Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing substituent,
Rb ²¹ and Rb ²² are each independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² may have a substituent Does not include electron-withdrawing substituents.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3.
X11-1 ^- is an organic anion represented by any one of formulas (a6-1-1) ~ (a6-1-3). In formulas (a6-1-1) to (a6-1-3), Rb ²⁰¹ is a chain alkenyl group which may have a substituent,
Rb ²⁰⁴ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent or a chain alkenyl group which may have a substituent,
Rb ²⁰⁵ is a chain alkenyl group which may have a substituent.
Rb ^{206 to} Rb ²⁰⁸ each independently represent a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent. (Wherein at least one of Rb ^{206 to} Rb ²⁰⁸ is a chain alkenyl group which may have a substituent).
Rb ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Yb ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. Vb ^{101 to} Vb ¹⁰³ are each independently a single bond, an alkylene group, a fluorinated alkylene group, an arylene group or a fluorinated arylene group. Lb ^{101 to} Lb ¹⁰² are each independently a single bond or an oxygen atom. Lb ^{103 to} Lb ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —. n ₁₀₁ is 0 or 1. ]

A third aspect of the present invention is a step of forming a resist film using the positive resist composition of the first or second aspect, a step of exposing the resist film, and a step of developing the resist film after the exposure. And a resist pattern forming method including a step of forming a resist pattern.

A fourth aspect of the present invention is a photoreactive quencher characterized by comprising a compound (md) represented by the following general formula (m0-d).

［一般式（ｍ０−ｄ）中、
Ｚ^０１〜Ｚ^０４は、それぞれ独立に電子吸引性の置換基であり、
Ｒｂ^２１及びＲｂ^２２は、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基であり（但し、Ｒｂ^２１及びＲｂ^２２が有していてもよい置換基に電子吸引性の置換基は含まないものとする。）、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数である。
Ｘ０⁻は、一般式（ｄ１−１）〜（ｄ１−３）のいずれかで表される有機アニオンである。
一般式（ｄ１−１）〜（ｄ１−３）中、Ｒｄ^１〜Ｒｄ^４は、それぞれ独立に、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、又は置換基を有していてもよい鎖状のアルケニル基である。ただし、式（ｄ１−２）中のＲｄ^２における、Ｓ原子に隣接する炭素原子にはフッ素原子は２つ以上結合していないものとする。Ｙｄ^１は単結合、又は２価の連結基である。］

[In the general formula (m0-d),
Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing substituent,
Rb ²¹ and Rb ²² are each independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² may have a substituent Does not include electron-withdrawing substituents.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3.
X0 ^- is an organic anion represented by any one of formulas (d1-1) ~ (d1-3).
In general formulas (d1-1) to (d1-3), Rd ^{1 to} Rd ⁴ each independently represent a cyclic group which may have a substituent, or a chain which may have a substituent. Is an alkyl group or a chain alkenyl group which may have a substituent. However, two or more fluorine atoms are not bonded to the carbon atom adjacent to the S atom in Rd ² in formula (d1-2). Yd ¹ is a single bond or a divalent linking group. ]

A fifth aspect of the present invention is a polymer compound having a structural unit derived from a compound represented by the following general formula (a6-1).

［一般式（ａ６−１）中、
Ｚ^０１〜Ｚ^０４は、それぞれ独立に電子吸引性の置換基であり、
Ｒｂ^２１及びＲｂ^２２は、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基であり（但し、Ｒｂ^２１及びＲｂ^２２が有していてもよい置換基に電子吸引性の置換基は含まないものとする。）、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数である。
Ｘ１１−１⁻は、一般式（ａ６−１−１）〜（ａ６−１−３）のいずれかで表される有機アニオンである。一般式（ａ６−１−１）〜（ａ６−１−３）中、Ｒｂ^２０１は、置換基を有していてもよい鎖状のアルケニル基であり、
Ｒｂ^２０４は、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基または置換基を有していてもよい鎖状のアルケニル基であり、
Ｒｂ^２０５は、置換基を有していてもよい鎖状のアルケニル基である。
Ｒｂ^２０６〜Ｒｂ^２０８は、それぞれ独立に、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基である（但し、Ｒｂ^２０６〜Ｒｂ^２０８の少なくとも１つは、置換基を有していてもよい鎖状のアルケニル基である）。
Ｒｂ^１０２は、フッ素原子または炭素数１〜５のフッ素化アルキル基である。Ｙｂ^１０１は、単結合または酸素原子を含む２価の連結基である。Ｖｂ^１０１〜Ｖｂ^１０３は、それぞれ独立に、単結合、アルキレン基、フッ素化アルキレン基、アリーレン基またはフッ素化アリーレン基である。Ｌｂ^１０１〜Ｌｂ^１０２は、それぞれ独立に、単結合または酸素原子である。Ｌｂ^１０３〜Ｌｂ^１０５は、それぞれ独立に、単結合、−ＣＯ−又は−ＳＯ_２−である。ｎ_１０１は０又は１である。］

[In general formula (a6-1),
Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing substituent,
Rb ²¹ and Rb ²² are each independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² may have a substituent Does not include electron-withdrawing substituents.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3.
X11-1 ^- is an organic anion represented by any one of formulas (a6-1-1) ~ (a6-1-3). In formulas (a6-1-1) to (a6-1-3), Rb ²⁰¹ is a chain alkenyl group which may have a substituent,
Rb ²⁰⁴ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent or a chain alkenyl group which may have a substituent,
Rb ²⁰⁵ is a chain alkenyl group which may have a substituent.
Rb ^{206 to} Rb ²⁰⁸ each independently represent a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent. (Wherein at least one of Rb ^{206 to} Rb ²⁰⁸ is a chain alkenyl group which may have a substituent).
Rb ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Yb ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. Vb ^{101 to} Vb ¹⁰³ are each independently a single bond, an alkylene group, a fluorinated alkylene group, an arylene group or a fluorinated arylene group. Lb ^{101 to} Lb ¹⁰² are each independently a single bond or an oxygen atom. Lb ^{103 to} Lb ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —. n ₁₀₁ is 0 or 1. ]

According to the present invention, it is possible to provide a resist composition capable of forming a resist pattern having excellent lithographic properties, and a method for forming a resist pattern using the resist composition.

In the present specification and claims, the term “aliphatic” is defined as a relative concept to aromatic and means a group, compound or the like having no aromaticity.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups.
Unless otherwise specified, the "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
The “halogenated alkyl group” is a group in which a part or all of hydrogen atoms of an alkyl group are substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The “fluorinated alkyl group” or “fluorinated alkylene group” refers to a group in which a part or all of the hydrogen atoms of the alkyl group or alkylene group is substituted with a fluorine atom.
The “constituent unit” means a monomer unit (monomer unit) that constitutes a polymer compound (resin, polymer, copolymer).
The “structural unit derived from an acrylate ester” means a constitutional unit formed by cleavage of an ethylenic double bond of an acrylate ester.
The “acrylic acid ester” is a compound in which a hydrogen atom at the carboxy group end of acrylic acid (CH ₂ ═CH—COOH) is substituted with an organic group.
In the acrylate ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R ^α ) for substituting the hydrogen atom bonded to the carbon atom at the α-position is an atom or a group other than a hydrogen atom, and examples thereof include an alkyl group having 1 to 5 carbon atoms and a halogenated group having 1 to 5 carbon atoms. Examples thereof include an alkyl group and a hydroxyalkyl group. The α-position carbon atom of the acrylate ester is a carbon atom to which a carbonyl group is bonded, unless otherwise specified.
Hereinafter, an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent may be referred to as an α-substituted acrylate ester. In addition, the acrylic ester and the α-substituted acrylic ester may be collectively referred to as “(α-substituted) acrylic ester”.
The “structural unit derived from a hydroxystyrene derivative” means a structural unit formed by cleavage of an ethylenic double bond of hydroxystyrene or a hydroxystyrene derivative.
The “hydroxystyrene derivative” is a concept including hydroxystyrene in which the hydrogen atom at the α-position is substituted with another substituent such as an alkyl group and a halogenated alkyl group, and derivatives thereof. As the derivatives thereof, those obtained by substituting the hydrogen atom of the hydroxyl group of hydroxystyrene with an organic group which may substitute the hydrogen atom at the α-position with an organic group, or the hydrogen atom at the α-position may be substituted with a substituent Examples thereof include those in which a substituent other than a hydroxyl group is bonded to the benzene ring of good hydroxystyrene. In addition, the α-position (carbon atom at the α-position) means a carbon atom to which a benzene ring is bonded, unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom at the α-position of hydroxystyrene include the same ones as the substituents at the α-position in the above α-substituted acrylate ester.
The “constituent unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative” means a constituent unit formed by cleavage of an ethylenic double bond of vinylbenzoic acid or a vinylbenzoic acid derivative.
The term “vinyl benzoic acid derivative” includes vinyl benzoic acid in which the α-position hydrogen atom is substituted with another substituent such as an alkyl group and a halogenated alkyl group, and a derivative thereof. Those derivatives include those in which the hydrogen atom of the carboxy group of vinylbenzoic acid, which may have a hydrogen atom at the α-position substituted by an organic group, and the hydrogen atom at the α-position are substituted by a substituent. And the like. Examples thereof include those in which a substituent other than a hydroxyl group and a carboxy group is bonded to the benzene ring of vinyl benzoic acid. In addition, the α-position (carbon atom at the α-position) means a carbon atom to which a benzene ring is bonded, unless otherwise specified.
The “styrene derivative” means one in which the hydrogen atom at the α-position of styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group.
The "structural unit derived from styrene" and the "structural unit derived from styrene derivative" mean a structural unit formed by cleavage of an ethylenic double bond of styrene or a styrene derivative.
The alkyl group as the α-position substituent is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
The halogenated alkyl group as the α-position substituent is specifically a group in which a part or all of the hydrogen atoms of the above-mentioned “alkyl group as the α-position substituent” is replaced with a halogen atom. To be Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
Specific examples of the hydroxyalkyl group as the α-position substituent include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as the α-position substituent” are substituted with hydroxyl groups. 1-5 are preferable and, as for the number of the hydroxyl groups in this hydroxyalkyl group, 1 is the most preferable.
Be referred to as a "may have a substituent", the case of replacing a hydrogen atom (-H) a monovalent group, methylene group - when substituting a divalent radical (-CH ₂₎ Including both.
“Exposure” is a concept that includes all radiation irradiation.

<Positive resist composition>
The positive resist composition according to the first aspect of the present invention (hereinafter may be simply referred to as “resist composition”) generates an acid upon exposure, and reacts with an alkali developer by the action of the acid. A positive resist composition having increased solubility, comprising a base material component (A) having increased solubility in an alkali developing solution by the action of an acid, and a compound (m) represented by the following general formula (m0). It is characterized by containing.

［一般式（ｍ０）中、
Ｚ^０１〜Ｚ^０４は、それぞれ独立に電子吸引性の置換基であり、
Ｒｂ^２１及びＲｂ^２２は、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基であり（但し、Ｒｂ^２１及びＲｂ^２２が有していてもよい置換基に電子吸引性の置換基は含まないものとする。）、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数であり、
Ｘ０^-は有機アニオンである。］

[In the general formula (m0),
Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing substituent,
Rb ²¹ and Rb ²² are each independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² may have a substituent Does not include electron-withdrawing substituents.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3,
X0 ^- is an organic anion. ]

In the present embodiment, the positive resist composition has an acid generating ability to generate an acid upon exposure, and the component (A) may generate an acid upon exposure, and is blended separately from the component (A). The added additive component may generate an acid upon exposure.
Specifically, in this embodiment, the positive resist composition is
(1) It may contain an acid generator component (B) which generates an acid upon exposure to light;
(2) The component (A) may be a component capable of generating an acid upon exposure to light;
(3) The component (A) may be a component which generates an acid upon exposure, and may further contain the component (B).
That is, in the cases of the above (2) and (3), the component (A) becomes "a base material component which generates an acid upon exposure and whose solubility in a developing solution is increased by the action of the acid". As the component (A) in this case, for example, a polymer compound having a structural unit (a6) derived from a compound represented by the general formula (a6-1) described later is preferable. As such a polymer compound, a resin having a structural unit that generates an acid upon exposure can be used. As the structural unit that generates an acid upon exposure, a known unit can be used.
In this embodiment, the resist composition is particularly preferably the case (1) above.

The base component (A), which has increased solubility in an alkaline developer due to the action of an acid contained in the positive resist composition of the first aspect of the present invention, will be described in the first embodiment of the present invention described later. The same material as the base material component (A) can be used.

[Compound (m)]
The compound (m) is represented by the following general formula (m0). The compound (m) is a compound that decomposes upon exposure to light to generate an acid.

［一般式（ｍ０）中、
Ｚ^０１〜Ｚ^０４は、それぞれ独立に電子吸引性の置換基であり、
Ｒｂ^２１及びＲｂ^２２は、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基であり（但し、Ｒｂ^２１及びＲｂ^２２が有していてもよい置換基に電子吸引性の置換基は含まないものとする。）、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数であり、
Ｘ０^-は有機アニオンである。］

[In the general formula (m0),
Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing substituent,
Rb ²¹ and Rb ²² are each independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² may have a substituent Does not include electron-withdrawing substituents.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3,
X0 ^- is an organic anion. ]

[Z ^{01 to} Z ⁰⁴ ]
In formula (m0), Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing group.
Examples of the electron-withdrawing substituent of Z ^{01 to} Z ⁰⁴ include a halogen atom, a halogenated alkyl group, an ester group, a sulfoxide group, a cyano group, an amide group, a carboxy group, a carbonyl group and the like.
Among these substituents, a halogen atom or a halogenated alkyl group is preferable from the viewpoint of improving the sensitivity of the resist composition.
As the halogen atom, a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.
As the halogenated alkyl group, a halogenated alkyl group having 1 to 5 carbon atoms is preferable, a halogenated alkyl group having 1 to 3 carbon atoms is more preferable, and a trifluoromethyl group is particularly preferable.

The electron-withdrawing substituents of Z ^{01 to} Z ⁰⁴ may be the same or different independently of each other, but from the viewpoint of facilitating operability in synthesis, Z ^{01 to} Z ⁰⁴ are the same electron-withdrawing group. It is preferable that the substituent is a volatile substituent, Z ^{01 to} Z ⁰⁴ are more preferably the same type of halogen atom, and Z ^{01 to} Z ⁰⁴ are particularly preferably a fluorine atom.

[Rb ²¹ and Rb ²² ]
In formula (m0), Rb ²¹ and Rb ²² each independently represent an alkyl group, an alicyclic hydrocarbon group which may have a substituent, or a hydroxyl group. However, the substituents that Rb ²¹ and Rb ²² may have do not include the above-mentioned electron-withdrawing substituents.

《Alkyl group》
The alkyl group for Rb ²¹ and Rb ²² is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.

<<Alicyclic hydrocarbon group which may have a substituent>>
The alicyclic hydrocarbon group for Rb ²¹ and Rb ²² may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from monocycloalkane. The monocycloalkane preferably has 3 to 8 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane and cyclooctane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically, Examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
Examples of the substituent that Rb ²¹ and Rb ²² may have include an alkyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

Among the above, as Rb ²¹ and Rb ²² , an alkyl group is preferable. As the alkyl group, an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.

[Rb ¹ ]
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.

<<Aryl group which may have a substituent>>
Examples of the aryl group for Rb ¹ include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.

<<Alkyl group which may have a substituent or alkenyl group which may have a substituent>>
The alkyl group for Rb ¹ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group for Rb ¹ preferably has 2 to 10 carbon atoms.

"Substituent in Rb ^1"
Examples of the substituent which Rb ¹ may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, an arylthio group, and the following general formula (ca-r- 1) to (ca-r-7) can be mentioned.

［一般式（ｃａ−ｒ−１）〜（ｃａ−ｒ−７）中、Ｒ’^２０１はそれぞれ独立に、水素原子、置換基を有していてもよい環式基、鎖状のアルキル基、または鎖状のアルケニル基である。］

[Formula (ca-r-1) in ~ (ca-r-7) , R '201 independently represents a hydrogen atom, which may have a substituent cyclic group, a chain alkyl group, Alternatively, it is a chain alkenyl group. ]

The cyclic group which may have a substituent, the chain alkyl group which may have a substituent or the chain alkenyl group which may have a substituent of R′ ²⁰¹ will be described later. In addition to those similar to R ¹⁰¹ in the general formula (b-1) described in the second embodiment, a cyclic group which may have a substituent or a substituent which may have a substituent may be mentioned. Examples of the chain alkyl group also include those similar to the acid dissociable group represented by the general formula (a1-r-2) described below.
As Rb ¹ , an aryl group which may have a substituent is preferable.

[N1 and n2]
n1 and n2 are each independently an integer of 0 to 3, more preferably 0 or 1.

The cation moiety of the compound represented by the general formula (m0) is preferably the cation moiety represented by the following general formula (m0-1).

［一般式（ｍ０−１）中、
Ｚ^０１１〜Ｚ^０１４は、それぞれ独立にハロゲン原子であり、
Ｒｂ^２２１及びＲｂ^２２２は、それぞれ独立に、アルキル基であり、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数である。］

[In the general formula (m0-1),
Z ^{011 to} Z ⁰¹⁴ are each independently a halogen atom,
Rb ²²¹ and Rb ²²² are each independently an alkyl group,
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3. ]

In formula (m0-1), Z ^{011 to} Z ⁰¹⁴ each independently represent a halogen atom, preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom.
In the general formula (m0-1), Rb ²²¹ and Rb ²²² are each independently an alkyl group, and the alkyl group is the same as the alkyl group described for Rb ²¹ and Rb ²² in the general formula (m0). Groups. Among them, Rb ²²¹ and Rb ²²² are preferably a methyl group or an ethyl group, and more preferably a methyl group.
In the general formula (m0-1), description of ^Rb 1, n1 and n2 are the in the general formula (m0), it is as described for ^Rb 1, n1 and n2.

Furthermore, the cation portion of the compound represented by the general formula (m0) is more preferably the cation portion represented by the following general formula (m0-1-1).

［一般式（ｍ０−１−１）中、
Ｒｂ^２２１及びＲｂ^２２２は、それぞれ独立に、アルキル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数であり、
Ｒｂ^３２１は、アルキル基又は前記一般式（ｃａ−ｒ−１）〜（ｃａ−ｒ−７）のいずれかで表される置換基であり、ｎ３１は０〜５の整数である。］

[In the general formula (m0-1-1),
Rb ²²¹ and Rb ²²² are each independently an alkyl group,
n1 and n2 are each independently an integer of 0 to 3,
Rb ³²¹ is an alkyl group or a substituent represented by any of the general formulas (ca-r-1) to (ca-r-7), and n31 is an integer of 0 to 5. ]

In general formula (m0-1-1), as Rb ²²¹ and Rb ²²² , an alkyl group having 1 to 5 carbon atoms is preferable as an alkyl group, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group or an ethyl group. Groups are particularly preferred.
n31 is an integer of 0 to 5, and more preferably an integer of 0 to 3.

In the general formula (m0-1-1), Rb ³²¹ is an alkyl group or a substituent represented by any of the general formulas (ca-r-1) to (ca-r-7).
When Rb ³²¹ is an alkyl group, a methyl group or an ethyl group is preferable.
When Rb ³²¹ is a substituent represented by any of the general formulas (ca-r-1) to (ca-r-7), it is represented by the general formula (ca-r-1). Groups are preferred. In this case, R′ ²⁰¹ in the group represented by the general formula (ca-r-1) is preferably an unsubstituted alkyl group having 1 to 5 carbon atoms.

Specific examples of the cation moiety of the compound (m0) are described below.

[X0 ^-]
X0 ^- in is not particularly restricted but includes organic anions represented, heretofore can be used various organic anions chemically amplified resist the acid generator or the like compounds have been proposed for.
X0 ^- for example, as an organic anion represented by a sulfonic acid anion, sulfonyl imide anion, methide anion, camphorsulfonic acid anion, and carboxylate anions and the like.

More specifically, the organic anion represented by X0 ⁻ is preferably an anion represented by any of the general formulas (m-an-1) to (m-an-3) described below, or a general formula described below. The same as the organic anion represented by any of (d1-1) to (d1-3) can be mentioned.

In the positive resist composition according to the first aspect of the present invention, the content ratio of the compound (m) is not particularly limited and can be appropriately adjusted according to the desired properties of the positive resist composition and the like.

The compound (m) represented by the general formula (m0) described above can be decomposed by exposure to generate an acid. The cation portion of the compound (m) has a structure that is easily decomposed by introducing an electron-withdrawing substituent. Therefore, the positive resist composition of the present invention has the effect of increasing the sensitivity when forming a resist pattern.

[Method for producing compound (m)]
The method for producing the compound (m) will be described.
The method for producing the compound (m) is not particularly limited, and the compound (m) can be produced using a known method, and can be obtained, for example, by the following first to third steps.

The compound (m) includes, for example, a first step in which a compound represented by the general formula (m1) is reacted with thionyl chloride (or a thionyl chloride derivative) to synthesize a compound represented by the general formula (m2). A second step of introducing a desired substituent into the obtained compound represented by the general formula (m2) to obtain a compound represented by the general formula (m3), and a second step represented by the obtained general formula (m3). The compound can be produced by a production method including the third step of obtaining the compound (m0) by salt exchange using the compound described above.

［式中、Ｒｚは前記一般式（ｍ０）におけるＺ^０１〜Ｚ^０４に対応し、それぞれ独立に電子吸引性の置換基である。
Ｒｂは、前記一般式（ｍ０）におけるＲｂ^２１及びＲｂ^２２に対応し、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基である。
ｎは前記一般式（ｍ０）におけるｎ１及びｎ２に対応し、それぞれ独立に、０〜３の整数である。］

Wherein, Rz corresponds to ^Z 01 ^{to Z 04} in the general formula (m0), are each independently an electron withdrawing group.
Rb corresponds to Rb ²¹ and Rb ²² in the general formula (m0), and is independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent, or a hydroxyl group.
n corresponds to n1 and n2 in the general formula (m0), and is independently an integer of 0 to 3. ]

［式中、Ｒｚは前記一般式（ｍ０）におけるＺ^０１〜Ｚ^０４に対応し、それぞれ独立に電子吸引性の置換基である。
Ｒｂは、前記一般式（ｍ０）におけるＲｂ^２１及びＲｂ^２２に対応し、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基である。
ｎは前記一般式（ｍ０）におけるｎ１及びｎ２に対応し、それぞれ独立に、０〜３の整数である。
Ｒｂ−ｍは、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基を有する化合物である。
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基である。］

Wherein, Rz corresponds to ^Z 01 ^{to Z 04} in the general formula (m0), are each independently an electron withdrawing group.
Rb corresponds to Rb ²¹ and Rb ²² in the general formula (m0), and is independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent, or a hydroxyl group.
n corresponds to n1 and n2 in the general formula (m0), and is independently an integer of 0 to 3.
Rb-m is a compound having an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent.
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. ]

［式中、Ｒｚは前記一般式（ｍ０）におけるＺ^０１〜Ｚ^０４に対応し、それぞれ独立に電子吸引性の置換基である。
Ｒｂは、前記一般式（ｍ０）におけるＲｂ^２１及びＲｂ^２２に対応し、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基である。
ｎは前記一般式（ｍ０）におけるｎ１及びｎ２に対応し、それぞれ独立に、０〜３の整数である。Ｘ０^-は有機アニオンである。
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基である。］

Wherein, Rz corresponds to ^Z 01 ^{to Z 04} in the general formula (m0), are each independently an electron withdrawing group.
Rb corresponds to Rb ²¹ and Rb ²² in the general formula (m0), and is independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent, or a hydroxyl group.
n corresponds to n1 and n2 in the general formula (m0), and is independently an integer of 0 to 3. X0 ^- is an organic anion.
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent. ]

As each of the compounds represented by the formulas (m1) to (m3), a commercially available compound may be used, or a compound synthesized by a known production method may be used.
As the solvent used in the first step to the second step, thionyl chloride to be used, compounds (m1) to (3), compound Rb-m, trifluoromethanesulfonic anhydride, etc. can be dissolved and do not react with them. What is necessary is just that, and for example, dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile and the like can be mentioned.
In the third step, an anion represented by any one of general formulas (m-an-1) to (m-an-3) described below, or general formulas (d1-1) to (d1-3) described below. The compound (m0) can be derived by salt exchange with the organic anion represented by any of the above.

After completion of the reaction, the compound in the reaction solution may be isolated and purified. For isolation and purification, conventionally known methods can be used, and for example, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography and the like can be used alone or in combination of two or more thereof.
The structure of the compound obtained as described above is as follows: ¹ H-nuclear magnetic resonance (NMR) spectroscopy, ¹³ C-NMR spectroscopy, ¹⁹ F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS) ) Method, elemental analysis method, X-ray crystal diffraction method and other general organic analysis methods.

Examples of the positive resist composition of the first aspect of the present invention include the positive resist compositions of the first and second embodiments described below.

«First embodiment»
The positive resist composition of the first embodiment (hereinafter, also referred to as “first positive resist composition”) generates an acid upon exposure, and the action of the acid increases the solubility in an alkali developing solution. A positive resist composition, which is a base component (A) whose solubility in an alkaline developer is increased by the action of an acid (hereinafter referred to as “component (A)”) and an acid which generates an acid upon exposure. A generator component (B1) (hereinafter referred to as “(B1) component”) and a photoreactive quencher (D1) (hereinafter referred to as “(D1) component”) are contained, and the above ( The component B1) is characterized by containing the compound (m).
When a resist film is formed by using the first positive resist composition and the resist film is selectively exposed, an acid is generated from the component (B1) in the exposed portion. The action of the acid increases the solubility of the component (A) in the alkaline developer. On the other hand, in the unexposed area, the solubility of the component (A) in the alkaline developer does not increase. Therefore, there is a difference in solubility in the alkali developing solution between the exposed area and the unexposed area. Therefore, when the resist film after the exposure is alkali-developed, the exposed portion is removed and a positive resist pattern is formed.

[(A) component]
The base component (A) contained in the positive resist composition of the present invention and having an increased solubility in an alkali developing solution under the action of an acid will be described.
In the present embodiment, the “base material component” is an organic compound having a film-forming ability, and an organic compound having a molecular weight of 500 or more is preferably used. When the molecular weight of the organic compound is 500 or more, the film forming ability is improved, and in addition, a nano-level photosensitive resin pattern is easily formed.
The organic compound used as the base material component is roughly classified into a non-polymer and a polymer.
As the non-polymer, one having a molecular weight of 500 or more and less than 4000 is usually used. Hereinafter, the term "low molecular weight compound" means a non-polymer having a molecular weight of 500 or more and less than 4000.
As the polymer, a polymer having a molecular weight of 1000 or more is usually used. Hereinafter, the term "resin" means a polymer having a molecular weight of 1,000 or more.
As the molecular weight of the polymer, the polystyrene-equivalent weight average molecular weight by GPC (gel permeation chromatography) is used.
As the component (A), a resin may be used, a low molecular weight compound may be used, or these may be used in combination.
The component (A) is one whose solubility in an alkaline developer is increased by the action of an acid.
Further, in the present embodiment, the component (A) may generate an acid upon exposure.

In the present embodiment, the component (A) preferably contains the resin component (A1) whose solubility in the developing solution changes. The resin component (A1) preferably has a structural unit (a9) represented by general formula (a9-1) or a structural unit (a10) containing an aromatic hydrocarbon group having a hydroxy group.
Further, in addition to the above structural unit (a9) or (a10), a structural unit containing an acid-decomposable group whose polarity increases due to the action of an acid (hereinafter sometimes referred to as “structural unit (a1)”), generally. structural unit represented by the formula (a12-1) (a12), - SO 2 - containing cyclic group, a lactone-containing cyclic group, the structural unit (hereinafter having a carbonate-containing cyclic group or a heterocyclic group other than those , A “structural unit (a2)”), a structural unit containing a polar group-containing aliphatic hydrocarbon group (hereinafter sometimes referred to as “structural unit (a3)”), or acid non-dissociation. It is preferable to have a structural unit containing a cyclic group (hereinafter sometimes referred to as “structural unit (a4)”).

(Structural unit (a9))
The structural unit (a9) is represented by general formula (a9-1) shown below.

［一般式（ａ９−１）中、Ｒは水素原子、炭素数１〜５のアルキル基または炭素数１〜５のハロゲン化アルキル基である。Ｙａ^９１は単結合または２価の連結基であり、Ｒ^９１は置換基を有していてもよい炭化水素基であり、Ｙａ^９２は２価の連結基である。］

[In general formula (a9-1), R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ya ⁹¹ is a single bond or a divalent linking group, R ⁹¹ is a hydrocarbon group which may have a substituent, and Ya ⁹² is a divalent linking group. ]

In general formula (a9-1), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group. , Isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.
n is a natural number, preferably 1 to 5, and more preferably 1 to 3.

In the general formula (a9-1), examples of the divalent linking group for Ya ⁹¹ include the same divalent linking groups for Ya ²¹ in the formula (a2-1) described below. Ya ⁹¹ is preferably a single bond.
In the formula (a9-1), the divalent linking group for Ya ⁹² is the same as the divalent linking group for Ya ^{91 and} the divalent linking group for Ya ²¹ in the formula (a2-1) described later. The same thing is mentioned. Among them, in the divalent linking group for Ya ⁹² in the formula (a9-1), the divalent hydrocarbon group which may have a substituent is a linear or branched aliphatic hydrocarbon. The group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, preferably a linear alkylene group, and specific examples include a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], trimethylene [ _{- (CH 2) 3 -]} , a tetramethylene group _{[- (CH 2) 4 -} ], a pentamethylene group _{[- (CH 2) 5 -} ] , and the like.
As the branched aliphatic hydrocarbon group, preferably a branched chain alkylene group, _{specifically, -CH (CH 3) -,} - CH (CH 2 CH 3) -, - C (CH 3) _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 Alkylethylene group such as CH ₃ ) ₂ —CH ₂ —; alkyltrimethylene group such as —CH(CH ₃ )CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ )CH ₂ —, —CH(CH ₃ ). Examples thereof include alkyl alkylene groups such as alkyl tetramethylene groups such as CH ₂ CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ )CH ₂ CH ₂ — and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

In the divalent linking group for Ya ⁹² in formula (a9-1), the divalent linking group optionally having a hetero atom includes —O— and —C(═O)—O—. , -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H is an alkyl group, with a substituent such as an acyl group which may be _{substituted), -. S -, -} S (= O) 2 -, - S (= O) 2 -O -, - C (= S) -, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -O - Y 21, [Y 21 -C (= ^{_{O) -O] m '-Y 22}} - or ^{-Y 21 -O-C (= O} ) -Y 22 - group [wherein represented ^{by, Y 21} and ^{Y 22} each independently have a substituent It is a divalent hydrocarbon group that may be present, O is an oxygen atom, and m′ is an integer of 0 to 3. ] Etc. are mentioned. Among them, -C(=O)- and -C(=S)- are preferable.

In general formula (a9-1), examples of the hydrocarbon group for R ⁹¹ include an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, and an aralkyl group.
The alkyl group for R ⁹¹ preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and may be linear or branched. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and the like can be mentioned as preferable ones.
The monovalent alicyclic hydrocarbon group for R ⁹¹ preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclobutane, cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically, Examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
The aryl group for R ⁹¹ preferably has 6 to 18 carbon atoms, more preferably 6 to 10 carbon atoms, and specifically preferably a phenyl group.
The aralkyl group for R ⁹¹ is also preferably an aralkyl group having 7 to 10 carbon atoms, and examples of the aralkyl group having 7 to 10 carbon atoms include a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, and a 1-naphthyl group. An arylalkyl group such as an ethyl group and a 2-naphthylethyl group can be mentioned.
The hydrocarbon group for R ⁹¹ is preferably such that a part or all of the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms, and 30 to 100% of the hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms. Is more preferable. Among them, it is particularly preferable that the above-mentioned alkyl group is a perfluoroalkyl group in which all the hydrogen atoms are substituted with fluorine atoms.

The hydrocarbon group for R ⁹¹ may have a substituent. Examples of the substituent include a halogen atom, an oxo group (= O), a hydroxyl group (-OH), a amino group _{(-NH 2), - SO 2} -NH 2 , and the like. Further, a part of the carbon atoms constituting the hydrocarbon group may be replaced with a substituent containing a hetero atom. Examples of the substituent containing the hetero atom include -O-, -NH-, -N=, -C(=O)-O-, -S-, -S(=O) _2- , -S(=O. ) _2- O- is mentioned.
Examples of the hydrocarbon group having a substituent in R ⁹¹ include lactone-containing cyclic groups represented by the above general formulas (a2-r-1) to (a2-r-7).

In R ⁹¹ , the hydrocarbon group having a substituent is a —SO ₂ — containing cyclic group represented by each of general formulas (a5-r-1) to (a5-r-4) described below; And a substituted aryl group, a monovalent heterocyclic group and the like. In the formulas (r-ar-1) to (r-ar-8) and (r-hr-1) to (r-hr-10) below, “*” represents a bond with Ya ⁹² .

Specific examples of the structural unit represented by the general formula (a9-1) are shown below. In the formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The constitutional unit represented by the general formula (a9-1) is preferably a constitutional unit represented by the following general formula (a9-1-1).

［式中、Ｒは水素原子、炭素数１〜５のアルキル基または炭素数１〜５のハロゲン化アルキル基である。Ｙａ^９１は単結合または２価の連結基であり、Ｒ^９１は置換基を有していてもよい炭化水素基であり、Ｒ^９２は酸素原子又は硫黄原子である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ya ⁹¹ is a single bond or a divalent linking group, R ⁹¹ is a hydrocarbon group which may have a substituent, and R ⁹² is an oxygen atom or a sulfur atom. ]

In general formula (a9-1-1), the description of Ya ⁹¹ , R ⁹¹ , and R is the same as above. R ⁹² is an oxygen atom or a sulfur atom.

Specific examples of the structural unit represented by the general formula (a9-1-1) are shown below. In the formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The structural unit (a9) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a9), the proportion of the structural unit (a9) is preferably 1 to 60 mol% based on the total of all the structural units constituting the component (A1), 3 to 55 mol% is more preferable, and 10 to 50 mol% is particularly preferable. When the proportion of the structural unit (a9) is at least the lower limit value, the development characteristics and lithographic characteristics such as EL margin are improved, and when it is at most the upper limit value, it becomes easy to balance with other structural units.

(Structural unit (a10))
The structural unit (a10) is a structural unit containing an aromatic hydrocarbon group having a hydroxy group.
As the structural unit (a10),
The following general formulas (a10)-1-1 to (a10)-1-2,
The following general formulas (a10)-2-1 to (a10)-2-2,
The following general formula (a10)-3-1 to (a10)-3-4,
The following general formulas (a10)-4-1 to (a10)-4-4,
The structural unit (a10) represented by any of the above is mentioned as a preferable example.

（式中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。ｎは自然数である。）

(In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. n is a natural number.)

（式中、ｎは自然数である。）

(In the formula, n is a natural number.)

（式中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。ｎは自然数である。）

(In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. n is a natural number.)

（式中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。ｎは自然数である。）

(In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. n is a natural number.)

In the structural unit (a10) represented by each of the above general formulas (a10)-1-2 and (a10)-3-3 to (a10)-3-4, R is a hydrogen atom and has 1 to 5 carbon atoms. It is an alkyl group or a halogenated alkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group. , Isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.
n is a natural number, preferably 1 to 9, more preferably 1 to 7, particularly preferably 1 to 5, and most preferably 1 to 3.

Specific examples of the structural unit represented by general formula (a10)-1-1 are described below.

Specific examples of the structural unit represented by the general formula (a10)-1-2 are described below.

Specific examples of the structural unit represented by general formula (a10)-2-1 will be described below.

Specific examples of the structural unit represented by the general formula (a10)-2-2 are described below.

Specific examples of the structural unit represented by general formula (a10)-3-1 are described below.

Specific examples of the structural unit represented by general formula (a10)-3-2 above are described below.

Specific examples of the structural unit represented by the general formula (a10)-3-3 are described below.

Specific examples of the structural unit represented by general formula (a10)-3-4 above are described below.

Specific examples of the structural unit represented by general formula (a10)-4-1 are described below.

Specific examples of the structural unit represented by general formula (a10)-4-2 are described below.

Specific examples of the structural unit represented by the general formula (a10)-4-3 are described below.

Specific examples of the structural unit represented by the general formula (a10)-4-4 are described below.

The structural unit (a10) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a10), the proportion of the structural unit (a10) is preferably 1 to 60 mol% based on the total of all the structural units constituting the component (A1), 10 to 50 mol% is more preferable. When the proportion of the structural unit (a10) is at least the lower limit value, the development characteristics and lithographic characteristics such as EL margin are improved, and when it is at most the upper limit value, it becomes easy to balance with other structural units.

(Structural unit (a1))
The structural unit (a1) is a structural unit containing an acid-decomposable group whose polarity increases due to the action of an acid.
The "acid-decomposable group" is an acid-decomposable group capable of cleaving at least a part of the bonds in the structure of the acid-decomposable group by the action of an acid.
Examples of the acid-decomposable group whose polarity increases by the action of an acid include groups that decompose to form a polar group by the action of an acid.
Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, a sulfo group _(-SO 3 H) and the like. Among these, a polar group containing —OH in the structure (hereinafter sometimes referred to as “OH-containing polar group”) is preferable, a carboxy group or a hydroxyl group is preferable, and a carboxy group is particularly preferable.
More specific examples of the acid-decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).
Here, the "acid dissociable group" means
(I) an acid dissociable group capable of cleaving a bond between the acid dissociable group and an atom adjacent to the acid dissociable group by the action of an acid, or
(Ii) A group capable of cleaving a bond between the acid dissociable group and an atom adjacent to the acid dissociable group by further decarboxylation reaction after a part of the bond is cleaved by the action of an acid. ,
To both sides.
The acid-dissociable group constituting the acid-decomposable group needs to be a group having a lower polarity than the polar group generated by dissociation of the acid-dissociable group. When is dissociated, a polar group having a higher polarity than the acid-dissociable group is generated to increase the polarity. As a result, the polarity of the entire component (A1) increases. The increase in polarity relatively changes the solubility in the developing solution, and decreases the solubility when the developing solution is an organic developing solution.

The acid dissociable group is not particularly limited, and those proposed so far as the acid dissociable group of the base resin for the chemically amplified resist can be used.
Among the polar groups, examples of the acid dissociable group that protects a carboxy group or a hydroxyl group include, for example, an acid dissociable group represented by the following general formula (a1-r-1) (hereinafter, for convenience, "acetal-type acid dissociable group"). Sometimes referred to as "group").

［式中、Ｒａ’^１、Ｒａ’^２は水素原子またはアルキル基、Ｒａ’^３は炭化水素基、Ｒａ’^３は、Ｒａ’^１、Ｒａ’^２のいずれかと結合して環を形成してもよい。＊は結合手を意味する。］

[In the formula, Ra′ ¹ and Ra′ ² are each a hydrogen atom or an alkyl group, Ra′ ³ is a hydrocarbon group, and Ra′ ³ is bonded to either Ra′ ¹ or Ra′ ² to form a ring. Good. * Means a bond. ]

In general formula (a1-r-1), examples of the alkyl group of Ra′ ¹ and Ra′ ² are the substituents that may be bonded to the α-position carbon atom in the description of the α-substituted acrylate ester. Examples of the alkyl group are the same as those described above, a methyl group or an ethyl group is preferable, and a methyl group is most preferable.

As the hydrocarbon group for Ra′ ³ , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable; a linear or branched alkyl group is preferable, and specifically, , Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylethyl group, 1,1-diethylpropyl group 2,2-dimethylpropyl group, 2,2,-dimethylbutyl group and the like can be mentioned.

When Ra′ ³ is a cyclic hydrocarbon group, it may be aliphatic or aromatic, and may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from monocycloalkane. The monocycloalkane preferably has 3 to 8 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane and cyclooctane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically, adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

When it becomes an aromatic hydrocarbon group, specific examples of the aromatic ring contained include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene; and the like of the carbon atoms constituting the aromatic hydrocarbon ring. Aromatic heterocycles partially substituted with heteroatoms; and the like. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group include a group in which one hydrogen atom is removed from the aromatic hydrocarbon ring (aryl group); a group in which one of hydrogen atoms in the aryl group is substituted with an alkylene group (for example, , Benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group and other arylalkyl groups); The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

When Ra′ ³ is bonded to either Ra′ ¹ or Ra′ ² to form a ring, the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

Among the polar groups, examples of the acid dissociable group that protects the carboxy group include acid dissociable groups represented by the following general formula (a1-r-2) (see the following formula (a1-r-2). Among the acid dissociable groups represented by (4), those composed of an alkyl group may be hereinafter referred to as "tertiary alkyl ester-type acid dissociable groups" for convenience).

［一般式（ａ１−ｒ−２）中、Ｒａ’^４〜Ｒａ’^６は炭化水素基であり、Ｒａ’^５、Ｒａ’^６は互いに結合して環を形成してもよい。＊は結合手を意味する。］

[In formula (a1-r-2), Ra '4 ~Ra' 6 is a hydrocarbon group, Ra ^'5, Ra' ⁶ may be bonded to each other to form a ring. * Means a bond. ]

Examples of the hydrocarbon group of Ra′ ^{4 to} Ra′ ⁶ include the same as those of Ra′ ³ . Ra′ ⁴ is preferably an alkyl group having 1 to 5 carbon atoms. When Ra′ ⁵ and Ra′ ⁶ are bonded to each other to form a ring, a group represented by general formula (a1-r2-1) shown below can be mentioned.
On the other hand, when Ra′ ^{4 to} Ra′ ⁶ are not bonded to each other and are independent hydrocarbon groups, groups represented by general formula (a1-r2-2) shown below can be mentioned.

［一般式（ａ１−ｒ２−１）又は（ａ１−ｒ２−２）中、Ｒａ’^１０は炭素数１〜１０のアルキル基、Ｒａ’^１１はＲａ’^１０が結合した炭素原子と共に脂肪族環式基を形成する基、Ｒａ’^１２〜Ｒａ’^１４は、それぞれ独立に炭化水素基を示す。＊は結合手を意味する。］

[Formula (a1-r2-1) or in (a1-r2-2), Ra ' 10 is an alkyl group having 1 to 10 carbon atoms, Ra' ¹¹ aliphatic cyclic together with the carbon atom to which Ra ^'10 is bonded The groups forming the group, Ra′ ^{12 to} Ra′ ¹⁴ , each independently represent a hydrocarbon group. * Means a bond. ]

In the general formula (a1-r2-1), the alkyl group of the alkyl group having 1 to ¹⁰ carbon atoms of Ra′ ¹⁰ is the linear or branched chain of Ra′ ³ in the general formula (a1-r-1). The groups mentioned as the alkyl group are preferred. In general formula (a1-r2-1), the aliphatic cyclic group which Ra′ ¹¹ constitutes is preferably the group exemplified as the cyclic alkyl group for Ra′ ³ in general formula (a1-r-1).

In general formula (a1-r2-2), Ra′ ¹² and Ra′ ¹⁴ are preferably each independently an alkyl group having 1 to 10 carbon atoms, and the alkyl group is represented by general formula (a1-r-1). The group mentioned as the straight chain or branched chain alkyl group of Ra′ ^{3 in} (4) is more preferable, the straight chain alkyl group having 1 to 5 carbon atoms is further preferable, and the methyl group or the ethyl group is preferable. Particularly preferred.
In general formula (a1-r2-2), Ra′ ¹³ is a linear, branched or cyclic alkyl group exemplified as the hydrocarbon group for Ra′ ³ in general formula (a1-r-1). It is preferable to have. Among these, the groups mentioned as the cyclic alkyl group of Ra′ ³ are more preferable.

Specific examples of the group represented by the general formula (a1-r2-1) are shown below. In the following formula, “*” indicates a bond.

Specific examples of the group represented by the general formula (a1-r2-2) are shown below.

Moreover, as an acid dissociable group which protects a hydroxyl group among the polar groups, for example, an acid dissociable group represented by the following general formula (a1-r-3) (hereinafter, referred to as "tertiary alkyloxycarbonyl acid for convenience" Sometimes referred to as a "dissociative group").

［一般式（ａ１−ｒ−３）中、Ｒａ’^７〜Ｒａ’^９はアルキル基を示す。＊は結合手を意味する。］

[In the formula (a1-r-3), Ra '7 ~Ra' 9 is an alkyl group. * Means a bond. ]

In general formula (a1-r-3), Ra′ ^{7 to} Ra′ ⁹ are preferably alkyl groups having 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.
The total number of carbon atoms in each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

The structural unit (a1) is a structural unit derived from an acrylate ester in which a hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent, and is an acid whose polarity increases by the action of an acid. A constitutional unit containing a decomposable group; a constitutional unit in which at least a part of hydrogen atoms in a hydroxyl group of the constitutional unit derived from hydroxystyrene or a hydroxystyrene derivative is protected by a substituent containing the acid-decomposable group; vinylbenzoic acid or Examples thereof include a structural unit in which at least a part of hydrogen atoms in -C(=O)-OH of a structural unit derived from a vinylbenzoic acid derivative is protected by a substituent containing the acid-decomposable group.

Among the above, the structural unit (a1) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.
As the structural unit (a1), a structural unit represented by general formula (a1-1) or (a1-2) shown below is preferable.

［一般式（ａ１−１）又は（ａ１−２）中、Ｒは水素原子、炭素数１〜５のアルキル基または炭素数１〜５のハロゲン化アルキル基である。Ｖａ^１はエーテル結合、ウレタン結合、又はアミド結合を有していてもよい２価の炭化水素基であり、ｎ_ａ１は０〜２であり、Ｒａ^１は上記一般式（ａ１−ｒ−１）〜（ａ１−ｒ−２）で表される酸解離性基である。Ｗａ^１はｎ_ａ２＋１価の炭化水素基であり、ｎ_ａ２は１〜３であり、Ｒａ^２は上記一般式（ａ１−ｒ−１）または（ａ１−ｒ−３）で表される酸解離性基である。］

[In general formula (a1-1) or (a1-2), R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Va ¹ is a divalent hydrocarbon group which may have an ether bond, a urethane bond, or an amide bond, na ₁ is 0 to 2, and Ra ¹ is the above general formula (a1-r-1). To (a1-r-2) are acid dissociable groups. Wa ¹ is a _{na 2} +1 valent hydrocarbon group, _{na 2} is 1 to 3, and Ra ² is an acid dissociation represented by the above general formula (a1-r-1) or (a1-r-3). It is a sexual group. ]

In the general formula (a1-1), the alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, a methyl group, an ethyl group, Examples thereof include propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group and neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.
The hydrocarbon group of Va ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group as the divalent hydrocarbon group in Va ¹ may be saturated or unsaturated, and is usually preferably saturated.
More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in the structure.
Examples of Va ¹ include the above divalent hydrocarbon groups bonded via an ether bond, a urethane bond, or an amide bond.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, preferably a linear alkylene group, and specific examples include a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], trimethylene [ _{- (CH 2) 3 -]} , a tetramethylene group _{[- (CH 2) 4 -} ], a pentamethylene group _{[- (CH 2) 5 -} ] , and the like.
As the branched aliphatic hydrocarbon group, preferably a branched chain alkylene group, _{specifically, -CH (CH 3) -,} - CH (CH 2 CH 3) -, - C (CH 3) _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 Alkylethylene group such as CH ₃ ) ₂ —CH ₂ —; alkyltrimethylene group such as —CH(CH ₃ )CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ )CH ₂ —, —CH(CH ₃ ). Examples thereof include alkyl alkylene groups such as alkyl tetramethylene groups such as CH ₂ CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ )CH ₂ CH ₂ — and the like. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group having a linear or branched structure. Examples thereof include a group bonded to the end of a chain-like aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is present in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same ones as described above.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically, adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring.
The aromatic hydrocarbon group as the divalent hydrocarbon group in Va ¹ has preferably 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, further preferably 5 to 20 carbon atoms, and 6 to 6 carbon atoms. 15 is particularly preferable, and 6 to 10 is the most preferable. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring included in the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; some of the carbon atoms constituting the aromatic hydrocarbon ring are heterocyclic. Aromatic heterocycles substituted with atoms; and the like. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group). Group in which one of the hydrogen atoms of () is substituted with an alkylene group (for example, arylalkyl such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group). Group in which one more hydrogen atom is removed from the aryl group in the group); The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

In the general formula (a1-2), the na ₂ +1 valent hydrocarbon group for Wa ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, may be saturated or unsaturated, and is usually preferably saturated. As the aliphatic hydrocarbon group, a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or a linear or branched aliphatic hydrocarbon group Examples thereof include groups in which an aliphatic hydrocarbon group containing a ring in the structure is combined, and specifically, the same groups as the groups represented by Va ¹ in the above general formula (a1-1) can be mentioned.
The _{na 2} +1 valence is preferably 2 to 4, and more preferably 2 or 3.

As the constitutional unit represented by the general formula (a1-2), a constitutional unit represented by the following general formula (a1-2-01) is particularly preferable.

In general formula (a1-2-01), Ra ² is an acid dissociable group represented by general formula (a1-r-1) or (a1-r-3) above. n _a2 is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. c is an integer of 0 to 3, preferably 0 or 1, and more preferably 1. R is the same as above.
Specific examples of the structural unit represented by the general formula (a1-1) or (a1-2) are shown below. In each formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The structural unit (a1) contained in the component (A1) may be one type or two or more types.
The proportion of the structural unit (a1) in the component (A1) is preferably 20 to 80 mol%, more preferably 20 to 75 mol%, and even more preferably 25 to 70 mol%, based on all the structural units constituting the component (A1). Is more preferable. By setting the content to the lower limit or more, the lithographic properties such as sensitivity, resolution and LWR are also improved. Further, by setting the content to the upper limit or less, it is possible to balance with other structural units.

(Structural unit (a12))
The structural unit (a12) is a structural unit containing an acid-decomposable group whose polarity increases due to the action of an acid, and is a structural unit represented by general formula (a12-1) shown below.

［一般式（ａ１２−１）中、Ｒは水素原子、炭素数１〜５のアルキル基または炭素数１〜５のハロゲン化アルキル基である。Ｙａは炭素原子である。ＸａはＹａとともに脂環式炭化水素基を形成するために必要な原子団である。Ｒａ^０１は置換基を有していてもよい芳香族炭化水素基である。］

[In general formula (a12-1), R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ya is a carbon atom. Xa is an atomic group necessary for forming an alicyclic hydrocarbon group together with Ya. Ra ⁰¹ is an aromatic hydrocarbon group which may have a substituent. ]

<<R>>
In the general formula (a12-1), the alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, methyl group, ethyl group. Group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.

<<Xa>>
In the general formula (a12-1), the number of carbon atoms of the alicyclic hydrocarbon group formed by Xa together with Ya is not particularly limited, but is preferably 5 to 25, more preferably 5 to 20, and further preferably 5 to 15.
The alicyclic hydrocarbon group may be monocyclic or polycyclic. Specific structures of the alicyclic moiety include, for example, structures represented by the following formulas (Xa-1) to (Xa-50).

In particular, the alicyclic hydrocarbon group formed by Xa together with Ya in the general formula (a12-1) is preferably a group having a monocyclo, bicyclo, tricyclo or tetracyclo structure.
Specific examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, and cyclododecanyl group; adamantyl group, noradamantyl group. Group, decalin residue (decalinyl group), tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group and the like.

Among these, cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group and cyclododecanyl group; adamantyl group, decalin residue, norbornyl group and the like are preferable. Particularly, it is preferably a cycloalkyl group having 5 to 15 carbon atoms.
Further, the alicyclic hydrocarbon group may be substituted or unsubstituted. Specific examples of the substituent include, for example, methyl group, ethyl group, propyl group, hydroxyl group, carboxy group, halogen atom (fluorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group). Etc.), an alkyloxycarboni group and the like.

<< Ra ⁰¹ >>
Examples of the aromatic hydrocarbon group which may have a substituent of Ra ⁰¹ include groups derived from the structures represented by the following formulas (Ra ⁰¹ -1) to (Ra ⁰¹ -3). You can
In addition, when Ra ⁰¹ is a group (that is, a naphthyl group) derived from the following (Ra ⁰¹ -2), the bonding positions for bonding to Ya in the general formula (a12-1) are 1-position and 2-position. It may be either.
Further, when Ra ⁰¹ is a group (that is, an anthryl group) derived from the following (Ra ⁰¹ -3), the bonding positions for bonding to Ya in the general formula (a12-1) are 1-position, 2-position and It may be in 9th place.
Moreover, this aryl group may have a substituent. Specific examples of the substituent include, for example, methyl group, ethyl group, propyl group, hydroxyl group, carboxy group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy group (methoxy group, ethoxy group, propoxy group). , Butoxy groups, etc.), alkyloxycarbonyl groups, and the like.

［一般式（ａ１２−１−１）において、Ｒは水素原子、炭素数１〜５のアルキル基または炭素数１〜５のハロゲン化アルキル基であり、Ｒａ^００１は炭素数１〜４のアルキル基であり、Ｙａは炭素原子であり、ＸａはＹａとともに脂環式炭化水素基を形成するのに必要な原子団であり、ｎ１は０〜３の整数である。］

[In general formula (a12-1-1), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Ra ⁰⁰¹ represents an alkyl group having 1 to 4 carbon atoms. And Ya is a carbon atom, Xa is an atomic group necessary for forming an alicyclic hydrocarbon group together with Ya, and n1 is an integer of 0 to 3. ]

Examples of the alkyl group having 1 to 4 carbon atoms represented by Ra ⁰⁰¹ in formula (a12-1-1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a 2-methylpropyl group. , 1-methylpropyl group, t-butyl group and the like.
Further, n1 in the general formula (a12-1-1) is an integer of 0 to 3, more preferably 0 or 1.
Regarding the “alicyclic hydrocarbon group formed by Xa together with Ya” in the general formula (a12-1-1), the “alicyclic hydrocarbon group formed by Xa together with Ya in the above general formula (a12-1) is represented. The explanation of “” can be applied as it is.

Specific examples of the structural unit (a12) are described below. In the following formulas, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

The structural unit (a12) contained in the component (A1) may be one type or two or more types.
The proportion of the structural unit (a12) in the component (A1) is preferably 50 to 80 mol%, more preferably 10 to 75 mol%, and further preferably 10 to 70 mol% with respect to all the structural units constituting the component (A1). Is more preferable. By setting the content to the lower limit or more, the lithographic properties such as sensitivity, resolution and LWR are also improved. Further, by setting the content to the upper limit or less, it is possible to balance with other structural units.

(Structural unit (a2))
The structural unit (a2) is a structural unit having a —SO ₂ — containing cyclic group, a lactone containing cyclic group, a carbonate containing cyclic group or a heterocyclic group other than these.
The —SO ₂ —-containing cyclic group, lactone-containing cyclic group, carbonate-containing cyclic group or heterocyclic group other than these in the structural unit (a2) is the same as when the component (A1) is used for forming a resist film. , Is effective in improving the adhesion of the resist film to the substrate.
In the case where the structural unit (a1) contains a —SO ₂ — containing cyclic group, a lactone containing cyclic group, a carbonate containing cyclic group or a heterocyclic group other than these in the structure, the structural unit Corresponds to the structural unit (a2), but such a structural unit corresponds to the structural unit (a1) and does not correspond to the structural unit (a2).

The structural unit (a2) is preferably a structural unit represented by general formula (a2-1) shown below.

［一般式（ａ２−１）中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基であり、Ｙａ^２１は単結合または２価の連結基であり、Ｌａ^２１は−Ｏ−、−ＣＯＯ−、−ＣＯＮ（Ｒ’）−、−ＯＣＯ−、−ＣＯＮＨＣＯ−又は−ＣＯＮＨＣＳ−であり、Ｒ’は水素原子またはメチル基を示す。ただしＬａ^２１が−Ｏ−の場合、Ｙａ^２１は−ＣＯ−にはならない。Ｒａ^２１は−ＳＯ_２−含有環式基、ラクトン含有環式基、カーボネート含有環式基又はこれら以外の複素環式基である。］

[In general formula (a2-1), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya ²¹ represents a single bond or a divalent linking group. , La ²¹ is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO- or -CONHCS-, and R'represents a hydrogen atom or a methyl group. However, when La ²¹ is -O-, Ya ²¹ does not become -CO-. Ra ²¹ is a —SO ₂ — containing cyclic group, a lactone containing cyclic group, a carbonate containing cyclic group or a heterocyclic group other than these. ]

The divalent linking group for Ya ²¹ is not particularly limited, but examples thereof include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom.

Divalent hydrocarbon group which may have a substituent The hydrocarbon group as the divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group containing a ring in the structure, and specifically, the above general formula (a1). The groups exemplified as Va ¹ in -1) are mentioned.

The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.

As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure (two hydrogen atoms are removed from the aliphatic hydrocarbon ring Group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group is linear or branched fat Examples thereof include groups intervening in the middle of the group hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same ones as described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
Specific examples of the cyclic aliphatic hydrocarbon group include the groups exemplified as Va ¹ in the above general formula (a1-1).
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group and the like.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a tert-butoxy group, and a methoxy group. Most preferred is the group ethoxy.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include groups in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom.
In the cyclic aliphatic hydrocarbon group, a part of carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As the substituent containing the hetero atom, -O-, -C(=O)-O-, -S-, -S(=O) _2- , and -S(=O) _2- O- are preferable.

Specific examples of the aromatic hydrocarbon group as the divalent hydrocarbon group include the groups exemplified for Va ¹ in the above general formula (a1-1).
In the aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group and the like.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
Examples of the alkoxy group, the halogen atom and the halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

Divalent linking group containing a hetero atom The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom. To be

When Ya ²¹ is a divalent linking group containing a hetero atom, preferable examples of the linking group include —O—, —C(═O)—O—, —C(═O)—, and —O—C. (=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H may be substituted with a substituent such as an alkyl group and an acyl group. _{.), - S -, -} S (= O) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 - C (= O) -O -, - C (= O) -O - Y 21, [Y 21 -C (= O) -O] m '-Y 22 - or ^-Y 21 -O-C (= O) -Y 22 ^- group [wherein represented by, Y ²¹ and Y ²² are each independently may be substituted divalent hydrocarbon group, O is an oxygen atom, m'is an integer of 0-3. ] Etc. are mentioned.
When the divalent linking group containing a hetero atom is -C(=O)-NH-, -NH-, -NH-C(=NH)-, H is a substituent such as an alkyl group or acyl. It may be substituted. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -O-Y 21, - [Y 21 -C ( _{= O) -O] m '-Y} 22 - or ^{-Y 21 -O-C (= O} ) -Y 22 - ^{in, Y 21} and ^{Y 22} each independently have a substituent It is a good divalent hydrocarbon group. Examples of the divalent hydrocarbon group include those similar to the “divalent hydrocarbon group which may have a substituent” mentioned in the description of the divalent linking group.
As Y ²¹ , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable.
Y ²² is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
Formula ^{- [Y 21 -C (= O} ) -O] m '-Y 22 - In the group represented by, m' is an integer of 0 to 3, preferably an integer of 0 to 2, 0 Alternatively, 1 is more preferable, and 1 is particularly preferable. In other words, the formula ^- Examples of the group represented by the formula ^{-Y 21 -C (= O) -O} -Y 22 - - [Y 21 -C (= O) -O] m '-Y 22 represented by Groups are particularly preferred. Among them, the formula _{- (CH 2) a '-C} (= O) -O- (CH 2) b' - a group represented by are preferred. In the formula, a′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. b′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1.

In the present embodiment, as Ya ²¹ , a single bond, an ester bond [—C(═O)—O—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof. Is preferred.

In the general formula (a2-1), Ra ²¹ is a —SO ₂ — containing cyclic group, a lactone containing cyclic group, a carbonate containing cyclic group, or a heterocyclic group other than these.

And _- "-SO 2 containing cyclic group", -SO 2 _- within the ring skeleton thereof shows a cyclic group containing a ring containing, in particular, -SO 2 _- sulfur atom (S) is in A cyclic group that forms a part of the ring skeleton of the cyclic group. A ring containing —SO ₂ — in its ring skeleton is counted as the first ring, and when it has only this ring, it is a monocyclic group, and when it has another ring structure, it is a polycyclic group regardless of its structure. Called. The —SO ₂ — containing cyclic group may be monocyclic or polycyclic.
The —SO ₂ — containing cyclic group is particularly a cyclic group containing —O—SO ₂ — in its ring skeleton, that is, —O—S— in —O—SO ₂ — forms a part of the ring skeleton. It is preferably a cyclic group containing a sultone ring to be formed. Specific examples of the —SO ₂ — containing cyclic group include groups represented by general formulas (a5-r-1) to (a5-r-4) shown below.

［式中、Ｒａ’^５１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子またはアルキル基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｎ’は０〜２の整数である。］

[Wherein Ra′ ⁵¹ is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group or a cyano group. R" is a hydrogen atom or an alkyl group; A" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and n'is 0 to 2 Is an integer. ]

In the general formulas (a5-r-1) to (a5-r-4), A″ is the same as A″ in the general formulas (a2-r-1) to (a2-r-7) described later. .. Examples of the alkyl group, alkoxy group, halogen atom, halogenated alkyl group, —COOR″, —OC(═O)R″, and hydroxyalkyl group for Ra′ ⁵¹ , which will be described later, include general formulas (a2-r-1) to (a2-r-1). The same as Ra' ^{21 in} a2-r-7).

Specific examples of the groups represented by general formulas (a5-r-1) to (a5-r-4) are shown below. “Ac” in the formula represents an acetyl group.

In the present embodiment, when the structural unit (a2) includes a —SO ₂ — containing cyclic group, among the above groups, the group represented by the general formula (a5-r-1) is preferable, and the chemical formula (r- sl-1-1), (r-sl-1-18), (r-sl-3-1) and (r-sl-4-1) are selected from the group consisting of It is more preferable to use at least one of the above, and the group represented by the chemical formula (r-sl-1-1) is most preferable.

The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing —O—C(═O)— in its ring skeleton. The lactone ring is counted as the first ring, and a lactone ring alone is referred to as a monocyclic group, and a lactone ring having another ring structure is referred to as a polycyclic group regardless of the structure. The lactone-containing cyclic group may be either a monocyclic group or a polycyclic group.
The lactone-containing cyclic group is not particularly limited and any one can be used. Specific examples include groups represented by general formulas (a2-r-1) to (a2-r-7) shown below. Hereinafter, “*” represents a bond.

［式中、Ｒａ’^２１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子またはアルキル基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｎ’は０〜２の整数であり、ｍ’は０または１である。］

[Wherein Ra′ ²¹ is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR”, —OC(═O)R”, a hydroxyalkyl group or a cyano group. R" is a hydrogen atom or an alkyl group; A" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and n'is 0 to 2 Is an integer and m′ is 0 or 1. ]

In the general formulas (a2-r-1) to (a2-r-7), A″ has 1 to 5 carbon atoms which may contain an oxygen atom (—O—) or a sulfur atom (—S—). The alkylene group of 1 to 5 carbon atoms in A″ is preferably a linear or branched alkylene group, and is a methylene group, an ethylene group, an n-propylene group, Examples include isopropylene group and the like. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which —O— or —S— is present at the terminal or carbon atom of the alkylene group, and for example, —O—CH _{2 -, - CH 2 -O-CH} 2 -, - S-CH 2 -, - CH 2 -S-CH 2 - , and the like. As A″, an alkylene group having 1 to 5 carbon atoms or —O— is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is most preferable. Ra′ ²¹ is independently an alkyl group or an alkoxy group. A group, a halogen atom, a halogenated alkyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group.
The alkyl group for Ra′ ²¹ is preferably an alkyl group having 1 to 5 carbon atoms.
As the alkoxy group for Ra′ ^21, an alkoxy group having 1 to 6 carbon atoms is preferable.
The alkoxy group is preferably linear or branched. Specific examples thereof include groups in which an alkyl group mentioned as the alkyl group in Ra′ ²¹ and an oxygen atom (—O—) are linked.
Examples of the halogen atom in Ra′ ²¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
'Examples of the halogenated alkyl group for ^21, the Ra' Ra part or all of the hydrogen atoms of the alkyl group in ²¹ can be mentioned it has been substituted with the aforementioned halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.
R" is a hydrogen atom or an alkyl group, and the alkyl group of R" is preferably an alkyl group having 1 to 5 carbon atoms.

Specific examples of the groups represented by general formulas (a2-r-1) to (a2-r-7) are shown below.

In the present embodiment, the structural unit (a2) is preferably a group represented by the general formula (a2-r-1) or (a2-r-2), and the chemical formula (r-lc-1-1). Or the group respectively represented by (r-lc-2-7) is more preferable.

The “carbonate-containing cyclic group” refers to a cyclic group containing a ring (carbonate ring) containing —O—C(═O)—O— in its ring skeleton. The carbonate ring is counted as the first ring, and when it has only a carbonate ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure. The carbonate-containing cyclic group may be either a monocyclic group or a polycyclic group.
The carbonate ring-containing cyclic group is not particularly limited, and any group can be used. Specific examples include groups represented by general formulas (ax3-r-1) to (ax3-r-3) shown below.

［式中、Ｒａ’^ｘ３１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子またはアルキル基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子でありｑ’は０または１である。ｐ’は、０〜３の整数である。］

[ ^Wherein Ra′ ^x31 is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group or a cyano group. R" is a hydrogen atom or an alkyl group; A" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and q'is 0 or 1. is there. p'is an integer of 0-3. ]

A" in the general formulas (ax3-r-1) to (ax3-r-3) is the same as A" in the general formula (a2-r-1).
The alkyl group, alkoxy group, halogen atom, halogenated alkyl group, —COOR″, —OC(═O)R″, and hydroxyalkyl group for Ra′ ³¹ are each represented by the general formula (a2-r-1) to ( The same as those mentioned in the description of Ra′ ^{21 in} a2-r-7) can be mentioned.

Specific examples of the groups represented by general formulas (ax3-r-1) to (ax3-r-3) are shown below.

The "heterocyclic group" other than the above means a cyclic group containing one or more atoms other than carbon in addition to carbon, and has the chemical formulas (r-hr-1) to (r-hr-16) described later. And a nitrogen-containing heterocyclic group and the like. Examples of the nitrogen-containing heterocyclic group include cycloalkyl groups having 3 to 8 carbon atoms which may be substituted with 1 or 2 oxo groups. Preferable examples of the nitrogen-containing cycloalkyl group include 2,5-dioxopyrrolidine and groups in which one or more hydrogen atoms have been removed from 2,6-dioxopiperidine.

The structural unit (a2) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a2), the proportion of the structural unit (a2) is preferably 1 to 80 mol% with respect to the total of all the structural units constituting the component (A1), It is more preferably from 5 to 70 mol %, further preferably from 10 to 65 mol %, particularly preferably from 10 to 60 mol %. When it is at least the lower limit value, the effect of containing the structural unit (a2) will be sufficiently obtained, and when it is at most the upper limit value, it will be possible to balance with other structural units, and various lithographic properties and patterns will be obtained. Good shape.

(Structural unit (a3))
The structural unit (a3) is a structural unit containing a polar group-containing aliphatic hydrocarbon group (excluding those corresponding to the structural units (a1) and (a2) described above).
It is considered that the component (A1) having the structural unit (a3) enhances the hydrophilicity of the component (A) and contributes to the improvement of the resolution.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, and a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom, and the hydroxyl group is particularly preferable.
Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be a monocyclic group or a polycyclic group, and can be appropriately selected and used from, for example, a large number of proposals for resins for resist compositions for ArF excimer lasers. The cyclic group is preferably a polycyclic group, and more preferably has 7 to 30 carbon atoms.
Among them, a structural unit derived from an acrylate ester containing an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of hydrogen atoms of a hydroxyl group, a cyano group, a carboxy group, or an alkyl group is substituted with a fluorine atom. Is more preferable. Examples of the polycyclic group include groups in which two or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane and the like. Specific examples include groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, a group in which two or more hydrogen atoms are removed from adamantane, a group in which two or more hydrogen atoms are removed from norbornane, and a group in which two or more hydrogen atoms are removed from tetracyclododecane are Industrially preferred.

The structural unit (a3) is not particularly limited as long as it contains a polar group-containing aliphatic hydrocarbon group, and any unit can be used.
The structural unit (a3) is a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and includes a polar group-containing aliphatic hydrocarbon group. Structural units are preferred.
As the structural unit (a3), when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, it is derived from hydroxyethyl ester of acrylic acid. When the hydrocarbon group is a polycyclic group, a structural unit represented by the following general formula (a3-1), a structural unit represented by the general formula (a3-2), The structural unit represented by general formula (a3-3) is mentioned as a preferable example.

［一般式（ａ３−１）〜（ａ３−３）中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基であり、ｊは１〜３の整数であり、ｋは１〜３の整数であり、ｔ’は１〜３の整数であり、ｌは１〜５の整数であり、ｓは１〜３の整数である。］

[In general formulas (a3-1) to (a3-3), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and j is an integer of 1 to 3] , K is an integer of 1 to 3, t'is an integer of 1 to 3, l is an integer of 1 to 5, and s is an integer of 1 to 3. ]

In general formulas (a3-1) to (a3-3), the description regarding R is the same as above.
In general formula (a3-1), j is preferably 1 or 2, and more preferably 1. When j is 2, the hydroxyl group is preferably bonded to the 3rd and 5th positions of the adamantyl group. When j is 1, it is preferable that the hydroxyl group be bonded to the 3-position of the adamantyl group.
j is preferably 1, and particularly preferably a hydroxyl group bonded to the 3-position of the adamantyl group.

In general formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5th or 6th position of the norbornyl group.
In general formula (a3-3), t′ is preferably 1. It is preferable that l is 1. It is preferable that s is 1. These preferably have a 2-norbornyl group or a 3-norbornyl group bonded to the terminal of the carboxy group of acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5th or 6th position of the norbornyl group.

The structural unit (a3) contained in the component (A1) may be one type or two or more types.
In the component (A1), the proportion of the structural unit (a3) is preferably 5 to 50 mol %, more preferably 5 to 40 mol% based on the total of all the structural units constituting the resin component (A1). It is preferably 5 to 25 mol %, and more preferably 5 to 25 mol %.
When the ratio of the structural unit (a3) is at least the lower limit value, the effect of containing the structural unit (a3) is sufficiently obtained, and when the ratio is at most the upper limit value, it is balanced with other structural units. It will be easier.

(Structural unit (a4))
The structural unit (a4) is a structural unit containing an acid non-dissociable cyclic group. When the component (A1) has the structural unit (a4), the dry etching resistance of the formed resist pattern is improved. Further, the hydrophobicity of the component (A1) is increased. It is considered that the improvement of the hydrophobicity contributes to the improvement of the resolution, the resist pattern shape, etc., especially in the case of the organic solvent development.
The “acid non-dissociable cyclic group” in the structural unit (a4) means that when an acid is generated from the component (B) described below by exposure, it does not dissociate even when the acid acts, and is directly present in the structural unit. It is the remaining cyclic group.
As the structural unit (a4), for example, a structural unit derived from an acrylate ester containing an acid non-dissociable aliphatic cyclic group is preferable. Examples of the cyclic group are the same as those exemplified in the case of the structural unit (a1) described above, for ArF excimer laser, KrF excimer laser (preferably for ArF excimer laser), etc. A large number of those conventionally known as those used as the resin component of the resist composition can be used.
In particular, at least one selected from a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group is preferable in terms of industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
Specific examples of the structural unit (a4) include structural units represented by any of general formulas (a4-1) to (a4-7) shown below.

［式（ａ４−１）〜（ａ４−７）中、Ｒ^αは、水素原子、メチル基またはトリフルオロメチル基を示す。］

[In the formulas (a4-1) to (a4-7), R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group. ]

The structural unit (a4) contained in the component (A1) may be one type or two or more types.
When the structural unit (a4) is contained in the component (A1), the proportion of the structural unit (a4) is preferably 1 to 30 mol% with respect to the total of all structural units constituting the component (A1), It is more preferably 10 to 20 mol %.

The component (A1) is
A copolymer having (a1) and (a10),
A copolymer having (a1) and (a12),
A copolymer having (a1) and (a9),
A copolymer having (a10) and (a12),
A copolymer having (a1), (a2) and (a10),
Is preferred.

The component (A1) is obtained by polymerizing a monomer that induces each structural unit by known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN) and dimethyl azobisisobutyrate. be able to.
Further, as the component (A1), a chain transfer agent such as HS—CH ₂ —CH ₂ —CH ₂ —C(CF ₃ ) ₂ —OH is used in combination during the above-mentioned polymerization, whereby -C and _{(CF 3)} 2 -OH group may be introduced into the. As described above, the copolymer having a hydroxyalkyl group in which a part of hydrogen atoms of the alkyl group is substituted with a fluorine atom is introduced, the development defects are reduced and LER (line edge roughness: uneven unevenness of line side wall) is obtained. Is effective in reducing

In the present embodiment, the weight average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of the component (A1) is not particularly limited and is preferably 1,000 to 50,000, more preferably 1,500 to 30,000. 2000-20000 is the most preferable. When it is at most the upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist, and when it is at least the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are good.

As the component (A1), one type may be used alone, or two or more types may be used in combination.
The proportion of the component (A1) in the base material component (A) is preferably 25% by mass or more, more preferably 50% by mass, further preferably 75% by mass, based on the total mass of the base material component (A). It may be% by mass. When the proportion is 25% by mass or more, the lithography characteristics are further improved.

In the present embodiment, as the component (A), one type may be used alone, or two or more types may be used in combination.
In the present embodiment, the content of the component (A) may be adjusted according to the resist film thickness to be formed and the like.

[(B1) component]
The acid generator component (B1) contained in the positive resist composition of the present invention and generating an acid upon exposure will be described.
The component (B1) is an acid generator component that generates an acid upon exposure, and is characterized by containing the compound (m) represented by the general formula (m0). In the first embodiment, the compound (m) is preferably a compound represented by the following general formula (m0-1).

［一般式（ｍ０−１）中、
Ｚ^０１〜Ｚ^０４は、それぞれ独立に電子吸引性の置換基であり、
Ｒｂ^２１及びＲｂ^２２は、それぞれ独立に、置換基を有していてもよいアルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基であり（但し、Ｒｂ^２１及びＲｂ^２２が有していてもよい置換基に電子吸引性の置換基は含まない。）、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数であり、
Ｘ１^-は基材成分（Ａ）のアルカリ現像液に対する溶解性を増大させることができる酸を発生し得る有機アニオンである。］

[In the general formula (m0-1),
Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing substituent,
Rb ²¹ and Rb ²² are each independently an alkyl group which may have a substituent, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² Does not include an electron-withdrawing substituent.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3,
X1 ⁻ is an organic anion capable of generating an acid capable of increasing the solubility of the base component (A) in an alkali developing solution. ]

In general formula (m0-1), the description regarding Z ^{01 to} Z ⁰⁴ , Rb ²¹ , Rb ²² , Rb ¹ , n1 and n2 is the same as the above description in general formula (m0).
In the general formula (m0-1), X1 ⁻ is an organic anion capable of generating an acid capable of increasing the solubility of the base component (A) in an alkali developing solution.
X1 ⁻ may be any organic anion capable of generating an acid having an acid strength capable of increasing the solubility of the base component (A) in an alkali developing solution.
On the other hand, the positive resist composition of the first embodiment contains the component (D1) described later. As will be described in detail later, the component (D1) is a component that acts as a quencher that traps the acid generated from the component (B1). Therefore, the anion part X1 ⁻ of the compound (m0-1) constituting the component (B1) is an anion part capable of generating an acid that becomes a strong acid with respect to the component (D1).

For example, an acid dissociation constant (pKa) is used as an index of acid strength for description.
In the present embodiment, the “acid dissociation constant (pKa)” refers to one generally used as an index showing the acid strength of the target substance. In addition, pKa in the present specification is a value under a temperature condition of 25° C. Further, the pKa value can be obtained by measuring by a known method. Further, a calculated value using a known software such as “ACD/Labs” (trade name, manufactured by Advanced Chemistry Development) can be used.

In the general formula (m0-1), the lower limit value of the acid dissociation constant (pKa) of the acid generated from X1 ⁻ is not particularly limited and is substantially about −15. The upper limit of the acid dissociation constant (pKa) of the acid generated from X1 ⁻ may be a value lower than the acid dissociation constant (pKa) of the acid generated from the component (D1), and for example, 1.5 to 2.0. It is a value of the degree. X1 ^- acid dissociation constant of the acid generated from the (pKa) even if on the order of 1.5 to 2.0, it is possible to increase the solubility in an alkali developing solution of the base material component (A).

More specifically, in the general formula (m0-1), X1 ⁻ is preferably an anion represented by any of the following general formulas (m-an-1) to (m-an-3).

［一般式（ｍ−ａｎ−１）〜（ｍ−ａｎ−３）中、
Ｒ^１０１、Ｒ^１０４〜Ｒ^１０８はそれぞれ独立に置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基である。
Ｒ^１０４、Ｒ^１０５は、相互に結合して環を形成していてもよい。
Ｒ^１０６〜Ｒ^１０７のいずれか２つは、相互に結合して環を形成していてもよい。
Ｒ^１０２はフッ素原子または炭素数１〜５のフッ素化アルキル基である。
Ｙ^１０１は単結合または酸素原子を含む２価の連結基である。
Ｖ^１０１〜Ｖ^１０３はそれぞれ独立に単結合、アルキレン基、またはフッ素化アルキレン基である。Ｌ^１０１〜Ｌ^１０２はそれぞれ独立に単結合または酸素原子である。Ｌ^１０３〜Ｌ^１０５はそれぞれ独立に単結合、−ＣＯ−又は−ＳＯ_２−である。
ａｎ１は０又は１である。］

[In the general formulas (m-an-1) to (m-an-3),
R ¹⁰¹ and R ^{104 to} R ¹⁰⁸ may each independently have a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is a chain alkenyl group.
R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring.
Any two of R ^{106 to} R ¹⁰⁷ may be bonded to each other to form a ring.
R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms.
Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom.
V ^{101 to} V ¹⁰³ are each independently a single bond, an alkylene group, or a fluorinated alkylene group. L ^{101 to} L ¹⁰² are each independently a single bond or an oxygen atom. L ^{103 to} L ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —.
an1 is 0 or 1. ]

-General formula (m-an-1)
In formula (m-an-1), R ¹⁰¹ has a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or a substituent. It may be a chain alkenyl group.

(A cyclic group which may have a substituent in R ¹⁰¹ )
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
The aromatic hydrocarbon group for R ¹⁰¹ is an aromatic hydrocarbon ring mentioned as the divalent aromatic hydrocarbon group for Va ¹ in the general formula (a1-1), or an aromatic compound containing two or more aromatic rings. And an aryl group obtained by removing one hydrogen atom from the above, and a phenyl group and a naphthyl group are preferable.
The cyclic aliphatic hydrocarbon group for R ¹⁰¹ is one obtained by removing one hydrogen atom from the monocycloalkane or polycycloalkane mentioned for the divalent aliphatic hydrocarbon group for Va ¹ of the general formula (a1-1). Examples thereof include an adamantyl group and a norbornyl group.
The cyclic hydrocarbon group for R ¹⁰¹ may contain a hetero atom such as a heterocycle, and is specifically represented by the general formulas (a2-r-1) to (a2-r-7). The lactone-containing cyclic group, the —SO ₂ —-containing cyclic group represented by each of the general formulas (a5-r-1) to (a5-r-4), and the following chemical formula (r-hr-1 ) To (r-hr-16).

Examples of the substituent in the cyclic hydrocarbon group of R ¹⁰¹ include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group and the like.
The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group, and a methoxy group. Most preferred is the group ethoxy.
Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
As the halogenated alkyl group as a substituent, some or all of hydrogen atoms such as an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group are the above A group substituted with a halogen atom may be mentioned.

(A chain alkyl group which may have a substituent in R ¹⁰¹ )
The chain alkyl group for R ¹⁰¹ may be linear or branched.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group. Group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group and the like.
The branched chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples thereof include a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group and a 4-methylpentyl group.

(A chain alkenyl group which may have a substituent in R ¹⁰¹ )
The chain alkenyl group for R ¹⁰¹ may be linear or branched and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 and even more preferably 2 to 4 Is particularly preferable. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group) and a butynyl group. Examples of the branched alkenyl group include a 1-methylpropenyl group and a 2-methylpropenyl group.
Among the above, the chain alkenyl group is particularly preferably a propenyl group.

Examples of the substituent in the chain alkyl group or alkenyl group for R ¹⁰¹ include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic group for R ¹⁰¹ above. Can be mentioned.

Among them, R ¹⁰¹ is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and each of the above general formulas (a2-r-1) to (a2-r-7). The lactone-containing cyclic group and the —SO ₂ — containing cyclic group represented by each of the general formulas (a5-r-1) to (a5-r-4) are preferable.

In formula (m-an-1), Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom.
When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, Y ¹⁰¹ may contain an atom other than an oxygen atom. Examples of the atom other than the oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom and a nitrogen atom.
Examples of the divalent linking group containing an oxygen atom include an oxygen atom (ether bond: —O—), an ester bond (—C(═O)—O—), an oxycarbonyl group (—O—C(═O). )-), amide bond (-C(=O)-NH-), carbonyl group (-C(=O)-), carbonate bond (-O-C(=O)-O-), etc. Examples include a combination of a non-hydrocarbon-based oxygen atom-containing linking group and an alkylene group. A sulfonyl group (—SO ₂ —) may be further linked to the combination. Examples of the combination include linking groups represented by the following general formulas (y-al-1) to (y-al-7).

［一般式（ｙ−ａｌ−１）〜（ｙ−ａｌ−７）中、Ｖ’^１０１は単結合または炭素数１〜５のアルキレン基であり、Ｖ’^１０２は炭素数１〜３０の２価の飽和炭化水素基である。］

[In general formulas (y-al-1) to (y-al-7), V′ ¹⁰¹ is a single bond or an alkylene group having 1 to 5 carbon atoms, and V′ ¹⁰² is a divalent group having 1 to 30 carbon atoms. Is a saturated hydrocarbon group. ]

The divalent saturated hydrocarbon group for V′ ¹⁰² is preferably an alkylene group having 1 to 30 carbon atoms.

The alkylene group for V′ ¹⁰¹ and V′ ¹⁰² may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferable.
As the alkylene group for V′ ¹⁰¹ and V′ ¹⁰² , specifically, a methylene group [—CH ₂ —]; —CH(CH ₃ )—, —CH(CH ₂ CH ₃ )—, and —C(CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as ethylene group _{[-CH 2 CH 2 -];} - CH (CH 3) CH 2 -, - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH ₃ ) Alkyl ethylene group such as CH ₂ —; trimethylene group (n-propylene group) [—CH ₂ CH ₂ CH ₂ —]; —CH(CH ₃ )CH ₂ CH ₂ —, —CH ₂ CH(CH ₃ ). tetramethylene group _{[-CH 2 CH 2 CH 2 CH} 2 -];; - CH 2 alkyltetramethylene groups such as _{- CH (CH 3) CH 2} CH 2 CH 2 -, - CH 2 CH (CH 3) CH 2 CH ₂ - and the like alkyl tetramethylene group; pentamethylene group _{[-CH 2 CH 2 CH 2 CH} 2 CH 2 -] , and the like.
Moreover, a part of the methylene groups in the alkylene group in V′ ¹⁰¹ or V′ ¹⁰² may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a divalent group obtained by removing one hydrogen atom from the cyclic aliphatic hydrocarbon group represented by Ra′ ^{3 in} the formula (a1-r-1), and is a cyclohexylene group. , 1,5-adamantylene group or 2,6-adamantylene group is more preferred.

As Y ¹⁰¹ , a divalent linking group having an ester bond or an ether bond is preferable, and a linking group represented by each of the general formulas (y-al-1) to (y-al-5) is preferable.

In general formula (m-an-1), V ¹⁰¹ is a single bond, an alkylene group, or a fluorinated alkylene group. The alkylene group and fluorinated alkylene group for V ¹⁰¹ preferably have 1 to 4 carbon atoms. ^Examples of the fluorinated alkylene group for V ¹⁰¹ include groups in which some or all of the hydrogen atoms of the alkylene group for V ¹⁰¹ are substituted with fluorine atoms. Among them, V ¹⁰¹ is preferably a single bond or a fluorinated alkylene group having 1 to 4 carbon atoms.

In formula (m-an-1), R ¹⁰² represents a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R ¹⁰² is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

Specific examples of the anion moiety represented by the general formula (m-an-1) include fluorinated alkylsulfonate anions such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion when Y ¹⁰¹ is a single bond. When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, an anion represented by any of the following general formulas (an-1) to (an-3) can be given.

［式中、Ｒ”^１０１は、置換基を有していてもよい脂肪族環式基、前記化学式（ｒ−ｈｒ−１）〜（ｒ−ｈｒ−６）でそれぞれ表される基、又は置換基を有していてもよい鎖状のアルキル基であり；Ｒ”^１０２は、置換基を有していてもよい脂肪族環式基、前記一般式（ａ２−ｒ−１）〜（ａ２−ｒ−７）でそれぞれ表されるラクトン含有環式基、又は前記一般式（ａ５−ｒ−１）〜（ａ５−ｒ−４）でそれぞれ表される−ＳＯ_２−含有環式基であり；Ｒ”^１０３は、置換基を有していてもよい芳香族環式基、置換基を有していてもよい脂肪族環式基、又は置換基を有していてもよい鎖状のアルケニル基であり；Ｖ”^１０１は、フッ素化アルキレン基であり；Ｌ”^１０１は、−Ｃ（＝Ｏ）−又は−ＳＯ_２−であり；ｖ”はそれぞれ独立に０〜３の整数であり、ｑ”はそれぞれ独立に１〜２０の整数であり、ｎ”は０または１である。］

[In the formula, R" ¹⁰¹ is an aliphatic cyclic group which may have a substituent, a group represented by each of the chemical formulas (r-hr-1) to (r-hr-6), or a substituent. Is a chain alkyl group which may have a group; R″ ¹⁰² is an aliphatic cyclic group which may have a substituent, and the general formulas (a2-r-1) to (a2- a lactone-containing cyclic group represented by each of r-7) or a -SO ₂ -containing cyclic group represented by each of the general formulas (a5-r-1) to (a5-r-4); R″ ¹⁰³ is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent. V″ ¹⁰¹ is a fluorinated alkylene group; L″ ¹⁰¹ is —C(═O)— or —SO ₂ —; v″ is each independently an integer of 0 to 3; "Independently represents an integer of 1 to 20, and n" is 0 or 1. ]

The aliphatic cyclic group which may have a substituent of R″ ¹⁰¹ , R″ ¹⁰² and R″ ¹⁰³ is preferably the group exemplified as the cyclic aliphatic hydrocarbon group for R ¹⁰¹ . Examples of the substituent include those similar to the substituent that may substitute the cyclic aliphatic hydrocarbon group for R ¹⁰¹ .

The aromatic cyclic group which may have a substituent in R″ ¹⁰³ is preferably the group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R ¹⁰¹ above. , R ¹⁰¹ may be the same as the substituent which may substitute the aromatic hydrocarbon group.

The chain alkyl group which may have a substituent in R″ ¹⁰¹ is preferably the group exemplified as the chain alkyl group in the above R ^101. The chain alkyl group which may have a substituent in R″ ¹⁰³ The chain alkenyl group which may be mentioned is preferably the group exemplified as the chain alkenyl group for R ¹⁰¹ . V″ ¹⁰¹ is preferably a fluorinated alkylene group having 1 to 3 carbon atoms, and particularly preferably —CF ₂ —, —CF ₂ CF ₂ —, —CHFCF ₂ —, and —CF(CF ₃ )CF ₂ —. _{, -CH (CF 3) CF 2} - it is.

In the general formula (m-an-1), an1 is 0 or 1.

-General formula (m-an-2)
In formula (m-an-2), R ¹⁰⁴ and R ¹⁰⁵ each independently represent a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, Alternatively, it is a chain alkenyl group which may have a substituent, and examples thereof include the same ones as R ¹⁰¹ in the general formula (m-an-1). However, R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring.
R ¹⁰⁴ and R ¹⁰⁵ are preferably chain alkyl groups that may have a substituent, and are linear or branched alkyl groups or linear or branched fluorinated alkyl groups. Is more preferable.
The chain-like alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and further preferably 1 to 3 carbon atoms. The carbon number of the chain alkyl group of R ¹⁰⁴ and R ¹⁰⁵ is preferably as small as possible within the range of the above carbon number for the reason that solubility in a resist solvent is also good. Further, in the chain alkyl group of R ¹⁰⁴ and R ¹⁰⁵ , as the number of hydrogen atoms substituted by fluorine atoms is larger, the strength of the acid is stronger, and the high-energy light of 200 nm or less or electron beams It is preferable because the transparency is improved. The ratio of fluorine atoms in the chain alkyl group, that is, the fluorination ratio is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are replaced with fluorine atoms. It is a perfluoroalkyl group.
In the general formula (m-an-2), V ¹⁰² and V ¹⁰³ each independently represent a single bond, an alkylene group, or a fluorinated alkylene group, and V ¹⁰² and V ¹⁰³ in the general formula (m-an-1) each represent V. ^{The same as 101} is mentioned.
In formula (m-an-2), L ^{101 to} L ¹⁰² each independently represent a single bond or an oxygen atom.

-General formula (m-an-3)
In formula (m-an-3), R ^{106 to} R ¹⁰⁸ each independently represent a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, Alternatively, it is a chain alkenyl group which may have a substituent, and examples thereof include the same ones as R ¹⁰¹ in the general formula (m-an-1).
L ^{103 to} L ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —.

As the component (B1), one type of the above-mentioned acid generator may be used alone, or two or more types may be used in combination.
In the present embodiment, when the resist composition contains the component (B1), the content of the component (B1) is preferably 0.5 to 60 parts by mass, and 1 to 50 parts by mass with respect to 100 parts by mass of the component (A). Parts is more preferable, and 1 to 40 parts by mass is even more preferable. By setting the content of the component (B1) within the above range, pattern formation is sufficiently performed. Further, the sensitivity when forming the resist pattern can be further increased.

[Photoreactive quencher (D1)]
The component (D1) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure from the component (B1).
The component (D1) in the present invention is a photoreactive quencher (D1) that is decomposed by exposure and loses acid diffusion controllability.

[(D1) component]
The component (D1) is not particularly limited as long as it decomposes upon exposure and loses acid diffusion controllability, and is a compound represented by the following general formula (d1-1) (hereinafter referred to as “(d1-1) component”). ), a compound represented by the following general formula (d1-2) (hereinafter referred to as “(d1-2) component”) and a compound represented by the following general formula (d1-3) (hereinafter referred to as “(d1- 3) component”). One or more compounds selected from the group consisting of) are preferable.
The components (d1-1) to (d1-3) do not act as a quencher in the exposed area because they decompose and lose the acid diffusion controllability (basicity), but act as a quencher in the unexposed area.

［式中、Ｒｄ^１〜Ｒｄ^４は置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基である。ただし、式（ｄ１−２）中のＲｄ^２における、Ｓ原子に隣接する炭素原子にはフッ素原子は結合していないものとする。Ｙｄ^１は単結合、または２価の連結基である。Ｍ^ｍ＋はそれぞれ独立にｍ価の有機カチオンである。］

[In the formula, Rd ^{1 to} Rd ⁴ are each a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent. Is an alkenyl group. However, a fluorine atom is not bonded to the carbon atom adjacent to the S atom in Rd ² in formula (d1-2). Yd ¹ is a single bond or a divalent linking group. M ^m+ is independently an m-valent organic cation. ]

{(D1-1) component}
Anion part In formula (d1-1), Rd ¹ has a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. Is also a chain alkenyl group, and examples thereof include those similar to R ¹⁰¹ .
Among these, Rd ¹ may have an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a substituent. A chain alkyl group is preferred. The substituent which these groups may have is a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom or a fluorinated alkyl group, and the above general formulas (a2-r-1) to (a2-r-7). ), a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof. When it contains an ether bond or an ester bond as a substituent, it may be via an alkylene group, and a linking group represented by each of the following formulas (y-al-1) to (y-al-5) is preferable.
As the aromatic hydrocarbon group, an aryl group such as a phenyl group or a naphthyl group is more preferable.
The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.
The chain hydrocarbon group is preferably a chain alkyl group. The chain alkyl group preferably has 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. Group, linear alkyl group such as decyl group; 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group A branched alkyl group such as a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group and a 4-methylpentyl group.

When the chain alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the carbon number of the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8 and 1 The fluorinated alkyl group with 4 to 4 being more preferable may contain an atom other than a fluorine atom. Examples of the atom other than the fluorine atom include an oxygen atom, a carbon atom, a hydrogen atom, a sulfur atom and a nitrogen atom.
Rd ¹ is preferably a fluorinated alkyl group in which some or all of the hydrogen atoms constituting the linear alkyl group are substituted with fluorine atoms, and the hydrogen atom of the linear alkyl group is preferably It is preferable that all are fluorinated alkyl groups substituted with fluorine atoms (linear perfluoroalkyl groups).

Preferred specific examples of the anion moiety of the component (d1-1) are shown below.

In the cation moiety formula (d1-1), M ^m+ is an m-valent organic cation (excluding the cation in the compound (D0) as in M′ ^m+ described later).
The organic cation of M ^m+ is not particularly limited, and examples thereof include those similar to the cations represented by the following general formulas (ca-1) to (ca-4), respectively. Cations represented by 1) to (ca-1-63) are preferable.
As the component (d1-1), one type may be used alone, or two or more types may be used in combination.

{(D1-2) component}
· During anion formula (d1-2), Rd ² is has an optionally substituted cyclic group which may have a substituent chain alkyl group or a substituted group, It may be a chain alkenyl group which may be the same as R ¹⁰¹ .
However, a fluorine atom is not bonded to the carbon atom adjacent to the S atom in Rd ² (not fluorine-substituted). Thereby, the anion of the component (d1-2) becomes an appropriate weak acid anion, and the quenching ability of the component (D) is improved.
Rd ² is preferably an aliphatic cyclic group which may have a substituent, and is a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like. (It may have a substituent); More preferably, it is a group obtained by removing one or more hydrogen atoms from camphor or the like.
The hydrocarbon group of Rd ² may have a substituent, and as the substituent, the hydrocarbon group in Rd ¹ of the above formula (d1-1) (aromatic hydrocarbon group, aliphatic hydrocarbon group) The same as the substituent which may have.

Specific preferred examples of the anion moiety of the component (d1-2) are shown below.

-Cation part In formula (d1-2), Mm ⁺ is an m-valent organic cation and is the same as Mm ⁺ in the formula (d1-1).
As the component (d1-2), one type may be used alone, or two or more types may be used in combination.

{(D1-3) component}
During Anion formula (d1-3), Rd ³ is have an optionally substituted cyclic group which may have a substituent chain alkyl group or a substituted group, Is a chain alkenyl group which may be the same as R ^101, and is preferably a cyclic group containing a fluorine atom, a chain alkyl group, or a chain alkenyl group. Among them, a fluorinated alkyl group is preferable, and a group similar to the fluorinated alkyl group for Rd ¹ is more preferable.

In the formula (d1-3), Rd ⁴ may have a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is a chain alkenyl group, and examples thereof include those similar to R ¹⁰¹ .
Of these, an alkyl group which may have a substituent, an alkoxy group, an alkenyl group and a cyclic group are preferable.
The alkyl group for Rd ⁴ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group. , Tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. A part of hydrogen atoms of the alkyl group of Rd ⁴ may be substituted with a hydroxyl group, a cyano group or the like.
The alkoxy group for Rd ⁴ is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n- Examples thereof include butoxy group and tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferable.

Examples of the alkenyl group for Rd ⁴ include those similar to the above R ^101, and a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, and a 2-methylpropenyl group are preferable. These groups may further have, as a substituent, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

Examples of the cyclic group for Rd ⁴ include the same groups as those for R ¹⁰¹ described above, and one or more hydrogen atoms are excluded from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane. Preferred are alicyclic groups and aromatic groups such as phenyl and naphthyl groups. When Rd ⁴ is an alicyclic group, the resist composition is well dissolved in the organic solvent, and thus the lithographic properties are good. Further, when Rd ⁴ is an aromatic group, the resist composition is excellent in light absorption efficiency in lithography using EUV or the like as an exposure light source, and sensitivity and lithographic characteristics are good.

In formula (d1-3), Yd ¹ is a single bond or a divalent linking group.
The divalent linking group for Yd ¹ is not particularly limited, but may be a divalent hydrocarbon group which may have a substituent (aliphatic hydrocarbon group, aromatic hydrocarbon group), a hetero atom-containing 2 Examples thereof include a valent linking group. Examples of each of these are the same as those mentioned in the description of the divalent linking group for Ya ²¹ in the formula (a2-1).
Yd ¹ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, further preferably a methylene group or an ethylene group.

Specific preferred examples of the anion moiety of the component (d1-3) are shown below.

-Cation part In formula (d1-3), Mm ⁺ is an m-valent organic cation and is the same as Mm ⁺ in the formula (d1-1).
As the component (d1-3), one type may be used alone, or two or more types may be used in combination.

As the component (D1), only one type of the above-mentioned components (d1-1) to (d1-3) may be used, or two or more types may be used in combination.
The content of the component (D1) is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and more preferably 1 to 8 with respect to 100 parts by mass of the component (A). More preferably, it is parts by mass.
When the content of the component (D1) is at least the preferred lower limit, particularly good lithographic properties and resist pattern shapes will be obtained. On the other hand, when it is at most the upper limit value, the sensitivity can be maintained well and the throughput is also excellent.

The method for producing the components (d1-1) to (d1-3) is not particularly limited, and any known method can be used.

The content of the component (D1) is preferably 0.5 to 15.0 parts by mass, more preferably 0.5 to 10.0 parts by mass, relative to 100 parts by mass of the component (A). , 1.0 to 8.0 parts by mass is more preferable. When it is at least the lower limit value of the above range, particularly good lithographic properties and resist pattern shape are obtained. When it is at most the upper limit of the above range, the sensitivity can be favorably maintained and the throughput is also excellent.

((D1-2) component)
The component (D1) may contain a nitrogen-containing organic compound component (hereinafter referred to as the component (D1-2)) that does not correspond to the component (D1).
The component (D1-2) is not particularly limited as long as it acts as an acid diffusion controller and does not correspond to the component (D1), and any known component may be used. Of these, aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines are preferred.
The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms.
Examples of the aliphatic amine include amines (alkylamines or alkylalcoholamines) or cyclic amines in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group having 12 or less carbon atoms or a hydroxyalkyl group.
Specific examples of the alkylamine and the alkylalcoholamine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine; diethylamine, di-n-propylamine, di-amine. Dialkylamines such as -n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine , Tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine and like trialkylamines; diethanolamine, triethanolamine, diisopropanolamine, tri Examples include alkyl alcohol amines such as isopropanol amine, di-n-octanol amine, and tri-n-octanol amine. Among these, a trialkylamine having 5 to 10 carbon atoms is more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

Examples of the cyclic amine include a heterocyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
The aliphatic polycyclic amine preferably has 6 to 10 carbon atoms, and specifically, 1,5-diazabicyclo[4.3.0]-5-nonene and 1,8-diazabicyclo[5. 4.0]-7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane and the like can be mentioned.

Other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2 -(1-Methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxy) Examples thereof include ethoxy)ethoxy}ethyl]amine and triethanolamine triacetate, with triethanolamine triacetate being preferred.

An aromatic amine may be used as the component (D2).
Examples of aromatic amines include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxy. Carbonyl pyrrolidine etc. are mentioned.

The component (D1-2) may be used alone or in combination of two or more.
The component (D1-2) is usually used in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the component (A). By setting the content within the above range, the resist pattern shape, the stability with leaving and the like are improved.

As the component (D), one type may be used alone, or two or more types may be used in combination.
When the resist composition of the present invention contains the component (D), the content of the component (D) is preferably 0.1 to 15 parts by mass, and 0.3 to 100 parts by mass of the component (A). It is more preferably 12 parts by mass, further preferably 0.5 to 12 parts by mass. When it is at least the lower limit value of the above range, the lithographic properties such as LWR are further improved when the composition is used as a resist composition. Further, a better resist pattern shape can be obtained. When it is at most the upper limit of the above range, the sensitivity can be favorably maintained and the throughput is also excellent.

[Specific compound (E)]
In the present embodiment, the resist composition contains, as an optional component, an organic carboxylic acid, and an oxo acid of phosphorus and its derivative for the purpose of preventing sensitivity deterioration and improving resist pattern shape, leaving stability over time, and the like. At least one compound (E) selected from the group consisting of (E) (hereinafter referred to as “component (E)”) can be contained.
As the organic carboxylic acid, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
Examples of phosphorus oxo acids include phosphoric acid, phosphonic acid, and phosphinic acid. Of these, phosphonic acid is particularly preferable.
Examples of phosphorus oxo acid derivatives include esters in which the hydrogen atom of the above oxo acid is substituted with a hydrocarbon group, and the like, and examples of the hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and 6 to 6 carbon atoms. The aryl group of 15 and the like can be mentioned.
Examples of the phosphoric acid derivative include phosphoric acid esters such as phosphoric acid di-n-butyl ester and phosphoric acid diphenyl ester.
Examples of the derivative of phosphonic acid include phosphonic acid dimethyl ester, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester.
Examples of the phosphinic acid derivative include phosphinic acid ester and phenylphosphinic acid.
As the component (E), one type may be used alone, or two or more types may be used in combination.
The component (E) is generally used in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the component (A).

[(F) component]
In the present embodiment, the resist composition may contain a fluorine additive (hereinafter referred to as “component (F)”) in order to impart water repellency to the resist film.
Examples of the component (F) are disclosed in JP2010-002870A, JP2010-032994A, JP2010-277043A, JP2011-13569A, and JP2011-128226A. The fluorine-containing polymer compounds described can be used.
Specific examples of the component (F) include polymers having a structural unit (f1) represented by general formula (f1-1) shown below. As the polymer, a polymer (homopolymer) consisting only of the structural unit (f1) represented by the following general formula (f1-1); the structural unit (f1) represented by the following general formula (f1-1) And a copolymer of the structural unit (a1); a structural unit (f1) represented by the following general formula (f1-1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit ( It is preferably a copolymer with a1). Here, as the structural unit (a1) copolymerized with the structural unit (f1) represented by the following general formula (f1-1), 1-ethyl-1-cyclooctyl (meth)acrylate or the general formula The structural unit represented by (a1-2-01) is preferable.

［一般式（ｆ１−１）中、Ｒは水素原子、炭素数１〜５のアルキル基または炭素数１〜５のハロゲン化アルキル基である。Ｒｆ^１０２およびＲｆ^１０３はそれぞれ独立して水素原子、ハロゲン原子、炭素数１〜５のアルキル基、又は炭素数１〜５のハロゲン化アルキル基を表し、Ｒｆ^１０２およびＲｆ^１０３は同じであっても異なっていてもよい。ｎｆ^１は１〜５の整数であり、Ｒｆ^１０１はフッ素原子を含む有機基である。］

[In general formula (f1-1), R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Rf ¹⁰² and Rf ¹⁰³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and Rf ¹⁰² and Rf ¹⁰³ may be the same. It may be different. nf ¹ is an integer of ¹ to 5, and Rf ¹⁰¹ is a fluorine atom-containing organic group. ]

In general formula (f1-1), R has the same meaning as described above. R is preferably a hydrogen atom or a methyl group.
In the general formula (f1-1), examples of the halogen atom of Rf ¹⁰² and Rf ¹⁰³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable. Examples of the alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ are the same as those of the alkyl group having 1 to 5 carbon atoms of R above, and a methyl group or an ethyl group is preferable. Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Can be mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable. Among them, Rf ¹⁰² and Rf ¹⁰³ are preferably a hydrogen atom, a fluorine atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom, a fluorine atom, a methyl group or an ethyl group is preferable.
In general formula (f1-1), nf ¹ is an integer of ¹ to 5, preferably an integer of 1 to 3, and more preferably 1 or 2.

In general formula (f1-1), Rf ¹⁰¹ is an organic group containing a fluorine atom, and is preferably a hydrocarbon group containing a fluorine atom.
The hydrocarbon group containing a fluorine atom may be linear, branched or cyclic, and preferably has 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms. Particularly preferably, the carbon number is 1 to 10.
Further, in the hydrocarbon group containing a fluorine atom, 25% or more of hydrogen atoms in the hydrocarbon group are preferably fluorinated, more preferably 50% or more, and more preferably 60% or more. Fluorination is particularly preferable because the hydrophobicity of the resist film during immersion exposure increases.
Among them, as Rf ¹⁰¹ , a fluorinated hydrocarbon group having 1 to 5 carbon atoms is particularly preferable, and a methyl group, —CH ₂ —CF ₃ , —CH ₂ —CF ₂ —CF ₃ , or —CH(CF ₃ ) _{2 is used. , -CH} 2 _-CH 2 _-CF 3, and most preferably _{-CH 2 -CH 2 -CF 2 -CF 2} -CF 2 -CF 3.

The weight average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of the component (F) is preferably from 1,000 to 50,000, more preferably from 5,000 to 40,000, and most preferably from 10,000 to 30,000. When it is at most the upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist, and when it is at least the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are good.
The dispersity (Mw/Mn) of the component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5.

As the component (F), one type may be used alone, or two or more types may be used in combination.
The component (F) is usually used in a proportion of 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A).

In the present embodiment, the resist composition further includes a miscible additive if desired, for example, an additional resin for improving the performance of the resist film, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent. Agents, dyes, and the like can be appropriately added and contained.

[(S) component]
In the present embodiment, the resist composition can be produced by dissolving the material in an organic solvent (hereinafter sometimes referred to as the (S) component).
As the component (S), any component capable of dissolving each component to be used to form a uniform solution may be used, and any one of the conventionally known solvents for chemically amplified resists may be used. Two or more kinds can be appropriately selected and used.
For example, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone (2-heptanone), and methyl isopentyl ketone; ethylene glycol, diethylene glycol, propylene glycol, diketone. Polyhydric alcohols such as propylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, polyhydric alcohols or compounds having an ester bond Derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether and monobutyl ether or monophenyl ethers [among these, propylene glycol monomethyl ether acetate (PGMEA ), propylene glycol monomethyl ether (PGME) are preferred]; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxy. Esters such as methyl propionate and ethyl ethoxypropionate; anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, Examples thereof include aromatic organic solvents such as cymene and mesitylene, and dimethyl sulfoxide (DMSO).
These organic solvents may be used alone or as a mixed solvent of two or more kinds.
Among them, PGMEA, PGME, γ-butyrolactone and EL are preferable.
A mixed solvent obtained by mixing PGMEA and a polar solvent is also preferable. The compounding ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. It is preferably within the range.
More specifically, when EL or cyclohexanone is blended as the polar solvent, the mass ratio of PGMEA:EL or cyclohexanone is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. .. When PGME is blended as the polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and further preferably 3:7 to 7:. It is 3.
In addition, as the component (S), a mixed solvent of γ-butyrolactone with at least one selected from PGMEA and EL is also preferable. In this case, as the mixing ratio, the mass ratio of the former and the latter is preferably 70:30 to 95:5.
The amount of the component (S) used is not particularly limited, and is appropriately set according to the coating film thickness at a concentration that can be applied to a substrate or the like. Generally, the resist composition is used so that the solid content concentration is in the range of 1 to 20% by mass, preferably 2 to 15% by mass.

«Second embodiment»
A second embodiment of the present invention will be described.
The second embodiment is a positive resist composition in which an acid is generated by exposure and the solubility in an alkali developing solution is increased by the action of the acid, and the solubility in the alkali developing solution is increased by the action of the acid. A base material component (A) (hereinafter referred to as “(A) component”) and an acid generator component (B2) that generates an acid upon exposure (hereinafter referred to as “(B2) component”). And a photoreactive quencher (D2) (hereinafter, referred to as “(D2) component”) is contained, and the photoreactive quencher (D2) is represented by the general formula (m0). A positive resist composition containing the compound (m).
The positive resist composition of the second embodiment contains a photoreactive quencher (D2), and the component (D2) contains the compound (m) represented by the general formula (m0).
In the second embodiment, the compound (m0) functions as a photoreactive quencher. The photoreactive quencher (D2) acts as a quencher (acid diffusion controller) that traps the acid generated from the component (B2).

[(A) component]
The description of the component (A) in the second embodiment is the same as the description of the component (A) in the first embodiment.

[Component (B2)]
The component (B2) in the second embodiment will be described. The component (B2) is not particularly limited, and those which have been proposed as acid generators for chemically amplified resists can be used.
Examples of such an acid generator include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators such as bisalkyl or bisarylsulfonyldiazomethanes and poly(bissulfonyl)diazomethanes. There are various types such as an acid generator, a nitrobenzyl sulfonate-based acid generator, an iminosulfonate-based acid generator, and a disulfone-based acid generator. Among these, it is preferable to use an onium salt-based acid generator.

Examples of the onium salt-based acid generator include a compound represented by the following general formula (b-1) (hereinafter also referred to as “(b-1) component”) and a general formula (b-2). A compound (hereinafter, also referred to as “(b-2) component”) or a compound represented by the general formula (b-3) (hereinafter, also referred to as “(b-3) component”) can be used.

［一般式（ｂ−１）〜（ｂ−３）中、Ｒ^１０１、Ｒ^１０４〜Ｒ^１０８はそれぞれ独立に置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基である。Ｒ^１０４、Ｒ^１０５は、相互に結合して環を形成していてもよい。Ｒ^１０６〜Ｒ^１０７のいずれか２つは、相互に結合して環を形成していてもよい。Ｒ^１０２はフッ素原子または炭素数１〜５のフッ素化アルキル基である。Ｙ^１０１は単結合または酸素原子を含む２価の連結基である。Ｖ^１０１〜Ｖ^１０３はそれぞれ独立に単結合、アルキレン基、またはフッ素化アルキレン基である。Ｌ^１０１〜Ｌ^１０２はそれぞれ独立に単結合または酸素原子である。Ｌ^１０３〜Ｌ^１０５はそれぞれ独立に単結合、−ＣＯ−又は−ＳＯ_２−である。Ｍ’^ｍ＋はｍ価の有機カチオンである。］

[In general formulas (b-1) to (b-3), R ¹⁰¹ and R ^{104 to} R ¹⁰⁸ may each independently have a cyclic group which may have a substituent, or a substituent which may have a substituent. It is a chain alkyl group or a chain alkenyl group which may have a substituent. R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring. Any two of R ^{106 to} R ¹⁰⁷ may be bonded to each other to form a ring. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. V ^{101 to} V ¹⁰³ are each independently a single bond, an alkylene group, or a fluorinated alkylene group. L ^{101 to} L ¹⁰² are each independently a single bond or an oxygen atom. L ^{103 to} L ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —. ^M'm+ is an m-valent organic cation. ]

{Anion part}
-Anion part of component (b-1) In the general formula (b-1), R ^<101> , Y ^<101> , V ^<101> , and R ^<102 > are described as anions represented by the general formula (m-an-1). This is the same as the description in the section.

-Anion part of component (b-2) In the general formula (b-2), R ^{104 to} R ¹⁰⁵ , L ^{101 to} L ¹⁰² , and V ^{102 to} V ¹⁰³ are described in the above general formula (m-an-2). ) Is the same as the explanation for the anion portion.

Anion part of component (b-3) In formula (b-3), R ^{106 to} R ¹⁰⁸ and L ^{103 to} L ¹⁰⁵ are described as anions represented by formula (m-an-3). This is the same as the description in the section.

{Cation part}
In the general formulas (b-1), (b-2) and (b-3), M′ ^m+ is an m-valent organic cation, preferably a sulfonium cation or an iodonium cation, and The cations represented by formulas (ca-1) to (ca-4) are particularly preferable.

［一般式（ｃａ−１）〜（ｃａ−４）中、Ｒ^２０１〜Ｒ^２０７、およびＲ^２１１〜Ｒ^２１２は、それぞれ独立に置換基を有していてもよいアリール基、アルキル基またはアルケニル基を表し、Ｒ^２０１〜Ｒ^２０３、Ｒ^２０６〜Ｒ^２０７、Ｒ^２１１〜Ｒ^２１２は、相互に結合して式中のイオウ原子と共に環を形成してもよい。Ｒ^２０８〜Ｒ^２０９はそれぞれ独立に水素原子または炭素数１〜５のアルキル基を表し、Ｒ^２１０は置換基を有していてもよいアリール基、アルキル基、アルケニル基、又は−ＳＯ_２−含有環式基であり、Ｌ^２０１は−Ｃ（＝Ｏ）−または−Ｃ（＝Ｏ）−Ｏ−を表し、Ｙ^２０１は、それぞれ独立に、アリーレン基、アルキレン基またはアルケニレン基を表し、ｘは１または２であり、Ｗ^２０１は（ｘ＋１）価の連結基を表す。］

[In general formulas (ca-1) to (ca-4), R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² each independently represent an aryl group, an alkyl group or an alkenyl group which may have a substituent. And R ^{201 to} R ²⁰³ , R ^{206 to} R ²⁰⁷ , and R ^{211 to} R ²¹² may be bonded to each other to form a ring together with the sulfur atom in the formula. R ^{208 to} R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²¹⁰ represents an aryl group, an alkyl group, an alkenyl group, or —SO ₂ — which may have a substituent. a cyclic ^{group, L 201} is -C (= O) - or -C (= O) represents ^{-O-, Y 201} each independently represent an arylene group, an alkylene group or alkenylene group, x 1 or 2 and W ²⁰¹ represents a (x+1)-valent linking group. ]

Examples of the aryl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.
The alkyl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² preferably has 2 to 10 carbon atoms.
Examples of the substituent which R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have include, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and arylthio. And the groups represented by the following general formulas (ca-r-1) to (ca-r-7).
The aryl group in the arylthio group as a substituent is the same as that described for R ¹⁰¹ , and specifically includes a phenylthio group or a biphenylthio group.

［一般式（ｃａ−ｒ−１）〜（ｃａ−ｒ−７）中、Ｒ’^２０１はそれぞれ独立に、水素原子、置換基を有していてもよい環式基、鎖状のアルキル基、または鎖状のアルケニル基である。］

[Formula (ca-r-1) in ~ (ca-r-7) , R '201 independently represents a hydrogen atom, which may have a substituent cyclic group, a chain alkyl group, Alternatively, it is a chain alkenyl group. ]

The cyclic group which may have a substituent, the chain alkyl group which may have a substituent, or the chain alkenyl group which may have a substituent of R′ ²⁰¹ is as defined above. In addition to those similar to R ¹⁰¹ in the general formula (b-1), a cyclic group which may have a substituent or a chain alkyl group which may have a substituent may be the above-mentioned general one. The same groups as the acid dissociable group represented by the formula (a1-r-2) can also be mentioned.

When R ^{201 to} R ²⁰³ , R ^{206 to} R ²⁰⁷ , and R ^{211 to} R ²¹² are bonded to each other to form a ring with a sulfur atom in the formula, a hetero atom such as a sulfur atom, an oxygen atom, or a nitrogen atom, or carbonyl _{group, -SO -, - SO 2 -} , - SO 3 -, - COO -, - CONH- , or -N _(R N) - (. the _{R N} is an alkyl group having 1 to 5 carbon atoms), etc. You may couple|bond together via the functional group of. As a ring to be formed, one ring containing a sulfur atom in the formula in its ring skeleton is preferably a 3 to 10-membered ring including a sulfur atom, and particularly preferably a 5 to 7-membered ring. preferable. Specific examples of the ring formed include, for example, thiophene ring, thiazole ring, benzothiophene ring, thianthrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring, phenoxathiin ring, tetrahydro. Examples thereof include a thiophenium ring and a tetrahydrothiopyranium ring.

R ^{208 to} R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they become an alkyl group, they are bonded to each other to form a ring. May be formed.

R ²¹⁰ may have an aryl group that may have a substituent, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. -SO ₂ - containing cyclic group.
^Examples of the aryl group for R ²¹⁰ include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.
The alkyl group for R ²¹⁰ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group for R ²¹⁰ preferably has 2 to 10 carbon atoms.
The —SO ₂ — containing cyclic group which may have a substituent in R ²¹⁰ is the same as the “—SO ₂ — containing cyclic group” of Ra ^{21 in} the general formula (a2-1) above. And the groups represented by the above general formula (a5-r-1) are preferable.

Y ^201's each independently represent an arylene group, an alkylene group or an alkenylene group.
Examples of the arylene group for Y ²⁰¹ include a group obtained by removing one hydrogen atom from the aryl group exemplified as the aromatic hydrocarbon group for R ¹⁰¹ in the general formula (b-1).
Examples of the alkylene group and alkenylene group for Y ²⁰¹ include the same ones as the aliphatic hydrocarbon group as the divalent hydrocarbon group for Va ¹ in the general formula (a1-1).

In the general formula (ca-4), x is 1 or 2.
W ²⁰¹ is a (x+1)-valent, that is, a divalent or trivalent linking group.
The divalent linking group for W ²⁰¹ is preferably a divalent hydrocarbon group which may have a substituent, and examples thereof include the same hydrocarbon group as Ya ²¹ in the general formula (a2-1). The divalent linking group for W ²⁰¹ may be linear, branched, or cyclic, and is preferably cyclic. Of these, a group in which two carbonyl groups are combined at both ends of the arylene group is preferable. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferable.
^Examples of the trivalent linking group for W ²⁰¹ include a group obtained by removing one hydrogen atom from the divalent linking group for W ²⁰¹ , a group in which the divalent linking group is further bonded to the divalent linking group, and the like. Can be mentioned. The trivalent linking group for W ²⁰¹ is preferably a group in which two carbonyl groups are bonded to an arylene group.

Specific examples of the suitable cation represented by the general formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-63).

［式（ｃａ−１−３４）〜（ｃａ−１−３６）中、ｇ１、ｇ２、ｇ３は繰返し数を示し、ｇ１は１〜５の整数であり、ｇ２は０〜２０の整数であり、ｇ３は０〜２０の整数である。］

[In formulas (ca-1-34) to (ca-1-36), g1, g2, and g3 represent the number of repetitions, g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 0-20. ]

［式（ｃａ−１−５８）中、Ｒ”^２０１は水素原子又は置換基であって、置換基としては前記Ｒ^２０１〜Ｒ^２０７、およびＲ^２１０〜Ｒ^２１２が有していてもよい置換基として挙げたものと同様である。］

[In the formula (ca-1-58), R″ ²⁰¹ is a hydrogen atom or a substituent, and as the substituent, the substituent which R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have. The same as those listed above.]

Specific examples of the suitable cation represented by the general formula (ca-3) include cations represented by the following general formulas (ca-3-1) to (ca-3-6).

Specific examples of the suitable cation represented by the general formula (ca-4) include cations represented by the following chemical formulas (ca-4-1) to (ca-4-2).

As the component (B2), one type of acid generator described above may be used alone, or two or more types may be used in combination.
In the present embodiment, when the resist composition contains the component (B2), the content of the component (B2) is preferably 0.5 to 60 parts by mass, and 1 to 50 parts by mass with respect to 100 parts by mass of the component (A). Parts is more preferable, and 1 to 40 parts by mass is even more preferable. By setting the content of the component (B2) within the above range, pattern formation is sufficiently performed. Further, when each component of the resist composition is dissolved in an organic solvent, a uniform solution is obtained, and the storage stability becomes favorable, which is preferable.

[Photoreactive quencher (D2)]
The component (D2) acts as a quencher (acid diffusion control agent) that traps the acid generated from the component (B2), and contains the compound (m) represented by the general formula (m0). Characterized by In the second embodiment, the compound (m) is preferably a compound represented by the following general formula (m0-2).

［一般式（ｍ０−１）中、
Ｚ^０１〜Ｚ^０４は、それぞれ独立に電子吸引性の置換基であり、
Ｒｂ^２１及びＲｂ^２２は、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基であり（但し、Ｒｂ^２１及びＲｂ^２２が有していてもよい置換基に電子吸引性の置換基は含まないものとする。）、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数であり、
Ｘ２^-は弱酸を発生し得る有機アニオンである。］

[In the general formula (m0-1),
Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing substituent,
Rb ²¹ and Rb ²² are each independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² may have a substituent Does not include electron-withdrawing substituents.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3,
X2 ^- is an organic anion capable of generating a weak acid. ]

In general formula (m0-2), the description regarding Z ^{01 to} Z ⁰⁴ , Rb ²¹ , Rb ²² , Rb ¹ , n1 and n2 is the same as the description in the above general formula (m0).
In Formula (m0-2), X2 ^- is an organic anion capable of generating a weak acid.
Here, the "weak acid" is an acid having a weaker acid strength than the acid generated from the component (B2), and has an acid dissociation constant (pKa) of 0 or more, preferably 0.2 or more, and the upper limit is particularly set. It is an acid which is not about 10 but is substantially about 10.

More specifically, in the general formula (m0-1), X1 ⁻ is represented by an organic anion represented by any one of the following general formulas (d1-an-1) to (d1-an-3). Anions are preferred.

［式中、Ｒｄ^１〜Ｒｄ^４は置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基である。ただし、式（ｄ１−ａｎ−２）中のＲｄ^２における、Ｓ原子に隣接する炭素原子には２つ以上のフッ素原子は結合していないものとする。Ｙｄ^１は単結合、または２価の連結基である。］

[In the formula, Rd ^{1 to} Rd ⁴ are each a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent. Is an alkenyl group. However, it is assumed that two or more fluorine atoms are not bonded to the carbon atom adjacent to the S atom in Rd ² in the formula (d1-an-2). Yd ¹ is a single bond or a divalent linking group. ]

In the general formula (d1-an-1) ~ (d1-an-3), description of Rd 1 ~ Rd ^4, the general formula in ^{(d1-1) ~ (d1-3),} Rd 1 ~Rd 4 Is the same as the description for.

As the component (D2), only one type of the above-mentioned components (d1-1) to (d1-3) may be used, or two or more types may be used in combination.
The content of the component (D2) is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and more preferably 1 to 8 with respect to 100 parts by mass of the component (A). More preferably, it is parts by mass.
When the content of the component (D2) is at least the preferred lower limit, particularly good lithographic properties and resist pattern shapes will be obtained. On the other hand, when it is at most the upper limit value, the sensitivity can be maintained well and the throughput is also excellent. Further, the sensitivity when forming the resist pattern can be further increased.

[(E)-(F) components]
The second embodiment preferably contains the components (E) to (F) as in the first embodiment.

<Positive resist composition>
The positive resist composition according to the second aspect of the present invention is a positive resist composition which generates an acid upon exposure to light and has increased solubility in a developer due to the action of an acid. A base component (A) having increased solubility in a liquid is contained, the base component (A) contains a resin component (A2), and the resin component (A2) has the following general formula (a6-1). ) Having a structural unit (a6) derived from a compound represented by

［式（ａ６−１）中、
Ｚ^０１〜Ｚ^０４は、それぞれ独立に電子吸引性の置換基であり、
Ｒｂ^２１及びＲｂ^２２は、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基であり（但し、Ｒｂ^２１及びＲｂ^２２が有していてもよい置換基に電子吸引性の置換基は含まないものとする。）、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数である。
Ｘ１１−１⁻は、前記の一般式（ａ６−１−１）〜（ａ６−１−３）のいずれかで表される有機アニオンである。式（ａ６−１−１）〜（ａ６−１−３）中、Ｒｂ^２０１は、置換基を有していてもよい鎖状のアルケニル基であり、Ｒｂ^２０４〜Ｒｂ^２０５は、それぞれ独立に、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基または置換基を有していてもよい鎖状のアルケニル基である（但し、Ｒｂ^２０４〜Ｒｂ^２０５の少なくとも一方は、置換基を有していてもよい鎖状のアルケニル基である）。Ｒｂ^２０６〜Ｒｂ^２０８は、それぞれ独立に、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基である（但し、Ｒｂ^２０６〜Ｒｂ^２０８の少なくとも１つは、置換基を有していてもよい鎖状のアルケニル基である）。Ｒｂ^１０２は、フッ素原子または炭素数１〜５のフッ素化アルキル基である。Ｙｂ^１０１は、単結合または酸素原子を含む２価の連結基である。Ｖｂ^１０１〜Ｖｂ^１０３は、それぞれ独立に、単結合、アルキレン基、フッ素化アルキレン基、アリーレン基またはフッ素化アリーレン基である。Ｌ^１０１〜Ｌ^１０２は、それぞれ独立に、単結合または酸素原子である。Ｌｂ^１０３〜Ｌｂ^１０５は、それぞれ独立に、単結合、−ＣＯ−又は−ＳＯ_２−である。ｎ_１０１は０又は１である。］

[In the formula (a6-1),
Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing substituent,
Rb ²¹ and Rb ²² are each independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² may have a substituent Does not include electron-withdrawing substituents.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3.
X11-1 ^- is an organic anion represented by any one of the above general formula (a6-1-1) ~ (a6-1-3). In formulas (a6-1-1) to (a6-1-3), Rb ²⁰¹ is a chain alkenyl group which may have a substituent, and Rb ^{204 to} Rb ²⁰⁵ are each independently, which may have a substituent cyclic group, a substituted also good chain alkyl group or may have a substituent group chain alkenyl group (provided, Rb ²⁰⁴ ~ At least one of Rb ²⁰⁵ is a chain alkenyl group which may have a substituent). Rb ^{206 to} Rb ²⁰⁸ each independently represent a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent. (Wherein at least one of Rb ^{206 to} Rb ²⁰⁸ is a chain alkenyl group which may have a substituent). Rb ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Yb ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. Vb ^{101 to} Vb ¹⁰³ are each independently a single bond, an alkylene group, a fluorinated alkylene group, an arylene group or a fluorinated arylene group. L ^{101 to} L ¹⁰² are each independently a single bond or an oxygen atom. Lb ^{103 to} Lb ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —. n ₁₀₁ is 0 or 1. ]

(Resin component (A2))
In the positive resist composition of the second aspect of the present invention, the substrate component (A) comprises an anion group that generates an acid upon exposure and a cation moiety of the compound represented by the general formula (m0). It contains a resin component (A2) having a structural unit (a6) derived from the compound having. The resin component (A2) (hereinafter, may be referred to as “(A2) component”) is a compound containing an anion group that generates an acid upon exposure in its side chain and represented by the general formula (m0). It is a polymer compound having a structural unit (a6) having a cation moiety of.

(Structural unit (a6))
The structural unit (a6) is represented by general formula (a6-1) above.

· General formula (a6-1) wherein the cation moiety of the compound represented by the general formula ^(a6-1), the description of ^{Z 01 ~Z 04, Rb 21,} Rb 22, Rb 1, n1 and n2, the The explanation is the same as in the general formula (m0).

In the formula (a6-1-1), Rb ²⁰¹ is the same group as the chain alkenyl group which may have a substituent in R ¹⁰¹ in the formula (m-an-1). To be
In the formula ^(a6-1-2), Rb 204 ~Rb ^205, the formula ^{(m-an-2) R} 104 in ^{to R 105,} which may have a substituent cyclic group in a substituted Examples thereof include the same groups as the chain alkyl group that may have a group or the chain alkenyl group that may have a substituent. Provided ^that at least one of ^Rb 204 ~Rb ²⁰⁵ is an alkenyl group which may chain have a substituent.
In the formula (a6-1-3), Rb ^{206 to} Rb ²⁰⁸ are each a cyclic group which may have a substituent, or a substituent, in R ^{106 to} R ¹⁰⁸ in the formula (m-an-3). Examples thereof include the same groups as the chain alkyl group which may have a group or the chain alkenyl group which may have a substituent. However, at least one of Rb ^{206 to} Rb ²⁰⁸ is a chain alkenyl group which may have a substituent.

Rb ¹⁰² , Yb ¹⁰¹ , Vb ^{101 to} Vb ¹⁰³ , Lb ^{101 to} Lb ¹⁰² , Lb ^{103 to} Lb ¹⁰⁵ are the above formulas (m-an-1), (m-an-2), and (m-an), respectively. It is the same as R ¹⁰² , Y ¹⁰¹ , V ^{101 to} V ¹⁰³ , L ^{101 to} L ¹⁰² , and L ^{103 to} L ^{105 in} -3).

In formulas (a6-1-1) to (a6-1-3), at least one of Rb ²⁰¹ , Rb ^{204 to} Rb ²⁰⁵ , and at least one of Rb ^{206 to} Rb ²⁰⁸ is a chain having no substituent. In the case of the alkenyl group of, it is preferable that (CH ₃ )C=CH-(propenyl group) or H ₂ C=CH-(vinyl group). In the case of a chain alkenyl group having a substituent, it is preferable that a divalent group is further bonded to the vinyl group or propenyl group. Examples of the divalent group, an ester bond, ether bond, amide bond, urethane bond, an alkylene group, (poly) cycloalkylene group, a fluorinated alkylene group, an arylene _{group, -SO 2 -O -, - SO} 2 -, Alternatively, a combination of these is preferable.

Specific examples of preferable anions represented by the formula (a6-1-1) are shown below. In each formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

Specific examples of preferable anions represented by the formula (a6-1-2) are shown below. In each formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

Specific examples of preferable anions represented by the formula (a6-1-3) are shown below. In each formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

As the structural unit derived from the compound represented by the general formula (a6-1), preferably, a structural unit represented by any of the following general formulas (a6-11) to (a6-13) can be mentioned. ..

［式中、Ｒ^α、Ｚ^０１〜Ｚ^０４、Ｒｂ^２１、Ｒｂ^２２、Ｒｂ^１、ｎ１、ｎ２、Ｒｂ^１０２、Ｒｂ^２０５、Ｒｂ^２０６、Ｒｂ^２０８、Ｙｂ^１０１、Ｖｂ^１０１〜Ｖｂ^１０３、Ｌｂ^１０１〜Ｌｂ^１０２、Ｌｂ^１０３〜Ｌｂ^１０５、ｎ_１０１は前記同様である。Ｌ^１１〜Ｌ^１３は、それぞれ独立に単結合または２価の連結基である。］

[In the formula, R ^α , Z ^{01 to} Z ⁰⁴ , Rb ²¹ , Rb ²² , Rb ¹ , n1, and n2, Rb ¹⁰² , Rb ²⁰⁵ , Rb ²⁰⁶ , Rb ²⁰⁸ , Yb ¹⁰¹ , Vb ^{101 to} Vb ¹⁰³ , and Lb ¹⁰¹ to Lb ^102, Lb ^{103 to} Lb ¹⁰⁵ , n ₁₀₁ are the same as above. L ^{11 to} L ¹³ are each independently a single bond or a divalent linking group. ]

In each of formulas (a6-11) to (a6-13), the divalent linking group for L ^{11 to} L ¹³ is an ester bond, an alkylene group having 1 to 10 carbon atoms, or a cycloalkylene group having 5 to 30 carbon atoms. , A polycycloalkylene group having 5 to 30 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a combination thereof.

In the component (A2), the structural unit derived from the compound represented by formula (a6-1) may be one type or two or more types.
In the component (A2), the proportion of the structural units derived from the compound represented by the general formula (a6-1) is 0.5 to 30 mols based on the total of all the structural units constituting the component (A2). %, more preferably 1 to 20 mol %, particularly preferably 1.5 to 15 mol %.
By setting the ratio of the structural unit derived from the compound represented by formula (a6-1) to the lower limit or more, the roughness is reduced and a good resist pattern shape is easily obtained. In addition, solvent solubility and sensitivity are also improved. By setting the content to the upper limit or less, it is possible to achieve a balance with other structural units, and it is possible to further enhance the sensitivity when forming a resist pattern.

(Structural unit (a6-2))
The resin component (A2) may have a structural unit (a6-2) derived from a compound represented by the following general formula (a6-2).

［式（ａ６−２）中、
Ｚ^０１〜Ｚ^０４は、それぞれ独立に電子吸引性の置換基であり、
Ｒｂ^２１及びＲｂ^２２は、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基であり（但し、Ｒｂ^２１及びＲｂ^２２が有していてもよい置換基に電子吸引性の置換基は含まないものとする。）、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数である。
Ｘ２１−１⁻は、前記の一般式（ａｍ０−２−１）〜（ａｍ０−２−３）のいずれかで表される有機アニオンである。式（ａｍ０−２−１）中、Ｒｄ^１００は、置換基を有していてもよい鎖状のアルケニル基である。式（ａｍ０−２−２）中、Ｒｄ^２００は、置換基を有していてもよい鎖状のアルケニル基である。ただし、Ｒｄ^２００における、Ｓ原子に隣接する炭素原子にはフッ素原子が結合していないものとする。式（ａｍ０−２−３）中、Ｒｄ^３００〜Ｒｄ^４００は、それぞれ独立に、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基である（但し、Ｒｄ^３００〜Ｒｄ^４００の少なくとも一方は、置換基を有していてもよい鎖状のアルケニル基である）。Ｙｄ^１０は、単結合または２価の連結基である。］

[In the formula (a6-2),
Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing substituent,
Rb ²¹ and Rb ²² are each independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² may have a substituent Does not include electron-withdrawing substituents.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3.
X21-1 ^- is an organic anion represented by any one of the above general formula (am0-2-1) ~ (am0-2-3). In the formula (am0-2-1), Rd ¹⁰⁰ is a chain alkenyl group which may have a substituent. In formula (am0-2-2), Rd ²⁰⁰ is a chain alkenyl group which may have a substituent. However, a fluorine atom is not bonded to the carbon atom adjacent to the S atom in Rd ²⁰⁰ . In formula (am0-2-3), Rd ^{300 to} Rd ⁴⁰⁰ each independently represent a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or It is a chain alkenyl group which may have a substituent (provided that at least one of Rd ^{300 to} Rd ⁴⁰⁰ is a chain alkenyl group which may have a substituent). Yd ¹⁰ is a single bond or a divalent linking group. ]

· General formula (a6-2) wherein the structural unit derived from a compound represented by the general formula ^(a6-2), for ^{Z 01 ~Z 04, Rb 21,} Rb 22, Rb 1, n1 and n2 The description is the same as the description of Z ^{01 to} Z ⁰⁴ , Rb ²¹ , Rb ²² , Rb ¹ , n1 and n2 in the formula (m1).

In the formula (am0-2-1), examples of Rd ¹⁰⁰ include the same groups as the chain alkenyl groups which may have a substituent in Rd ¹ in the formula (d1-1).
In the formula (am0-2-2), examples of Rd ²⁰⁰ include the same groups as the chain alkenyl groups which may have a substituent in Rd ² in the formula (d1-2).
In the formula (am0-2-3), Rd ^{300 to} Rd ⁴⁰⁰ represent a cyclic group and a substituent which may have a substituent, in Rd ³ to Rd ⁴ in the formula (d1-3). Examples thereof include the same groups as the chain alkyl group that may have and the chain alkenyl group that may have a substituent. However, at least one of Rd ^{300 to} Rd ⁴⁰⁰ is a chain alkenyl group which may have a substituent. In the formula (am0-2-3), Yd ¹⁰ is the same as the single bond or the divalent linking group in Yd ¹ in the formula (d1-3).

When at least one of Rd ¹⁰⁰ , Rd ²⁰⁰ , and Rd ^{300 to} Rd ^{400 in} the formulas (am0-2-1) to (am0-2-3) is a chain alkenyl group having no substituent, , (CH ₃ )C═CH—(propenyl group) or H ₂ C═CH—(vinyl group). In the case of a chain alkenyl group having a substituent, it is preferable that a divalent group is further bonded to the vinyl group or propenyl group. The divalent group is preferably an ester bond, an ether bond, an amide bond, a urethane bond, an alkylene group, a (poly)cycloalkylene group, an arylene group, or a combination thereof.

Specific examples of preferable anions represented by the formula (am0-2-1) are shown below. In each formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group. m is an integer of 0-3.

Specific examples of preferable anions represented by the formula (am0-2-2) are shown below. In each formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

Specific examples of preferable anions represented by the formula (am0-2-3) are shown below. In each formula below, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

As the structural unit derived from the compound represented by the general formula (a6-2), preferably, a structural unit represented by any of the following general formulas (am0-21) to (am0-23) can be mentioned. ..

［式中、Ｒ^α、Ｚ^０１〜Ｚ^０４、Ｒｂ^２１、Ｒｂ^２２、Ｒｂ^１、ｎ１、ｎ２、Ｙｄ^１０、Ｒｄ^３００は前記同様である。Ｌ^１〜Ｌ^３は、それぞれ独立に単結合または２価の連結基である。］

[In the formula, R ^α , Z ^{01 to} Z ⁰⁴ , Rb ²¹ , Rb ²² , Rb ¹ , n1, n2, Yd ¹⁰ and Rd ³⁰⁰ are the same as described above. L ^{1 to} L ³ are each independently a single bond or a divalent linking group. ]

In each of formulas (am0-21) to (am0-23), the divalent linking group for L ^{1 to} L ³ includes an ester bond, an alkylene group having 1 to 10 carbon atoms, and a cycloalkylene group having 5 to 30 carbon atoms. , A polycycloalkylene group having 5 to 30 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a combination thereof.

In the component (A2), the structural unit derived from the compound represented by formula (a6-2) may be one type or two or more types.
In the component (A2), the proportion of the structural units derived from the compound represented by the general formula (a6-2) is 0.5 to 30 mols based on the total of all the structural units constituting the component (A2). %, more preferably 1 to 20 mol %, particularly preferably 1.5 to 15 mol %.
By setting the ratio of the structural unit derived from the compound (a6-2) to the lower limit or more, the roughness is reduced and a good resist pattern shape is easily obtained. In addition, solvent solubility and sensitivity are also improved. By setting the content to the upper limit or less, it is possible to achieve a balance with other structural units, and it is possible to further enhance the sensitivity when forming a resist pattern.

As the component (A2), it is preferable to use a polymer compound having the structural unit (a1) in addition to the structural unit (a6).
In addition to the structural unit (a6) and the structural unit (a1), the component (A2) further includes the structural unit (a10), the structural unit (a12), or any other structural unit (the structural unit (a2), etc.). ) May be included.

The component (A2) is a copolymer having the structural unit (a6),
As such a copolymer,
A copolymer having (a6), (a1) and (a10),
A copolymer having (a6), (a1) and (a12),
A copolymer having (a6), (a1) and (a9),
A copolymer having (a6), (a10) and (a12),
A copolymer having (a6), (a1), (a2) and (a10),
Is preferred.

The mass average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of the component (A2) is not particularly limited and is preferably 1000 to 50000, more preferably 1500 to 30000, most preferably 2000 to 20000. preferable. When it is at most the upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist, and when it is at least the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are good.
The molecular weight dispersity (Mw/Mn) of the component (A2) is not particularly limited and is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and 1.2 to 2.5 is most preferred.

<<Other Embodiments>>
The positive resist composition of the present invention is a positive resist composition containing, in addition to the first to second embodiments of the first aspect and the second aspect, a nitrogen-containing compound component as a photoreactive quencher. It may be a type resist composition.

Nitrogen-Containing Compound Component The nitrogen-containing compound component is not particularly limited as long as it acts as an acid diffusion controller and does not correspond to the components (D1) to (D2), and any known compound can be used. Good. Of these, aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines are preferred.
The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms.
Examples of the aliphatic amine include amines (alkylamines or alkylalcoholamines) or cyclic amines in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group having 12 or less carbon atoms or a hydroxyalkyl group.
Specific examples of the alkylamine and the alkylalcoholamine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine; diethylamine, di-n-propylamine, di-amine. Dialkylamines such as -n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine , Tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine and like trialkylamines; diethanolamine, triethanolamine, diisopropanolamine, tri Examples include alkyl alcohol amines such as isopropanol amine, di-n-octanol amine, and tri-n-octanol amine. Among these, a trialkylamine having 5 to 10 carbon atoms is more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

Examples of the cyclic amine include a heterocyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
The aliphatic polycyclic amine preferably has 6 to 10 carbon atoms, and specifically, 1,5-diazabicyclo[4.3.0]-5-nonene and 1,8-diazabicyclo[5. 4.0]-7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane and the like can be mentioned.

Other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2 -(1-Methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxy) Examples thereof include ethoxy)ethoxy}ethyl]amine and triethanolamine triacetate, with triethanolamine triacetate being preferred.

An aromatic amine may be used as the nitrogen-containing compound component.
Examples of aromatic amines include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxy. Carbonyl pyrrolidine etc. are mentioned.

The nitrogen-containing compound component may be used alone or in combination of two or more kinds.
The nitrogen-containing compound component is usually used in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the component (A). By setting the content within the above range, the resist pattern shape, the stability with leaving and the like are improved.

As the nitrogen-containing compound component, one type may be used alone, or two or more types may be used in combination.
In the present invention, when the resist composition contains a nitrogen-containing compound component, the nitrogen-containing compound component is preferably 0.1 to 15 parts by mass, and 0.3 to 100 parts by mass of the component (A). It is more preferably 12 parts by mass, further preferably 0.5 to 12 parts by mass. When it is at least the lower limit value of the above range, the lithographic properties such as LWR are further improved when the composition is used as a resist composition. Further, a better resist pattern shape can be obtained. When it is at most the upper limit of the above range, the sensitivity can be favorably maintained and the throughput is also excellent.

<Method of forming resist pattern>
A third aspect of the present invention is a step of forming a resist film on a support using the positive resist composition of the first or second aspect of the present invention, a step of exposing the resist film, And a resist pattern forming method for forming a positive resist pattern by alkali developing the exposed resist film.
The resist pattern forming method can be performed as follows, for example.
First, the above-mentioned dist composition is coated on a support with a spinner or the like, and a baking (post-apply bake (PAB)) treatment is performed, for example, at a temperature condition of 80 to 150° C. for 40 to 120 seconds, preferably 60 to 90. It is applied for 2 seconds to form a resist film.
Next, the resist film is exposed or masked through a mask (mask pattern) on which a predetermined pattern is formed, using an exposure device such as an ArF exposure device, an electron beam drawing device, and an EUV exposure device. After performing selective exposure such as drawing by direct irradiation of an electron beam without intervention, baking (post exposure bake (PEB)) treatment is performed for 40 to 120 seconds, preferably 60 to 60 at a temperature condition of 80 to 150°C. Apply for 90 seconds.
Next, the resist film is developed.
The development process is performed using an alkaline developer.
After the development processing, rinsing processing is preferably performed. The rinse treatment is preferably a water rinse using pure water in the case of an alkali developing process, and preferably a rinse liquid containing an organic solvent in the case of a solvent developing process.
After development or rinsing, drying is performed. In some cases, a bake treatment (post bake) may be performed after the above development treatment. In this way, a resist pattern can be obtained.
In the present invention, the development treatment may be an alkali development process or a solvent development process.

[Support]
The support is not particularly limited, and a conventionally known support can be used, and examples thereof include a substrate for electronic parts and a support having a predetermined wiring pattern formed thereon. More specifically, a silicon wafer, a substrate made of metal such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold or the like can be used.
Further, the support may be the above-mentioned substrate provided with an inorganic and/or organic film. Examples of the inorganic film include an inorganic antireflection film (inorganic BARC). Examples of the organic film include an organic antireflection film (organic BARC) and an organic film such as a lower organic film in a multilayer resist method.
Here, the multi-layer resist method means that at least one organic film (lower organic film) and at least one resist film (upper resist film) are provided on a substrate, and the resist pattern formed on the upper resist film is used as a mask. It is a method of patterning the lower organic film, and is said to be capable of forming a pattern with a high aspect ratio. That is, according to the multi-layer resist method, since the required thickness can be secured by the lower organic film, the resist film can be thinned and a fine pattern with a high aspect ratio can be formed.
The multi-layer resist method basically includes a method of forming a two-layer structure of an upper resist film and a lower organic film (two-layer resist method), and one or more intermediate layers between the upper resist film and the lower organic film. It is divided into a method of forming a multi-layer structure of three or more layers (three-layer resist method) provided with (metal thin film or the like).

The wavelength used for exposure is not particularly limited, and includes ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. It can be done using radiation. The resist composition is highly useful for KrF excimer laser, ArF excimer laser, EB or EUV, and more particularly useful for EB or EUV.

The exposure method of the resist film may be a normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or a liquid immersion exposure (Liquid Immersion Lithography).
In the immersion exposure, the space between the resist film and the lens at the lowest position of the exposure apparatus is previously filled with a solvent (immersion medium) having a refractive index higher than that of air, and exposure (immersion exposure) is performed in that state. It is an exposure method.
As the liquid immersion medium, a solvent having a refractive index higher than that of air and lower than that of the resist film to be exposed is preferable. The refractive index of the solvent is not particularly limited as long as it falls within the above range.
Examples of the solvent having a refractive index higher than that of air and lower than that of the resist film include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent.
Specific examples of the fluorine-based inert liquid include a fluorine-based compound such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , and C ₅ H ₃ F ₇ as a main component. Examples thereof include liquids, those having a boiling point of 70 to 180° C. are preferable, and those having a boiling point of 80 to 160° C. are more preferable. It is preferable that the fluorine-based inert liquid has a boiling point in the above range because the medium used for immersion can be removed by a simple method after the exposure is completed.
As the fluorine-based inert liquid, a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group are replaced with fluorine atoms is particularly preferable. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.
More specifically, examples of the perfluoroalkyl ether compound include perfluoro(2-butyl-tetrahydrofuran) (boiling point 102° C.), and examples of the perfluoroalkylamine compound include perfluorotributylamine( The boiling point is 174° C.).
As the liquid immersion medium, water is preferably used from the viewpoints of cost, safety, environmental problems, versatility and the like.

Examples of the alkali developing solution include an aqueous solution of tetramethylammonium hydroxide (TMAH) of 0.1 to 10% by mass.

The development treatment can be carried out by a known development method, for example, a method of dipping the support in a developing solution for a certain period of time (dip method), or raising the developing solution to the surface of the support by surface tension and leaving it stationary for a certain period of time. Method (paddle method), spraying the developer on the surface of the support (spray method), and applying the developer while scanning the developer application nozzle at a constant speed on the support rotating at a constant speed. A continuous method (dynamic dispensing method) and the like can be mentioned.

The rinse treatment (washing treatment) using the rinse liquid can be performed by a known rinse method. Examples of the method include a method in which the rinse solution is continuously applied onto the support rotating at a constant speed (rotational coating method), a method in which the support is immersed in the rinse solution for a certain time (dip method), and the surface of the support. And a method of spraying a rinse liquid on the surface (spray method).

<Photoreactive quencher>
A fourth aspect of the present invention is a photoreactive quencher characterized by comprising a compound (m) represented by the following general formula (m0).

［一般式（ｍ０）中、
Ｚ^０１〜Ｚ^０４は、それぞれ独立に電子吸引性の置換基であり、
Ｒｂ^２１及びＲｂ^２２は、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基であり（但し、Ｒｂ^２１及びＲｂ^２２が有していてもよい置換基に電子吸引性の置換基は含まないものとする。）、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数である。
Ｘ０⁻は、一般式（ｄ１−ａｎ−１）〜（ｄ１−ａｎ−３）のいずれかで表される有機アニオンである。
一般式（ｄ１−ａｎ−１）〜（ｄ１−ａｎ−３）中、Ｒｄ^１〜Ｒｄ^４は置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、又は置換基を有していてもよい鎖状のアルケニル基である。ただし、式（ｄ１−ａｎ−２）中のＲｄ^２における、Ｓ原子に隣接する炭素原子にはフッ素原子は２つ以上結合していないものとする。Ｙｄ^１は単結合、又は２価の連結基である。］

[In the general formula (m0),
Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing substituent,
Rb ²¹ and Rb ²² are each independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² may have a substituent Does not include electron-withdrawing substituents.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3.
X0 ^- the general formula (d1-an-1) is an organic anion represented by any one of the ~ (d1-an-3) .
In general formulas (d1-an-1) to (d1-an-3), Rd ^{1 to} Rd ⁴ each represent a cyclic group which may have a substituent, or a chain which may have a substituent. It is an alkyl group or a chain alkenyl group which may have a substituent. However, two or more fluorine atoms are not bonded to the carbon atom adjacent to the S atom in Rd ² in formula (d1-an-2). Yd ¹ is a single bond or a divalent linking group. ]

The description of the compound (m) contained in the acid diffusion controller of the present invention is the same as the description of the compound (m) described in the first aspect of the present invention.

<Polymer compound>
A fifth aspect of the present invention is a polymer compound having a structural unit derived from a compound represented by the following general formula (a6-1).

［一般式（ａ６−１）中、
Ｚ^０１〜Ｚ^０４は、それぞれ独立に電子吸引性の置換基であり、
Ｒｂ^２１及びＲｂ^２２は、それぞれ独立に、アルキル基、置換基を有していてもよい脂環式炭化水素基又は水酸基であり（但し、Ｒｂ^２１及びＲｂ^２２が有していてもよい置換基に電子吸引性の置換基は含まないものとする。）、
Ｒｂ^１は、置換基を有していてもよいアリール基、置換基を有していてもよいアルキル基又は置換基を有していてもよいアルケニル基であり、
ｎ１及びｎ２は、それぞれ独立に、０〜３の整数である。
Ｘ１１−１⁻は、前記の一般式（ａ６−１−１）〜（ａ６−１−３）のいずれかで表される有機アニオンである。式（ａ６−１−１）〜（ａ６−１−３）中、Ｒｂ^２０１は、置換基を有していてもよい鎖状のアルケニル基であり、Ｒｂ^２０４〜Ｒｂ^２０５は、それぞれ独立に、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基または置換基を有していてもよい鎖状のアルケニル基である（但し、Ｒｂ^２０４〜Ｒｂ^２０５の少なくとも一方は、置換基を有していてもよい鎖状のアルケニル基である）。Ｒｂ^２０６〜Ｒｂ^２０８は、それぞれ独立に、置換基を有していてもよい環式基、置換基を有していてもよい鎖状のアルキル基、または置換基を有していてもよい鎖状のアルケニル基である（但し、Ｒｂ^２０６〜Ｒｂ^２０８の少なくとも１つは、置換基を有していてもよい鎖状のアルケニル基である）。Ｒｂ^１０２は、フッ素原子または炭素数１〜５のフッ素化アルキル基である。Ｙｂ^１０１は、単結合または酸素原子を含む２価の連結基である。Ｖｂ^１０１〜Ｖｂ^１０３は、それぞれ独立に、単結合、アルキレン基、フッ素化アルキレン基、アリーレン基またはフッ素化アリーレン基である。Ｌ^１０１〜Ｌ^１０２は、それぞれ独立に、単結合または酸素原子である。Ｌｂ^１０３〜Ｌｂ^１０５は、それぞれ独立に、単結合、−ＣＯ−又は−ＳＯ_２−である。ｎ_１０１は０又は１である。］

[In general formula (a6-1),
Z ^{01 to} Z ⁰⁴ are each independently an electron-withdrawing substituent,
Rb ²¹ and Rb ²² are each independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² may have a substituent Does not include electron-withdrawing substituents.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3.
X11-1 ^- is an organic anion represented by any one of the above general formula (a6-1-1) ~ (a6-1-3). In formulas (a6-1-1) to (a6-1-3), Rb ²⁰¹ is a chain alkenyl group which may have a substituent, and Rb ^{204 to} Rb ²⁰⁵ are each independently, which may have a substituent cyclic group, a substituted also good chain alkyl group or may have a substituent group chain alkenyl group (provided, Rb ²⁰⁴ ~ At least one of Rb ²⁰⁵ is a chain alkenyl group which may have a substituent). Rb ^{206 to} Rb ²⁰⁸ each independently represent a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain which may have a substituent. (Wherein at least one of Rb ^{206 to} Rb ²⁰⁸ is a chain alkenyl group which may have a substituent). Rb ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Yb ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. Vb ^{101 to} Vb ¹⁰³ are each independently a single bond, an alkylene group, a fluorinated alkylene group, an arylene group or a fluorinated arylene group. L ^{101 to} L ¹⁰² are each independently a single bond or an oxygen atom. Lb ^{103 to} Lb ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —. n ₁₀₁ is 0 or 1. ]

The description of the polymer compound having a constitutional unit derived from the compound represented by formula (a6-1) will be made from the compound represented by formula (a6-1) described in the first aspect of the invention. The same applies to the description regarding the polymer compound to be derived.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples.

<Production of compound (m0)>
[Production Example 1]
(First step)
Of 3,5-difluorophenyl magnesium bromide prepared by a conventional method using 96.5 g (0.50 mol) of 1-bromo-3,5-difluorobenzene, 13.4 g (0.55 mol) of magnesium and 400 g of tetrahydrofuran. To the tetrahydrofuran solution, a solution prepared by diluting 28.6 g (0.48 mol) of thionyl chloride in 50 g of tetrahydrofuran was added dropwise so that the system temperature did not exceed -5°C. After completion of the dropping, the reaction was continued at room temperature for 1 hour to complete the reaction.
This solution was added to 500 g of ion-exchanged water so that the temperature did not exceed 15° C., and the mixture was stirred for 1 hour. Then, 300 g of ethyl acetate was added and stirred for 1 hour. After removing the aqueous layer, it was washed 3 times with 300 g of ion-exchanged water. The organic layer was desolvated, and the obtained brown residue was recrystallized from cyclohexane to obtain 26.0 g of bis(3,5-difluorophenyl)sulfoxide.
Hereinafter, bis(3,5-difluorophenyl)sulfoxide may be referred to as “compound (m2)”.

(Second step)
6.86 g (0.025 mol) of bis(3,5-difluorophenyl) sulfoxide synthesized in the first step was dissolved in 30 g of benzene, and 8.46 g (0.03 mol) of trifluoromethanesulfonic anhydride was added to the system. The mixture was added dropwise within the range where the internal temperature did not exceed -5°C.
After completion of the dropping, the reaction was continued at room temperature for 1 hour to complete the reaction. The supernatant was removed, and 50 g of ion-exchanged water was added to the oily precipitate so as not to exceed 15° C., 75 g of tetrahydrofuran and 30 g of toluene were added, and the mixture was stirred for 1 hour. The upper layer was removed, and the remaining solution was washed twice with 30 g of toluene. Thereafter, the solution was neutralized with sodium hydrogen carbonate, 100 g of dichloromethane was added for extraction, the aqueous layer was removed, and the organic layer was washed 3 times with 50 g of ion-exchanged water. The organic layer was desolvated, and when crystals were precipitated, 150 g of methyl-tert-butyl ether was added to precipitate white crystals. The crystals were filtered, collected, and dried under reduced pressure to obtain 6.53 g (purity 99.9% or more) of the target product, [bis(3,5-difluorophenyl)]phenylsulfonium trifluoromethanesulfonate. ..
Hereinafter, [bis(3,5-difluorophenyl)]phenylsulfonium trifluoromethanesulfonate may be referred to as “compound (m3)”.

(Third step)
The compound (m3) (10.0 g) obtained in the third step was dissolved in dichloromethane (200.0 g). Then, water (100.0 g) and compound 2 (11.5 g) were added and stirred for 30 minutes. After that, the organic solvent phase was repeatedly washed with water (100.0 g) three times. The obtained organic solvent phase was added dropwise to methyl-tert-butyl ether (800.0 g) over 60 minutes, stirred for 30 minutes, and filtered. The obtained powder was dried at room temperature for 12 hours to obtain the following compound (m0)-1 (13.3 g).

[Production Example 2]
(First and second steps)
In the second step of Production Example 1, the first step and the second step were performed by the same method as in Production Example 1 except that 3,5-dimethyl-4-methoxybenzene was used instead of benzene. Then, the following compound (m3-1) was obtained.

(Third step)
The compound (m3-1) (10.00 g) obtained in the first step and the second step was dissolved in dichloromethane (200.0 g). Then, water (100.0 g) and compound 2 (10.2 g) were added and stirred for 30 minutes. After that, the organic solvent phase was repeatedly washed with water (100.0 g) three times. The obtained organic solvent phase was added dropwise to methyl-tert-butyl ether (600.0 g) over 60 minutes, stirred for 30 minutes, and filtered. The obtained powder was dried at room temperature for 12 hours to obtain the following compound (m0)-5 (13.0 g).

The following compounds (m0)-2 to (m0)-4 and (m0)-6 were obtained in the same manner as above. The compounds (m0)-1 to (m0)-6 are described below.

<Preparation of positive resist composition>
Positive resist compositions of Examples 1 to 12 and Comparative Examples 1 to 7 shown in Tables 1 and 2 below were prepared.

In Tables 1 and 2 above, each symbol has the following meaning. The numerical value in [] means the blending amount (parts by mass).
-(A)-1 to (A)-6: The following polymer compounds (A)-1 to (A)-6.
-(B)-1 to (B)-10: the above compounds (m0)-1 to (m0)-5 and the following (B)-6 to (B)-10.
-(D)-1, (D)-3 to (D)-4: the following compounds (D)-1, (D)-3 to (D)-4.
-(D)-2: (m0)-6 above.
-(S)-1: PGMEA/PGME = 60/40 (mass ratio) mixed solvent.

<Formation of positive resist pattern>
Each of the positive resist compositions of Examples 1 to 12 and Comparative Examples 1 to 7 was applied onto a 8-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a spinner, and the temperature was adjusted on a hot plate at a temperature of A pre-baking (PAB) treatment was performed at 100° C. for 60 seconds, followed by drying to form a positive resist film having a film thickness of 50 nm.
Next, an electron beam drawing apparatus JEOL-JBX-9300FS (manufactured by JEOL Ltd.) was used for the positive resist film, and the target size was 1:1 line and line width 50 to 26 nm at an accelerating voltage of 100 kV. Drawing (exposure) as a space pattern (hereinafter, "LS pattern") was performed.
Then, alkali development was performed at 23° C. for 60 seconds using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution “NMD-3” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.).
Then, it was rinsed with pure water for 15 seconds and subjected to post-exposure heating (PEB) treatment at 110° C. for 60 seconds.
As a result, a 1:1 LS pattern having a line width of 50 to 26 nm was formed.

[Evaluation of sensitivity (Eop)]
The optimum exposure dose (μC/cm ² ) with which the LS pattern of the target size is formed by the above-described method of forming a positive resist pattern was determined. The results are shown in Tables 3 to 4 as “sensitivity (μC/cm ² )”.

[Resolution evaluation]
The minimum resolution of the above Eop, specifically, the minimum size of the pattern that is resolved without falling when the LS pattern is formed by gradually increasing the exposure amount from the optimum exposure amount Eop, the scanning electron microscope (acceleration The voltage was 800 V, the trade name: S-9380, manufactured by Hitachi High-Technologies Corporation).
The results are shown in Tables 3 to 4 as "resolution (nm)".

[Evaluation of LWR (linewise roughness)]
With respect to the positive type distant pattern formed above, 3σ, which is a scale showing LWR, was determined.
“3σ” is a standard deviation obtained by measuring 400 line positions in the longitudinal direction of the line with a scanning electron microscope (accelerating voltage 800 V, trade name: S-9380, manufactured by Hitachi High-Technologies Corporation), and obtaining the measurement results. The triple value (3σ) of (σ) (unit: nm) is shown.
The smaller the value of 3σ, the smaller the roughness of the line side wall, which means that a positive resist pattern having a more uniform width was obtained. The results are shown in Tables 3 and 4 as "LWR (nm)".

As shown in Tables 3 to 4 above, when a resist pattern is formed using the positive resist composition of the present invention, a resist pattern having better sensitivity than the comparative example, better resolution, and reduced LWR is obtained. I was able to confirm that.

Claims (3)

A positive resist composition which generates an acid upon exposure and whose solubility in an alkali developing solution is increased by the action of the acid,
A base component (A) whose solubility in an alkaline developer is increased by the action of an acid,
An acid generator component (B1) that generates an acid upon exposure,
A photoreactive quencher (D1),
Containing
The acid generator component (B1) contains a compound (m) represented by the following general formula (m0),
Positive resist composition.

[In the general formula (m0),
Z ^{01 to} Z ⁰⁴ are fluorine atoms,
Rb ²¹ and Rb ²² are each independently an alkyl group, an alicyclic hydrocarbon group which may have a substituent or a hydroxyl group (provided that Rb ²¹ and Rb ²² may have a substituent Does not include electron-withdrawing substituents.),
Rb ¹ is an aryl group which may have a substituent, an alkyl group which may have a substituent or an alkenyl group which may have a substituent,
n1 and n2 are each independently an integer of 0 to 3,
X0 ^- is an organic anion. ] The base material component (A) contains a resin component (A1),
The resin component (A1) is
A structural unit (a9) represented by general formula (a9-1) shown below,
Or, having a structural unit (a10) containing an aromatic hydrocarbon group having a hydroxy group,
The positive resist composition according to claim 1.

[In general formula (a9-1), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya ⁹¹ represents a single bond or a divalent linking group. , R ⁹¹ is a hydrocarbon group which may have a substituent, and Ya ⁹² is a divalent linking group. ] A step of forming a resist film on the support using the positive resist composition according to claim 1, a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern. A method for forming a resist pattern including a step of forming.