JP2022093096A - Resist composition and resist pattern forming method - Google Patents

Abstract

To provide a resist composition having good sensitivity, CDU suitability, and resolution.SOLUTION: The resist composition contains: a base component (A) whose solubility in a developer changes by the action of an acid; a compound (D01) represented by general formula (d01-1); a compound (D02) represented by general formula (d02-1); and a polymer compound (F01) having a constituent unit (f01) represented by general formula (f01-1) and a constituent unit (f02) represented by general formula (f02-1). Rd01 and Rd02 are each a cyclic group, an alkyl group or an alkenyl group; Mm+ is an m-valent organic cation; R is a hydrogen atom, an alkyl group or a halogenated alkyl group; Vf01 is a divalent linking group; Rf01 is a monovalent organic group containing a fluorine atom; Vf02 is a divalent linking group; nf02 is an integer of 0-2; and Rf02 is an acid-dissociable group.SELECTED DRAWING: None

Description

The present invention relates to a resist composition and a resist pattern forming method.

In lithography technology, 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. And the development process is performed to form a resist pattern having a predetermined shape on the resist film. A resist material whose exposed portion changes to a characteristic that dissolves in a developing solution is called a positive type, and a resist material whose exposed portion changes to a characteristic that does not dissolve in a developing solution is called a negative type.

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 method for miniaturizing a pattern, generally, the wavelength of an exposure light source is shortened (energy is increased). Specifically, in the past, ultraviolet rays typified by g-rays and i-rays were used, but nowadays, mass production of semiconductor devices using KrF excimer lasers and ArF excimer lasers has started. Further, studies are being conducted on electron beams having a shorter wavelength (high energy) than these excimer lasers, EUV (extreme ultraviolet rays), X-rays, and the like. The resist material is required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing fine dimensional patterns. As a resist material satisfying such a requirement, a chemically amplified resist composition containing a substrate component whose solubility in an alkaline developer changes by the action of an acid and an acid generator component that generates an acid by exposure is used. Has been done.

As one of the methods for improving the resolution, exposure (immersion exposure) is performed by interposing a liquid (immersion medium) having a higher refractive index than air between the objective lens of the exposure machine and the sample. A lithography method, so-called immersion lithography (Liquid Imaging Lithography, hereinafter sometimes referred to as "immersion exposure"), is known. According to the immersion exposure, even if a light source having the same exposure wavelength is used, the same high resolution as when using a light source having a shorter wavelength or when using a high NA lens can be achieved, and the depth of focus width can be increased. It is said that there is no decline. Further, the immersion exposure can be performed by using an existing exposure apparatus. Therefore, immersion exposure has been heavily used in recent years because it can realize the formation of a resist pattern having low cost, high resolution, and excellent depth of focus width. Immersion exposure is effective in forming any pattern shape, and it is said that it can be combined with super-resolution techniques such as a phase shift method and a modified illumination method. Currently, as an immersion exposure technique, a technique using an ArF excimer laser as a light source is being actively studied. Water is mainly considered as the immersion medium.

In the above immersion exposure, a resist material having characteristics corresponding to the immersion exposure technique is required in addition to the usual lithography characteristics (sensitivity, resolution, etching resistance, etc.). For example, in immersion exposure, when the resist film and the immersion solvent come into contact with each other, elution of the substance in the resist film into the immersion solvent occurs (substance elution). The elution of the substance causes phenomena such as deterioration of the resist layer and change of the refractive index of the immersion solvent, and deteriorates the lithography characteristics. Since the amount of this substance elution is affected by the characteristics of the resist film surface (for example, hydrophilicity, hydrophobicity, etc.), for example, by increasing the hydrophobicity of the resist film surface, the substance elution is reduced and the lithography characteristics are improved. It is planned.

In the resist composition used for such immersion exposure, it has been proposed to add a compound containing a fluorine atom. For example, Patent Document 1 discloses a fluorine-containing polymer compound having a structural unit having a fluorine atom and a structural unit containing an acid dissociative group as a compound containing a fluorine atom to be added to a resist composition. ..

Japanese Unexamined Patent Publication No. 2013-181126

With the further progress of lithography technology and the miniaturization of resist patterns, further high sensitivity and improvement of lithography characteristics are required. However, in the conventional resist composition as described above, when the sensitivity to the exposure light source is increased, the roughness of the resist pattern tends to increase, and it is difficult to satisfy all of these characteristics.

The present invention has been made in view of the above circumstances, and is a resist composition capable of forming a resist pattern having good sensitivity and reduced roughness, and a resist pattern using the resist composition. The subject is to provide a forming method.

In order to solve the above problems, the present invention has adopted the following configuration.
That is, the first aspect of the present invention is a resist composition in which an acid is generated by exposure and the solubility in a developing solution is changed by the action of the acid, and the solubility in the developing solution is changed by the action of the acid. The substrate component (A) to be processed, the compound (D01) represented by the following general formula (d01-1), the compound (D02) represented by the following general formula (d02-1), and the following general formula (f01). A resist composition containing a polymer compound (F01) having a structural unit (f01) represented by -1) and a structural unit (f02) represented by the following general formula (f02-1).

［式中、Ｒｄ^０１及びＲｄ^０２は、それぞれ独立に、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基である。但し、式（ｄ０１－２）中のＲｄ^０２において、式（ｄ０１－２）中の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。ｍはそれぞれ独立に１以上の整数であって、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 ⁰¹ and Rd ⁰² may 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. However, in Rd ⁰² in the formula (d01-2), it is assumed that the fluorine atom is not bonded to the carbon atom adjacent to the S atom in the formula (d01-2). m is an integer of 1 or more independently, and M ^{m +} is an organic cation having an m valence independently. ]

［式中、Ｒは、それぞれ独立に、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基であり；Ｖｆ^０１は、２価の連結基であり；Ｒｆ^０１は、フッ素原子を含む１価の有機基であり；Ｖｆ^０２は、２価の連結基であり；ｎｆ^０２は、０～２の整数であり；Ｒｆ^０２は、酸解離性基である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, respectively; Vf ⁰¹ is a divalent linking group; Rf ⁰¹ is a monovalent organic group containing a fluorine atom; Vf ⁰² is a divalent linking group; nf ⁰² is an integer of 0 to 2; Rf ⁰² is an acid dissociable group. .. ]

A second aspect of the present invention is a step of forming a resist film on a support using the resist composition according to the first aspect, a step of exposing the resist film, and a step of exposing the resist film after exposure. It is a resist pattern forming method including a step of developing and forming a resist pattern.

According to the present invention, it is possible to provide a resist composition capable of forming a resist pattern having good sensitivity and reduced roughness, and a resist pattern forming method using the resist composition.

As used herein and in the claims, "aliphatic" is defined as a relative concept to aromatics, meaning groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the "alkyl group" shall include linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups.
Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The "constituent unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When it is described that "may have a substituent", the hydrogen atom (-H) is replaced with a monovalent group, and the methylene group ( _-CH2- ) is replaced with a divalent group. Including both.
"Exposure" is a concept that includes general irradiation of radiation.

An "acid-degradable group" is a group having an acid-degradable property in which at least a part of the bonds in the structure of the acid-degradable group can be cleaved by the action of an acid.
Examples of the acid-degradable group whose polarity is increased by the action of an acid include a group which is decomposed by the action of an acid to form a polar group.
Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, a sulfo group (-SO _3H ) and the like.
More specifically, the acid-degradable group includes a group in which the polar group is protected by an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group).

The "acid dissociative group" is (i) a group having acid dissociation that allows the bond between the acid dissociative group and an atom adjacent to the acid dissociative group to be cleaved by the action of an acid, or a group having acid dissociation. (Ii) A group capable of cleaving the bond between the acid dissociative group and an atom adjacent to the acid dissociative group by further decarbonation reaction after the partial bond is cleaved by the action of the acid. , Both.
The acid dissociative group constituting the acid-degradable group needs to be a group having a lower polarity than the polar group produced by the dissociation of the acid dissociative group, whereby the acid dissociative group is affected by the action of the acid. When is dissociated, a polar group having a higher polarity than the acid dissociative group is generated and the polarity is increased. As a result, the polarity of the entire (A1) component increases. As the polarity increases, the solubility in the developer changes relatively, the solubility increases when the developer is an alkaline developer, and the solubility increases when the developer is an organic developer. Decrease.

The "base material component" is an organic compound having a film-forming ability. Organic compounds used as base material components are roughly classified into non-polymers and polymers. As the non-polymer, one having a molecular weight of 500 or more and less than 4000 is usually used. Hereinafter, the term "small molecule 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", "polymer compound" or "polymer" means a polymer having a molecular weight of 1000 or more. As the molecular weight of the polymer, a polystyrene-equivalent weight average molecular weight by GPC (gel permeation chromatography) shall be used.

The "derived structural unit" means a structural unit composed of cleaved multiple bonds between carbon atoms, for example, an ethylenic double bond.
In the "acrylic acid ester", a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent. The substituent (R ^αx ) that replaces the hydrogen atom bonded to the carbon atom at the α-position is an atom or group other than the hydrogen atom. In addition, an itaconic acid diester in which the substituent (R ^αx ) is substituted with a substituent containing an ester bond, and an α-hydroxyacrylic ester in which the substituent (R ^αx ) is substituted with a hydroxyalkyl group or a group modified with a hydroxyl group thereof are also available. It shall include. The carbon atom at the α-position of the acrylic acid ester is a carbon atom to which the carbonyl group of acrylic acid is bonded, unless otherwise specified.
Hereinafter, an acrylic acid 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 acrylic acid ester.

The term "derivative" is a concept including a hydrogen atom at the α-position of the target compound substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. As those derivatives, the hydrogen atom at the α-position may be substituted with a substituent. The hydrogen atom of the hydroxyl group of the target compound is substituted with an organic group; even if the hydrogen atom at the α-position is substituted with a substituent. Examples of a good target compound include those to which a substituent other than a hydroxyl group is bonded. The α-position refers to the first carbon atom adjacent to the functional group unless otherwise specified.
Examples of the substituent that replaces the hydrogen atom at the α-position of hydroxystyrene include those similar to R ^αx .

In the present specification and claims, depending on the structure represented by the chemical formula, an asymmetric carbon may be present, and an enantiomer or a diastereomer may be present. In that case, those isomers are represented by one chemical formula. These isomers may be used alone or as a mixture.

(Resist composition)
The resist composition of the present embodiment generates an acid by exposure and changes its solubility in a developing solution by the action of the acid.
The resist composition of the present embodiment is represented by a substrate component (A) (hereinafter, also referred to as “(A) component”) whose solubility in a developing solution is changed by the action of an acid and a general formula (d01-1). The compound (D01) (hereinafter, also referred to as “(D01)” component) and the compound (D02) represented by the general formula (d02-1) (hereinafter, also referred to as “(D02)” component) are generally used. The polymer compound (F01) having a structural unit (f01) represented by the formula (f01-1) and a structural unit (f02) represented by the general formula (f02-1) (hereinafter, also referred to as “(F01)” component. ) And.

When a resist film is formed using the resist composition of the present embodiment and selective exposure is performed on the resist film, an acid is generated in the exposed portion of the resist film, and the component (A) is generated by the action of the acid. While the solubility of the resist film in the developing solution changes, the solubility of the component (A) in the developing solution does not change in the unexposed portion of the resist film, so that the resist film is developed between the exposed portion and the unexposed portion. There is a difference in solubility in the liquid. Therefore, when the resist film is developed, if the resist composition is a positive type, the exposed portion of the resist film is dissolved and removed to form a positive type resist pattern, and if the resist composition is a negative type, the resist film is not formed. The exposed portion is melted and removed to form a negative resist pattern. In the present specification, a resist composition in which a resist film exposed portion is melted and removed to form a positive resist pattern is referred to as a positive resist composition, and a resist film unexposed portion is melted and removed to form a negative resist pattern. The resist composition to be used is called a negative resist composition.

The resist composition of this embodiment may be a positive resist composition or a negative resist composition.
Further, the resist composition of the present embodiment may be for an alkaline developing process using an alkaline developer for the developing process at the time of forming a resist pattern, or for a solvent developing process using an organic developer for the developing process. You may.

The resist composition of the present embodiment has an acid-generating ability to generate an acid by exposure, and the component (A) may generate an acid by exposure, and is added separately from the component (A). The agent component may generate an acid upon exposure.
Specifically, the resist composition of the present embodiment is
(1) It may contain an acid generator component (B) (hereinafter referred to as "(B) component") that generates an acid by exposure.
(2) The component (A) may be a component that generates an acid by exposure.
(3) The component (A) may be a component that generates an acid by exposure and may further contain the component (B).
That is, in the cases of (2) and (3) above, the component (A) is "a base material component that generates an acid by exposure and whose solubility in a developing solution is changed by the action of the acid". When the component (A) is a base material component that generates an acid by exposure and whose solubility in a developer changes due to the action of the acid, the component (A1) described later generates an acid by exposure and the solubility in the developer changes. It is preferably a polymer compound whose solubility in a developing solution changes due to the action of an acid. 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 by exposure, a known one can be used.

The resist composition of the present embodiment is preferably the case of (1) above among the above-mentioned ones. That is, a resist composition containing a component (A), a component (D01), a component (D02), a component (F01), and a component (B) is preferable.

<Ingredient (A)>
In the resist composition of the present embodiment, the component (A) preferably contains a resin component (A1) (hereinafter, also referred to as "component (A1)") whose solubility in a developing solution is changed by the action of an acid. By using the component (A1), the polarity of the base material component changes before and after exposure, so that good development contrast can be obtained not only in the alkaline development process but also in the solvent development process.
As the component (A), at least the component (A1) is used, and other high molecular weight compounds and / or low molecular weight compounds may be used in combination with the component (A1).

When an alkaline developing process is applied, the substrate component containing the component (A1) is sparingly soluble in an alkaline developer before exposure. For example, when an acid is generated from the component (B) by exposure, the acid is used. The action increases the polarity and increases the solubility in an alkaline developer. Therefore, in the formation of the resist pattern, when the resist composition is selectively exposed to the resist film obtained by applying the resist composition on the support, the resist film exposed portion changes from sparingly soluble to alkaline developer to soluble. On the other hand, since the unexposed portion of the resist film remains hardly soluble in alkali, a positive resist pattern is formed by developing with alkali.

On the other hand, when a solvent developing process is applied, the substrate component containing the component (A1) is highly soluble in an organic developer before exposure, and for example, when acid is generated from the component (B) by exposure, Due to the action of the acid, the polarity is increased and the solubility in an organic developer is reduced. Therefore, in forming a resist pattern, when the resist composition is selectively exposed to a resist film obtained by applying the resist composition on a support, the resist film exposed portion becomes soluble to sparingly soluble in an organic developer. While it changes, the unexposed part of the resist film remains soluble and does not change. Therefore, by developing with an organic developer, a contrast can be added between the exposed part and the unexposed part, and a negative resist pattern can be obtained. It is formed.

In the resist composition of the present embodiment, the component (A) may be used alone or in combination of two or more.

-Regarding the component (A1) The component (A1) is a resin component whose solubility in a developing solution changes due to the action of an acid.
The component (A1) preferably has a structural unit (a1) containing an acid-degradable group whose polarity is increased by the action of an acid.
The component (A1) may have other structural units in addition to the structural unit (a1), if necessary.

<< Structural unit (a1) >>
The structural unit (a1) is a structural unit containing an acid-degradable group whose polarity is increased by the action of an acid.

Examples of the acid dissociable group include those proposed as an acid dissociable group of a base resin for a chemically amplified resist composition.
Specifically, as the acid dissociative group of the base resin for the chemically amplified resist composition, the "acetal type acid dissociative group" and the "tertiary alkyl ester type acid dissociative group" described below are described below. Examples include "group" and "tertiary alkyloxycarbonyl acid dissociable group".

Acetal-type acid dissociative group:
Among the polar groups, the acid dissociable group that protects the carboxy group or the hydroxyl group is, for example, an acid dissociable group represented by the following general formula (a1-r-1) (hereinafter referred to as “acetal type acid dissociative group”). There are times.).

［式中、Ｒａ’^１、Ｒａ’^２は水素原子またはアルキル基である。Ｒａ’^３は炭化水素基であって、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。］

[In the formula, ^Ra'1 and ^Ra'2 are hydrogen atoms or alkyl groups. ^Ra'3 is a hydrocarbon group, and ^Ra'3 may be bonded to either ^Ra'1 or ^Ra'2 to form a ring. ]

In the formula (a1-r-1), it is preferable that at ^{least one} of Ra'1 and Ra'2 is a hydrogen atom, and it is more preferable that both are hydrogen atoms.
When ^Ra'1 or ^Ra'2 is an alkyl group, the alkyl group includes the alkyl group mentioned as a substituent that may be bonded to the carbon atom at the α-position in the above description of the α-substituted acrylic acid ester. The same can be mentioned, and an alkyl group having 1 to 5 carbon atoms is preferable. Specifically, a linear or branched alkyl group is preferable. More specifically, 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, a neopentyl group and the like can be mentioned, and a methyl group or an ethyl group can be used. More preferably, a methyl group is particularly preferable.

In the formula (a1-r-1), examples of the hydrocarbon group of ^Ra'3 include a linear or branched alkyl group or a cyclic hydrocarbon group.
The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

The branched-chain alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group and the like, and an isopropyl group is preferable.

When ^Ra'3 is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms. Examples include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

When the cyclic hydrocarbon group of ^Ra'3 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, as the aromatic hydrocarbon group in ^Ra'3 , a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle; two or more aromatic rings. A group obtained by removing one hydrogen atom from an aromatic compound (eg, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (eg, a benzyl group). , Penetyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group and other arylalkyl groups) and the like. The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2 carbon atoms, and 1 carbon atom. Is particularly preferred.

The cyclic hydrocarbon group in ^Ra'3 may have a substituent. Examples of this substituent include those similar to Ra ^x5 described above.

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.

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

［式中、Ｒａ’^４～Ｒａ’^６はそれぞれ炭化水素基であって、Ｒａ’^５、Ｒａ’^６は互いに結合して環を形成してもよい。］

[In the formula, ^Ra'4 to ^Ra'6 are hydrocarbon groups, respectively, and ^Ra'5 and ^Ra'6 may be bonded to each other to form a ring. ]

Examples of the hydrocarbon group of ^Ra'4 include a linear or branched alkyl group, a chain or cyclic alkenyl group, or a cyclic hydrocarbon group.
Linear or branched alkyl group in ^Ra'4 , cyclic hydrocarbon group (monocyclic group, aliphatic hydrocarbon group, polycyclic group, aliphatic hydrocarbon group, aromatic hydrocarbon group) ) Is the same as that of ^Ra'3 .
The chain or cyclic alkenyl group in ^Ra'4 is preferably an alkenyl group having 2 to 10 carbon atoms.
Examples of the hydrocarbon group of ^Ra'5 and ^Ra'6 include the same as those of ^Ra'3 .

When ^Ra'5 and ^Ra'6 are bonded to each other to form a ring, a group represented by the following general formula (a1-r2-1) and a group represented by the following general formula (a1-r2-2). , The group represented by the following general formula (a1-r2-3) is preferably mentioned.
On the other hand, when ^Ra'4 to ^Ra'6 do not bind to each other and are independent hydrocarbon groups, the group represented by the following general formula (a1-r2-4) is preferably mentioned.

［式（ａ１－ｒ２－１）中、Ｒａ’^１０は、一部がハロゲン原子又はヘテロ原子含有基で置換されていてもよい直鎖状又は分岐鎖状の炭素原子数１～１２のアルキル基を示す。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を示す。式（ａ１－ｒ２－２）中、Ｙａは炭素原子である。Ｘａは、Ｙａと共に環状の炭化水素基を形成する基である。この環状の炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。Ｒａ^１０１～Ｒａ^１０３は、それぞれ独立して、水素原子、炭素原子数１～１０の１価の鎖状飽和炭化水素基又は炭素原子数３～２０の１価の脂肪族環状飽和炭化水素基である。この鎖状飽和炭化水素基及び脂肪族環状飽和炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。Ｒａ^１０１～Ｒａ^１０３の２つ以上が互いに結合して環状構造を形成していてもよい。式（ａ１－ｒ２－３）中、Ｙａａは炭素原子である。Ｘａａは、Ｙａａと共に脂肪族環式基を形成する基である。Ｒａ^１０４は、置換基を有してもよい芳香族炭化水素基である。式（ａ１－ｒ２－４）中、Ｒａ’^１２及びＲａ’^１３は、それぞれ独立に、炭素原子数１～１０の１価の鎖状飽和炭化水素基又は水素原子である。この鎖状飽和炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。Ｒａ’^１４は、置換基を有してもよい炭化水素基である。＊は結合手を示す。］

[In the formula (a1-r2-1), ^Ra'10 is a linear or branched alkyl group having 1 to 12 carbon atoms which may be partially substituted with a halogen atom or a heteroatom-containing group. Is shown. ^Ra'11 indicates a group forming an aliphatic cyclic group together with a carbon atom to which Ra ^'10 is bonded. In the formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. A part or all of the hydrogen atom contained in this cyclic hydrocarbon group may be substituted. Ra ¹⁰¹ to Ra ¹⁰³ are independently hydrogen atoms, monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms, or monovalent aliphatic cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms. be. A part or all of the hydrogen atoms contained in the chain saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group may be substituted. Two or more of Ra ¹⁰¹ to Ra ¹⁰³ may be bonded to each other to form an annular structure. In the formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra ¹⁰⁴ is an aromatic hydrocarbon group which may have a substituent. In the formula (a1-r2-4), ^Ra'12 and ^Ra'13 are independently monovalent chain saturated hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms. A part or all of the hydrogen atom contained in this chain saturated hydrocarbon group may be substituted. ^Ra'14 is a hydrocarbon group which may have a substituent. * Indicates a bond. ]

In the above formula (a1-r2-1), ^Ra'10 is a linear or branched alkyl having 1 to 12 carbon atoms which may be partially substituted with a halogen atom or a heteroatom-containing group. It is the basis.

The linear alkyl group in Ra'10 has 1 to 12 carbon atoms, preferably 1 to ¹⁰ carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Examples of the branched-chain alkyl group in ^Ra'10 include those similar to those in ^Ra'3 .

The alkyl group in ^Ra'10 may be partially substituted with a halogen atom or a heteroatom-containing group. For example, a part of the hydrogen atom constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group. Further, a part of the carbon atom (methylene group or the like) constituting the alkyl group may be substituted with a heteroatom-containing group.
Examples of the hetero atom here include an oxygen atom, a sulfur atom, and a nitrogen atom. Heteroatom-containing groups include (-O-), -C (= O) -O-, -OC (= O)-, -C (= O)-, and -OC (= O)-. Examples thereof include O-, -C (= O) -NH-, -NH-, -S-, -S (= O) _2- , -S (= O) ₂ -O-, and the like.

In the formula (a1-r2-1), ^Ra'11 (an aliphatic cyclic group formed together with a carbon atom bonded to ^Ra'10 ) is a monocyclic group of ^Ra'3 in the formula (a1-r-1). Alternatively, the group listed as an aliphatic hydrocarbon group (lipocyclic hydrocarbon group) which is a polycyclic group is preferable. Among them, a monocyclic alicyclic hydrocarbon group is preferable, specifically, a cyclopentyl group and a cyclohexyl group are more preferable, and a cyclopentyl group is further preferable.

In the formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa together with Ya is the cyclic monovalent hydrocarbon group (lipid group) in ^Ra'3 in the formula (a1-r-1). A group obtained by further removing one or more hydrogen atoms from a hydrocarbon group) can be mentioned.
The cyclic hydrocarbon group that Xa forms with Ya may have a substituent. Examples of this substituent include the same substituents that the cyclic hydrocarbon group in ^Ra'3 may have.
In the formula (a1-r2-2), examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra ¹⁰¹ to Ra ¹⁰³ include a methyl group, an ethyl group, a propyl group and a butyl group. Examples thereof include a pentyl group, a hexyl group, a heptyl group, an octyl group and a decyl group.
Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in Ra ¹⁰¹ to Ra ¹⁰³ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Monocyclic aliphatic saturated hydrocarbon groups such as cyclodecyl group and cyclododecyl group; bicyclo [2.2.2] octanyl group, tricyclo [5.2.2.102,6] decanyl group, tricyclo [3.3. Examples thereof include a polycyclic aliphatic saturated hydrocarbon group such as 1.13,7] decanyl group, tetracyclo [6.2.1.13, 6.02,7] dodecanyl group and adamantyl group.
Among Ra ¹⁰¹ to Ra ¹⁰³ , hydrogen atoms and monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms are preferable from the viewpoint of easiness of synthesis, and among them, hydrogen atoms, methyl groups and ethyl groups are preferable. More preferably, a hydrogen atom is particularly preferable.

Examples of the substituent contained in the chain saturated hydrocarbon group represented by Ra ¹⁰¹ to Ra ¹⁰³ or the aliphatic cyclic saturated hydrocarbon group include the same groups as Ra ^{x 5} described above.

Examples of the group containing a carbon-carbon double bond generated by two or more of Ra ¹⁰¹ to Ra ¹⁰³ bonding to each other to form a cyclic structure include a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, and a methyl. Examples thereof include a cyclohexenyl group, a cyclopentylideneethenyl group, a cyclohexylideneethenyl group and the like. Among these, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylideneethenyl group are preferable from the viewpoint of easiness of synthesis.

In the formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is an aliphatic hydrocarbon which is a monocyclic group or a polycyclic group of ^Ra'3 in the formula (a1-r-1). The groups listed as hydrogen groups are preferred.
In the formula (a1-r2-3), examples of the aromatic hydrocarbon group in Ra ¹⁰⁴ include a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra ¹⁰⁴ is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, and more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene. Preferably, a group having one or more hydrogen atoms removed from benzene, naphthalene or anthracene is more preferable, a group having one or more hydrogen atoms removed from benzene or naphthalene is particularly preferable, and a group having one or more hydrogen atoms removed from benzene is particularly preferable. Most preferred.

Examples of the substituent that Ra ¹⁰⁴ in the formula (a1-r2-3) may have include a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, a halogen atom and an alkoxy group (methoxy group, Ethoxy group, propoxy group, butoxy group, etc.), alkyloxycarbonyl group and the like can be mentioned.

In the formula (a1-r2-4), ^Ra'12 and ^Ra'13 are independently monovalent chain saturated hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms. As the monovalent chain-saturated hydrocarbon group having 1 to 10 carbon atoms in ^Ra'12 and ^Ra'13 , the monovalent chain-saturated hydrocarbon group having 1 to 10 carbon atoms in Ra ¹⁰¹ to Ra ¹⁰³ described above is used. The same as the hydrocarbon group can be mentioned. A part or all of the hydrogen atom contained in this chain saturated hydrocarbon group may be substituted.
Among ^Ra'12 and ^Ra'13 , a hydrogen atom and an alkyl group having 1 to 5 carbon atoms are preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, a methyl group and an ethyl group are more preferable, and a methyl group is more preferable. Is particularly preferable.
When the chain saturated hydrocarbon group represented by ^Ra'12 and ^Ra'13 is substituted, examples of the substituent include the same groups as Ra ^{x 5} described above.

In the formula (a1-r2-4), ^Ra'14 is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group in ^Ra'14 include a linear or branched alkyl group or a cyclic hydrocarbon group.

The linear alkyl group in ^Ra'14 preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

The branched-chain alkyl group in ^Ra'14 preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group and the like, and an isopropyl group is preferable.

When ^Ra'14 is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms. Examples include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

Examples of the aromatic hydrocarbon group in Ra ^'14 include the same as the aromatic hydrocarbon group in Ra ¹⁰⁴ . Among them, ^Ra'14 is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, and a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene. More preferably, a group having one or more hydrogen atoms removed from benzene, naphthalene or anthracene is further preferable, a group having one or more hydrogen atoms removed from naphthalene or anthracene is particularly preferable, and a group having one or more hydrogen atoms removed from naphthalene is particularly preferable. Is most preferable.
Examples of the substituent that Ra ^'14 may have include the same substituents that Ra ¹⁰⁴ may have.

When Ra'14 in the formula (a1- ^r2-4 ) is a naphthyl group, the position of bonding with the tertiary carbon atom in the formula (a1-r2-4) is at the 1-position or the 2-position of the naphthyl group. It may be either.
When Ra'14 in the formula (a1- ^r2-4 ) is an anthryl group, the position at which the tertiary carbon atom is bonded in the formula (a1-r2-4) is the 1-position, 2-position or the anthryl group. It may be any of the 9th place.

Specific examples of the group represented by the above formula (a1-r2-1) are given below.

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

Specific examples of the group represented by the above formula (a1-r2-3) are given below.

Specific examples of the group represented by the above formula (a1-r2-4) are given below.

Tertiary alkyloxycarbonylic acid dissociative group:
Among the polar groups, the acid dissociable group that protects the hydroxyl group is, for example, an acid dissociable group represented by the following general formula (a1-r-3) (hereinafter, for convenience, “tertiary alkyloxycarbonylic acid dissociable group”. ") Can be mentioned.

［式中、Ｒａ’^７～Ｒａ’^９はそれぞれアルキル基である。］

[In the formula, ^Ra'7 to ^Ra'9 are alkyl groups, respectively. ]

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

As the structural unit (a1), a structural unit derived from an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent, a structural unit derived from acrylamide, hydroxystyrene or hydroxy. A structural unit in which at least a part of the hydrogen atom in the hydroxyl group of the structural unit derived from the styrene derivative is protected by the substituent containing the acid-degradable group, vinyl benzoic acid or a structural unit derived from the vinyl benzoic acid derivative- Examples thereof include a structural unit in which at least a part of a hydrogen atom in C (= O) -OH is protected by a substituent containing the acid-degradable group.

Among the above, the structural unit (a1) is preferably a structural unit derived from an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent.
Preferred specific examples of such a structural unit (a1) include a structural unit represented by the following general formula (a1-1) or (a1-2).

［式中、Ｒは、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基である。Ｖａ^１は、エーテル結合を有していてもよい２価の炭化水素基である。ｎ_ａ１は、０～２の整数である。Ｒａ^１は、上記の一般式（ａ１－ｒ－１）又は（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の整数であり、Ｒａ^２は上記の一般式（ａ１－ｒ－１）又は（ａ１－ｒ－３）で表される酸解離性基である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Va ¹ is a divalent hydrocarbon group that may have an ether bond. n _a1 is an integer of 0 to 2. Ra ¹ is an acid dissociative group represented by the above general formula (a1-r-1) or (a1-r-2). Wa ¹ is a n _a2 + 1 valent hydrocarbon group, na ₂ is an integer of 1 to 3, and Ra ² is represented by the above general formula (a1-r-1) or (a1-r-3). It is an acid dissociative group. ]

In the above formula (a1-1), the alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and more specifically, a methyl group. Examples thereof include 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 the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, 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.

In the above formula (a1-1), the divalent hydrocarbon group in Va ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group as the divalent hydrocarbon group in Va ¹ may be saturated or unsaturated, and is usually preferably saturated.
More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in its structure, and the like.

The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and 1 to 1 to 4 carbon atoms. 3 is the most preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], a trimethylene group [ -(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ] and the like can be mentioned.
The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and 3 carbon atoms. Most preferred.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -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 -etc. Alkyl methylene groups;- 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 ) CH ₃ ) ₂ -CH ₂ -etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include alkylalkylene groups such as alkyltetramethylene 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.

As the aliphatic hydrocarbon group containing a ring in the structure, an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from the alicyclic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the terminal of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like. Examples of the linear or branched aliphatic hydrocarbon group include the same as the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group.
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 a polycyclic type or a monocyclic type. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. 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 a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, specifically. Examples thereof include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group as a divalent hydrocarbon group in Va ¹ is a hydrocarbon group having an aromatic ring.
The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, still more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. preferable. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.
Specific examples of the aromatic ring contained 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 heterogeneous. Examples thereof include aromatic heterocycles substituted with atoms. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
Specifically, the aromatic hydrocarbon group is 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). ) Is a group in which one of the hydrogen atoms is substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group and the like. A group in which one hydrogen atom is further removed from the aryl group in the group) and the like can be mentioned. The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

In the above formula (a1-1), Ra ¹ is an acid dissociative group represented by the above formula (a1-r-1) or (a1-r-2).

In the above formula (a1-2), the _na2 + 1-valent hydrocarbon group in Wa ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in the structure, and a linear or branched aliphatic hydrocarbon group. Examples thereof include a group combined with an aliphatic hydrocarbon group containing a ring in the structure.
_{The na2} + 1 valence is preferably 2 to 4 valences, more preferably 2 or 3 valences.

In the above formula (a1-2), Ra ² is an acid dissociative group represented by the above general formula (a1-r-1) or (a1-r-3).

Specific examples of the structural units represented by the above formula (a1-1) are shown below. In each of the following formulas, 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 kind or two or more kinds.
As the structural unit (a1), the structural unit represented by the above formula (a1-1) is more preferable because it is easy to improve the characteristics (sensitivity, shape, etc.) in lithography by electron beam or EUV.
Among these, as the structural unit (a1), a unit including a structural unit represented by the following general formula (a1-1-1) is particularly preferable.

［式中、Ｒａ^１”は、一般式（ａ１－ｒ２－１）、（ａ１－ｒ２－３）又は（ａ１－ｒ２－４）で表される酸解離性基である。］

[In the formula, Ra ¹ "is an acid dissociative group represented by the general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4)].

In the formula ( _a1-1-1 ), R, Va ¹ and na 1 are the same as R, Va ¹ and _na 1 in the formula (a 1-1).
The description of the acid dissociative group represented by the general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4) is as described above. Among them, it is preferable to select a cyclic group having an acid dissociative group because it is suitable for EB or EUV because of its increased reactivity.

In the above formula (a1-1-1), Ra ¹ "is an acid dissociative group represented by the general formula (a1-r2-1) or the general formula (a1-r2-3) among the above. Is preferable, and it is more preferable that it is an acid dissociative group represented by the general formula (a1-r2-1).

The ratio of the constituent unit (a1) in the component (A1) is preferably 5 to 80 mol%, preferably 10 to 75 mol%, based on the total (100 mol%) of all the constituent units constituting the component (A1). Is more preferable, 10 to 70 mol% is further preferable, and 10 to 60 mol% is particularly preferable.
By setting the ratio of the structural unit (a1) to be equal to or higher than the lower limit of the above-mentioned preferable range, the lithography characteristics such as sensitivity, resolution, and roughness improvement are improved. On the other hand, when it is not more than the upper limit of the above-mentioned preferable range, it is possible to balance with other constituent units and various lithography characteristics are improved.

≪Other building blocks≫
The component (A1) may have other structural units, if necessary, in addition to the above-mentioned structural unit (a1).
The other structural unit includes, for example, a structural unit (a10) represented by the general formula (a10-1) described later; a lactone-containing cyclic group, a _—SO2 -containing cyclic group, or a carbonate-containing cyclic group. Unit (a2); Constituent unit containing a polar group-containing aliphatic hydrocarbon group (a3); Constituent unit containing an acid non-dissociable aliphatic cyclic group (a4); Constituent unit derived from styrene or a styrene derivative (a4) st) and the like.

About the structural unit (a10):
The structural unit (a10) is a structural unit represented by the following general formula (a10-1).

［式中、Ｒは、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基である。Ｙａ^ｘ１は、単結合又は２価の連結基である。Ｗａ^ｘ１は、置換基を有してもよい芳香族炭化水素基である。ｎ_ａｘ１は、１以上の整数である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. Ya ^x1 is a single bond or divalent linking group. Wa ^x1 is an aromatic hydrocarbon group which may have a substituent. n _ax1 is an integer of 1 or more. ]

In the formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms.
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, a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. Examples thereof include an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
The halogenated alkyl group having 1 to 5 carbon atoms in R is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, 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, a methyl group or a trifluoromethyl group is preferable because of easy industrial availability. Is more preferable, a hydrogen atom or a methyl group is further preferable, and a methyl group is particularly preferable.

In the formula (a10-1), Ya ^x1 is a single bond or a divalent linking group.
In the above chemical formula, the divalent linking group in Ya ^x1 is not particularly limited, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom and the like are suitable. Is mentioned as.

A divalent hydrocarbon group that may have a substituent:
When Ya ^x1 is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group in Ya ^x1 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, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

... Linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. , 1 to 4 carbon atoms are more preferable, and 1 to 3 carbon atoms are most preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], a trimethylene group [ -(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ] and the like can be mentioned.
The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and 3 carbon atoms. Most preferred.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -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 -etc. Alkyl methylene groups;- 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 ) CH ₃ ) ₂ -CH ₂ -etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include alkylalkylene groups such as alkyltetramethylene 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.

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, a carbonyl group and the like.

... An aliphatic hydrocarbon group containing a ring in the structure As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group may contain a substituent containing a hetero atom in the ring structure. (A group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, the cyclic fat. Examples thereof include a group in which a group hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. 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 a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically. Examples include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

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, an alkyl halide group, a hydroxyl group, a carbonyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are more preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are more preferable. , A methoxy group and an ethoxy group are more preferable.
As the halogen atom as the substituent, a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
The cyclic aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom as a part of the carbon atom constituting the ring structure. As the substituent containing the heteroatom, —O—, —C (= O) —O—, —S—, —S (= O) _2- , —S (= O) ₂ -O— are preferable.

Aromatic hydrocarbon group in Ya ^x1 The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings. A group from which two hydrogen atoms have been removed from (for example, biphenyl, fluorene, etc.); one of the hydrogen atoms of the group (aryl group or heteroaryl group) from which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocyclic ring. Hydrogen from an aryl group in an arylalkyl group such as a group substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group). A group from which one atom is further removed) and the like can be mentioned. The number of carbon atoms of the alkylene group bonded to the aryl group or the heteroaryl group is preferably 1 to 4, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom number. ..

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, an alkyl halide group, a hydroxyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are more preferable.
Examples of the alkoxy group, the halogen atom and the alkyl halide group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.

-A divalent linking group containing a heteroatom:
When Ya ^x1 is a divalent linking group containing a hetero atom, the preferred linking groups are -O-, -C (= O) -O-, -OC (= O)-,-. C (= O)-, -OC (= O) -O-, -C (= O) -NH-, -NH-, -NH-C (= NH)-(H is an alkyl group or an acyl group) , Etc.), -S-, -S (= O) _2- , -S (= O) ₂ -O-, general formula-Y ²¹ -OY ^22- , -Y ²¹ -O-, -Y ^{21-C (= O) -O-, -C (= O) -O-Y 21-,-[Y 21 - C} (= O) -O] _{m "} -Y ^22- , -Y ²¹ -OC (= O) -Y ^{22- or -Y 21 -} S (= O) ₂ -O-Y ^22- [In the formula, Y ²¹ and Y ²² are Each is a divalent hydrocarbon group which may have a substituent independently, O is an oxygen atom, and m "is an integer of 0 to 3. ] And so on.
The divalent linking group containing the hetero atom is -C (= O) -NH-, -C (= O) -NH-C (= O)-, -NH-, -NH-C (= NH). In the case of −, the H may be substituted with a substituent such as an alkyl group or an acyl. 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.
General 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-, -Y ²¹ - ^OC (= O) -Y ^{22- or -Y 21 -} S (= O) ₂ -O-Y ²² -Medium, Y ²¹ and Y ²² are divalent hydrocarbon groups which may independently have a substituent. The divalent hydrocarbon group is described as a divalent linking group in Ya ^x1 . The same as those mentioned in (divalent hydrocarbon group which may have a substituent) can be mentioned.
As ^Y21 , 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 preferable. Especially preferable.
As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkyl methylene group is more preferable. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
In the group represented by the formula- [Y ²¹ -C (= O) -O] _{m "} -Y ^22- , m" is an integer of 0 to 3, preferably an integer of 0 to 2, and 0. Or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula- [Y ²¹ -C (= O) -O] _{m "} -Y ^22- is represented by the formula-Y ²¹ -C ⁽ = O) -OY 22-. A group is particularly preferable. Among them, a group represented by the formula- (CH ₂ ) _a' -C (= O) -O- (CH ₂ ) b'-is preferable. In the formula, _a'is 1 to 1 to. It is an integer of 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 and 1 to 8. Is preferred, an integer of 1 to 5 is more preferred, 1 or 2 is even more preferred, and 1 is most preferred.

Among the above, as Ya ^x1 , single bond, ester bond [-C (= O) -O-, -OC (= O)-], ether bond (-O-), linear or branched chain It is preferably a alkylene group in the form of an alkylene group or a combination thereof, and a single bond or an ester bond [-C (= O) -O-, -OC (= O)-] is more preferable.

In the above formula (a10-1), Wa ^x1 is an aromatic hydrocarbon group which may have a substituent.
Examples of the aromatic hydrocarbon group in Wa ^x1 include a group obtained by removing (n _ax1 + 1) hydrogen atoms from an aromatic ring which may have a substituent. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specifically, the aromatic ring is an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, or phenanthrene; an aromatic heterocycle in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom or the like. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Further, as the aromatic hydrocarbon group in Wa ^x1 , (n _ax1 + 1) hydrogen atoms are removed from aromatic compounds (for example, biphenyl, fluorene, etc.) containing an aromatic ring which may have two or more substituents. There is also a group.
Among the above, Wa ^x1 is preferably a group obtained by removing (n _ax1 + 1) hydrogen atoms from benzene, naphthalene, anthracene or biphenyl, and a group obtained by removing (n _ax1 + 1) hydrogen atoms from benzene or naphthalene. Is more preferable, and a group obtained by removing (n _ax1 + 1) hydrogen atoms from benzene is even more preferable.

The aromatic hydrocarbon group in Wa ^x1 may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group and the like. Examples of the alkyl group, alkoxy group, halogen atom, and alkyl halide group as the substituent include those similar to those mentioned as the substituent of the cyclic aliphatic hydrocarbon group in Ya ^x1 . The substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and is an ethyl group or methyl. Groups are more preferred, and methyl groups are particularly preferred. The aromatic hydrocarbon group in Wa ^x1 preferably has no substituent.

In the above formula (a10-1), n _ax1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably 1, 2 or 3, and 1 or 2. Especially preferable.

Hereinafter, a specific example of the structural unit (a10) represented by the above formula (a10-1) will be shown.
In each of the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The structural unit (a10) contained in the component (A1) may be one kind or two or more kinds.
When the component (A1) has a constituent unit (a10), the ratio of the constituent unit (a10) in the component (A1) is the total (100 mol%) of all the constituent units constituting the component (A1). 5 to 80 mol% is preferable, 10 to 75 mol% is more preferable, 30 to 70 mol% is further preferable, and 30 to 60 mol% is particularly preferable.
By setting the ratio of the structural unit (a10) to the lower limit value or more, the sensitivity can be more easily increased. On the other hand, by setting the value to the upper limit or less, it becomes easier to balance with other constituent units.

About the structural unit (a2):
The component (A1) is a structural unit (a2) containing a lactone-containing cyclic group, a _—SO2 -containing cyclic group or a carbonate-containing cyclic group (provided that the structural unit (a01) or the structural unit (a1) is used. It may have (excluding applicable ones).
The lactone-containing cyclic group, _-SO2 -containing cyclic group, or carbonate-containing cyclic group of the structural unit (a2) adheres to the substrate of the resist film when the component (A1) is used for forming the resist film. It is effective in enhancing sex. In addition, having the structural unit (a2) has the effects of, for example, appropriately adjusting the acid diffusion length, enhancing the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development, resulting in lithography characteristics. Etc. are good.

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 when it has only a lactone 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 lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
As the lactone-containing cyclic group in the structural unit (a2), any one can be used without particular limitation. Specifically, the groups represented by the following general formulas (a2-r-1) to (a2-r-7) can be mentioned.

［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、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は－ＳＯ_２－含有環式基であり；Ａ”は酸素原子（－Ｏ－）もしくは硫黄原子（－Ｓ－）を含んでいてもよい炭素原子数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。］

[In the formula, ^Ra'21 is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, -COOR ", -OC (= O) R", a hydroxyalkyl group or a cyano group. Yes; R "is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ₂ -containing cyclic group; A" is an oxygen atom (-O-) or a sulfur atom (-). It is an alkylene group having 1 to 5 carbon atoms, an oxygen atom or a sulfur atom which may contain S-), n'is an integer of 0 to 2, and m'is 0 or 1. ]

In the general formulas (a2-r-1) to (a2-r-7), the alkyl group in ^Ra'21 is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. 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, a neopentyl group and a hexyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
As the alkoxy group in ^Ra'21 , an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specifically, the group in which the alkyl group mentioned as the alkyl group in ^Ra'21 and the oxygen atom (—O—) are linked can be mentioned.
As the halogen atom in ^Ra'21 , a fluorine atom is preferable.
Examples of the alkyl halide group in ^Ra'21 include a group in which a part or all of the hydrogen atom of the alkyl group in ^Ra'21 is replaced with the halogen atom. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

In -COOR "and -OC (= O) R" in Ra ^'21 , R "is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or _-SO2 -containing cyclic group. Is.
The alkyl group in "R" may be linear, branched or cyclic, and the number of carbon atoms is preferably 1 to 15.
When R "is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is a methyl group or an ethyl group. Is particularly preferable.
When R "is a cyclic alkyl group, the number of carbon atoms is preferably 3 to 15, more preferably 4 to 12, and most preferably 5 to 10 carbon atoms. , A group obtained by removing one or more hydrogen atoms from a monocycloalkane that may or may not be substituted with a fluorine atom or a fluorinated alkyl group; such as bicycloalkane, tricycloalkane, tetracycloalkane, etc. Examples thereof include a group obtained by removing one or more hydrogen atoms from a polycycloalkane. More specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane and cyclohexane; Examples thereof include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as isobornane, tricyclodecane, and tetracyclododecane.
Examples of the lactone-containing cyclic group in "R" include the same groups as those represented by the general formulas (a2-r-1) to (a2-r-7).
The carbonate-containing cyclic group in "R" is the same as the carbonate-containing cyclic group described later, and specifically, the groups represented by the general formulas (ax3-r-1) to (ax3-r-3), respectively. Can be mentioned.
The —SO ₂ -containing cyclic group in R ”is the same as the —SO ₂ -containing cyclic group described later, and specifically, the general formulas (a5-r-1) to (a5-r-4). The groups represented by are listed below.
The hydroxyalkyl group in ^Ra'21 is preferably one having 1 to 6 carbon atoms, and specific examples thereof include a group in which at least one hydrogen atom of the alkyl group in ^Ra'21 is substituted with a hydroxyl group. Be done.
^Ra'21 preferably has at least one cyano group.

In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A "is a linear or branched alkylene group. The alkylene group of the above is preferable, and examples thereof include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and the like. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include the terminal of the alkylene group or Examples include groups in which -O- or -S- intervenes between carbon atoms, such as O-CH _2- , -CH ₂ -O-CH _2- , -S-CH _2- , -CH ₂ -SCH. 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.

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

The "-SO ₂ -containing cyclic group" refers to a cyclic group containing a ring containing -SO _2- in its ring skeleton, and specifically, the sulfur atom (S) in -SO _2- A cyclic group that forms part of the cyclic skeleton of the cyclic group. A ring containing -SO _2- in its ring skeleton is counted as the first ring, and if it is only the ring, it is a monocyclic group, and if it has another ring structure, it is a polycyclic group regardless of its structure. It is called. -SO ₂ -The contained cyclic group may be a monocyclic group or a polycyclic group.
-SO ₂ -containing cyclic groups are particularly cyclic groups containing -O-SO ₂ -in their cyclic skeleton, that is, -OS- in -O-SO _2- contains a part of the cyclic skeleton. It is preferably a cyclic group containing a sultone ring to be formed.
More specifically, examples of the _-SO2 -containing cyclic group include groups represented by the following general formulas (a5-r-1) to (a5-r-4).

［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、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は－ＳＯ_２－含有環式基であり；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原子数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。］

[In the formula, ^Ra'51 is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, -COOR ", -OC (= O) R", a hydroxyalkyl group or a cyano group. Yes; R "is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ₂ -containing cyclic group; A" is a carbon containing an oxygen atom or a sulfur atom. It is an alkylene group having 1 to 5 atoms, an oxygen atom or a sulfur atom, and n'is an integer of 0 to 2. ]

In the general formulas (a5-r-1) to (a5-r-2), A "is a general formula (a2-r-2), (a2-r-3), (a2-r-5). It is the same as A "inside.
The alkyl group, alkoxy group, halogen atom, halogenated alkyl group, -COOR ", -OC (= O) R", and hydroxyalkyl group in Ra ^'51 are the above-mentioned general formulas (a2-r-1) to (1), respectively. 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 the general formulas (a5-r-1) to (a5-r-4) are given below. "Ac" in the formula indicates an acetyl group.

The “carbonate-containing cyclic group” refers to a cyclic group containing a ring (carbonate ring) containing —O—C (= O) —O— in its cyclic 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 a monocyclic group or a polycyclic group.
As the carbonate ring-containing cyclic group, any one can be used without particular limitation. Specifically, the groups represented by the following general formulas (ax3-r-1) to (ax3-r-3) can be mentioned.

［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、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は－ＳＯ_２－含有環式基であり；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原子数１～５のアルキレン基、酸素原子または硫黄原子であり、ｐ’は０～３の整数であり、ｑ’は０または１である。］

[In the formula, ^Ra'x31 is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, -COOR ", -OC (= O) R", a hydroxyalkyl group or a cyano group. Yes; R "is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ₂ -containing cyclic group; A" is a carbon containing an oxygen atom or a sulfur atom. It is an alkylene group having 1 to 5 atoms, an oxygen atom or a sulfur atom, p'is an integer of 0 to 3, and q'is 0 or 1. ]

In the general formulas (ax3-r-2) to (ax3-r-3), A "is a general formula (a2-r-2), (a2-r-3), (a2-r-5). It is the same as A "inside.
The alkyl group, alkoxy group, halogen atom, halogenated alkyl group, -COOR ", -OC (= O) R", and hydroxyalkyl group in Ra ^'31 are the above-mentioned general formulas (a2-r-1) to (1), respectively. 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 the general formulas (ax3-r-1) to (ax3-r-3) are given below.

As the structural unit (a2), a structural unit derived from an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent is preferable.
The structural unit (a2) is preferably a structural unit represented by the following general formula (a2-1).

［式中、Ｒは水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基である。Ｙａ^２１は単結合または２価の連結基である。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はラクトン含有環式基、カーボネート含有環式基、又は－ＳＯ_２－含有環式基である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. Ya ²¹ is a single bond or divalent linking group. La ²¹ is -O-, -COO-, -CON (R')-, -OCO-, -CONHCO- or -CONHCS-, where R'represents a hydrogen atom or a methyl group. However, when La ²¹ is -O-, Ya ²¹ is not -CO-. Ra ²¹ is a lactone-containing cyclic group, a carbonate-containing cyclic group, or a _-SO2 -containing cyclic group. ]

In the formula (a2-1), R is the same as described above. 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 particularly preferable from the viewpoint of industrial availability.

In the formula (a2-1), examples of the divalent linking group in Ya ²¹ include the same divalent linking group in Ya ^x1 in the general formula (a10-1).

Among the above, Ya ²¹ may be a single bond, an ester bond [-C (= O) -O-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof. It is preferable to have.

In the formula (a2-1), Ra ²¹ is a lactone-containing cyclic group, a _—SO2 -containing cyclic group, or a carbonate-containing cyclic group.
The lactone-containing cyclic group, _-SO2 -containing cyclic group, and carbonate-containing cyclic group in Ra ²¹ are represented by the above-mentioned general formulas (a2-r-1) to (a2-r-7), respectively. Group, groups represented by the general formulas (a5-r-1) to (a5-r-4), and groups represented by the general formulas (ax3-r-1) to (ax3-r-3), respectively. Is preferably mentioned.
Of these, a lactone-containing cyclic group or a _-SO2 -containing cyclic group is preferable, and the general formulas (a2-r-1), (a2-r-2), (a2-r-6) or (a5-r) are preferable. The groups represented by -1) are more preferable. Specifically, the chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-18), (r- Any group represented by lc-6-1), (r-sl-1-1), and (r-sl-1-18) is more preferable, and the above chemical formula (r-lc-2-1) is more preferable. ) Or (r-lc-2-12) is more preferable, and the group represented by the chemical formula (r-lc-2-12) is particularly preferable.

The structural unit (a2) contained in the component (A1) may be one kind or two or more kinds.
When the component (A1) has a constituent unit (a2), the ratio of the constituent unit (a2) is 5 to 95 mol% with respect to the total (100 mol%) of all the constituent units constituting the component (A1). It is preferably 10 to 90 mol%, more preferably 20 to 90 mol%, and particularly preferably 30 to 90 mol%.
When the ratio of the constituent unit (a2) is at least the preferable lower limit value, the effect of containing the constituent unit (a2) is sufficiently obtained by the above-mentioned effect, and when it is at least the upper limit value, it is different from other constituent units. It can be balanced and has good various lithography characteristics.

About the structural unit (a3):
The component (A1) is further divided into a constituent unit (a3) containing a polar group-containing aliphatic hydrocarbon group (provided that the constituent unit (a01), the constituent unit (a1), the constituent unit (a2) or the constituent unit (a8). It may have (excluding applicable ones). Since the component (A1) has the constituent unit (a3), the hydrophilicity of the component (A1) is increased, which contributes to the improvement of the resolution. In addition, the acid diffusion length can be appropriately adjusted.

Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group and the like, and a 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 for example, in the resin for the resist composition for ArF excimer laser, it can be appropriately selected from a large number of proposed ones and used.

When the cyclic group is a monocyclic group, the number of carbon atoms is more preferably 3 to 10. Among them, a structural unit derived from an acrylic acid ester containing an aliphatic monocyclic group containing a hydroxyl group, a cyano group, or a carboxy group is more preferable. As the monocyclic group, a group obtained by removing two or more hydrogen atoms from a monocycloalkane can be exemplified. Specific examples thereof include groups obtained by removing two or more hydrogen atoms from monocycloalkanes such as cyclopentane, cyclohexane and cyclooctane. Among these monocyclic groups, a group obtained by removing two or more hydrogen atoms from cyclopentane and a group obtained by removing two or more hydrogen atoms from cyclohexane are industrially preferable.

When the cyclic group is a polycyclic group, the number of carbon atoms of the polycyclic group is more preferably 7 to 30. Among them, a structural unit derived from an acrylic acid ester containing an aliphatic polycyclic group containing a hydroxyl group, a cyano group, or a carboxy group is more preferable. Examples of the polycyclic group include a group obtained by removing two or more hydrogen atoms from a bicycloalkane, a tricycloalkane, a tetracycloalkane, or the like. Specific examples thereof include groups obtained by removing two or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, there are a group in which two or more hydrogen atoms are removed from adamantan, a group in which two or more hydrogen atoms are removed from norbornan, and a group in which two or more hydrogen atoms are removed from tetracyclododecane. Industrially preferable.

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 acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent and includes a polar group-containing aliphatic hydrocarbon group. Constituent 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, the hydroxyethyl ester of acrylic acid is used. Derived building blocks are preferred.
Further, as the structural unit (a3), the structural unit represented by the following formula (a3-1) and the structural unit represented by the formula (a3-2) are preferable.

［式中、Ｒは前記と同じであり、ｊは１～３の整数であり、ｋは１～３の整数である。］

[In the equation, R is the same as above, j is an integer of 1 to 3, and k is an integer of 1 to 3. ]

In the formula (a3-1), j is preferably 1 or 2, and more preferably 1. When j is 2, it is preferable that the hydroxyl group is bonded to the 3-position and the 5-position of the adamantyl group. When j is 1, it is preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group.
It is preferable that j is 1, and it is particularly preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group.

In the formula (a3-2), k is preferably 1. The cyano group is preferably attached to the 5- or 6-position of the norbornyl group.

The structural unit (a3) contained in the component (A1) may be one type or two or more types.
When the component (A1) has a constituent unit (a3), the ratio of the constituent unit (a3) is 1 to 30 mol% with respect to the total (100 mol%) of all the constituent units constituting the component (A1). It is preferably present, more preferably 2 to 25 mol%, still more preferably 5 to 20 mol%.
By setting the ratio of the constituent unit (a3) to be equal to or higher than the preferable lower limit value, the effect of containing the constituent unit (a3) can be sufficiently obtained by the above-mentioned effect, and if it is not more than the preferable upper limit value, other configurations are obtained. It can be balanced with the unit and various lithography characteristics are improved.

About the structural unit (a4):
The component (A1) may further have a structural unit (a4) containing an acid non-dissociative aliphatic cyclic group.
Since the component (A1) has the structural unit (a4), the dry etching resistance of the resist pattern to be formed is improved. In addition, the hydrophobicity of the component (A1) is increased. The improvement of hydrophobicity contributes to the improvement of resolution, resist pattern shape, etc., especially in the case of solvent development process.
The "acid non-dissociative cyclic group" in the structural unit (a4) means that when an acid is generated in the resist composition by exposure (for example, the acid is generated from the structural unit or the component (B) that generates acid by exposure. It is a cyclic group that remains in the constituent unit as it is without dissociation even if the acid acts on it.

As the structural unit (a4), for example, a structural unit derived from an acrylic acid ester containing an acid non-dissociative aliphatic cyclic group is preferable. As the cyclic group, many conventionally known ones can be used as the resin component of the resist composition for ArF excimer laser, KrF excimer laser (preferably for ArF excimer laser) and the like. ..
The cyclic group is preferably at least one selected from a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group from the viewpoint of industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
As the structural unit (a4), specifically, the structural units represented by the following general formulas (a4-1) to (a4-7) can be exemplified.

［式中、Ｒ^αは前記と同じである。］

[In the formula, R ^α is the same as above. ]

The structural unit (a4) contained in the component (A1) may be one type or two or more types.
When the component (A1) has a constituent unit (a4), the ratio of the constituent unit (a4) is 1 to 40 mol% with respect to the total (100 mol%) of all the constituent units constituting the (A1) component. It is preferably 1 to 20 mol%, and more preferably 1 to 20 mol%.
By setting the ratio of the constituent unit (a4) to be equal to or higher than the preferable lower limit value, the effect of containing the constituent unit (a4) can be sufficiently obtained, while by setting the ratio to be equal to or lower than the preferable upper limit value, other constituent units can be obtained. It becomes easier to balance with.

About the structural unit (st):
The structural unit (st) is a structural unit derived from styrene or a styrene derivative. "Constituent unit derived from styrene" means a structural unit composed by cleavage of the ethylenic double bond of styrene. The “constituent unit derived from the styrene derivative” means a structural unit formed by cleaving the ethylenic double bond of the styrene derivative (however, excluding those corresponding to the structural unit (a10)).

By "styrene derivative" is meant a compound in which at least a portion of the hydrogen atom of styrene is substituted with a substituent. Examples of the styrene derivative include those in which the hydrogen atom at the α-position of styrene is substituted with a substituent, those in which one or more hydrogen atoms in the benzene ring of styrene are substituted with a substituent, and the hydrogen atom at the α-position of styrene. And one in which one or more hydrogen atoms of the benzene ring are substituted with a substituent and the like.

Examples of the substituent substituting the hydrogen atom at the α-position of styrene include an alkyl group having 1 to 5 carbon atoms and an alkyl halide group having 1 to 5 carbon atoms.
As the alkyl group having 1 to 5 carbon atoms, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. Examples thereof include an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
The alkyl halide 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 are substituted with a halogen atom. As the halogen atom, a fluorine atom is particularly preferable.
As the substituent that replaces the hydrogen atom at the α-position of styrene, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms or carbon is preferable. A fluorinated alkyl group having 1 to 3 atoms is more preferable, and a methyl group is further preferable from the viewpoint of industrial availability.

Examples of the substituent that substitutes the hydrogen atom of the benzene ring of styrene include an alkyl group, an alkoxy group, a halogen atom, and an alkyl halide group.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are more preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are more preferable. , A methoxy group and an ethoxy group are more preferable.
As the halogen atom as the substituent, a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
As the substituent for substituting the hydrogen atom of the benzene ring of styrene, an alkyl group having 1 to 5 carbon atoms is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is further preferable.

As the structural unit (st), the structural unit derived from styrene, or the hydrogen atom at the α-position of styrene was replaced with an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms. A structural unit derived from a styrene derivative is preferable, a structural unit derived from styrene, or a structural unit derived from a styrene derivative in which the hydrogen atom at the α-position of styrene is substituted with a methyl group is more preferable, and the structural unit is derived from styrene. The structural unit is more preferable.

The structural unit (st) contained in the component (A1) may be one type or two or more types.
When the component (A1) has a constituent unit (st), the ratio of the constituent unit (st) is 1 to 30 mol% with respect to the total (100 mol%) of all the constituent units constituting the (A1) component. It is preferably 1 to 20 mol%, and more preferably 1 to 20 mol%.

As the component (A1) contained in the resist composition of the present embodiment, one type may be used alone, or two or more types may be used in combination.
In the resist composition of the present embodiment, the component (A1) includes a polymer compound having a repeating structure of the structural unit (a1).
Preferred (A1) components include polymer compounds having a repeating structure of a structural unit (a1) and a structural unit (a2).

In a polymer compound having a repeating structure of a structural unit (a1) and a structural unit (a2), the ratio of the structural unit (a1) in the polymer compound is the total of all the structural units constituting the polymer compound. With respect to (100 mol%), 5 to 90 mol% is preferable, 5 to 80 mol% is more preferable, 10 to 70 mol% is further preferable, and 10 to 60 mol% is particularly preferable.
In a polymer compound having a repeating structure of a structural unit (a1) and a structural unit (a2), the ratio of the structural unit (a2) in the polymer compound is the total of all the structural units constituting the polymer compound. With respect to (100 mol%), 10 to 95 mol% is preferable, 20 to 95 mol% is more preferable, 30 to 90 mol% is further preferable, and 40 to 90 mol% is particularly preferable.

In the component (A1), a monomer inducing each structural unit is dissolved in a polymerization solvent, and a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (for example, V-601) is used therein. Can be produced by adding and polymerizing.
Alternatively, the component (A1) includes a monomer that induces a structural unit (a1) and, if necessary, a monomer that induces a structural unit other than the structural unit (a1) (for example, a monomer that induces the structural unit (a2)). And are dissolved in a polymerization solvent, a radical polymerization initiator as described above is added thereto for polymerization, and then a deprotection reaction is carried out to produce the product.
In addition, at the time of polymerization, for example, by using a chain transfer agent such as HS-CH ₂ -CH ₂ -CH ₂ -C (CF ₃ ) ₂ -OH in combination, -C (CF ₃ ) is used at the end. ₂ -OH groups may be introduced. In this way, the copolymer in which the hydroxyalkyl group in which a part of the hydrogen atom of the alkyl group is replaced with the fluorine atom is introduced can reduce development defects and LER (line edge roughness: non-uniform unevenness of the line side wall). It is effective in reducing the amount of hydrogen.

The weight average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography (GPC)) of the component (A1) is not particularly limited, and is preferably 1000 to 50000, more preferably 2000 to 30000, and 3000 to 3000. 20000 is even more preferred.
When the Mw of the component (A1) is not more than a preferable upper limit value in this range, there is sufficient solubility in a resist solvent to be used as a resist, and when it is more than a preferable lower limit value in this range, dry etching resistance and dry etching resistance are obtained. The resist pattern has a good cross-sectional shape.
The dispersity (Mw / Mn) of the component (A1) is not particularly limited, and is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. .. Mn indicates a number average molecular weight.

-Regarding the component (A2) The resist composition of the present embodiment has a base component (A2) whose solubility in a developing solution is changed by the action of an acid, which does not correspond to the component (A1). ) Ingredients ”) may be used in combination.
The component (A2) is not particularly limited, and may be arbitrarily selected and used from a large number of conventionally known base material components for chemically amplified resist compositions.
As the component (A2), one kind of a high molecular weight compound or a low molecular weight compound may be used alone, or two or more kinds may be used in combination.

The ratio of the component (A1) to the component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, further preferably 75% by mass or more, and 100% by mass with respect to the total mass of the component (A). May be. When the ratio is 25% by mass or more, a resist pattern excellent in various lithography characteristics such as high sensitivity, resolution, and roughness improvement is likely to be formed.

The content of the component (A) in the resist composition of the present embodiment may be adjusted according to the resist film thickness to be formed and the like.

<Base component (D)>
The resist composition of the present embodiment contains a base component (hereinafter referred to as "(D) component" component). The component (D) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure in the resist composition. The resist composition of the present embodiment contains the component (D01) and the component (D02) as the component (D).

≪ (D01) component ≫
The component (D01) is a compound represented by the following general formula (d01-1).

［式中、Ｒｄ^０１は、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基である。ｍは、１以上の整数であって、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 ⁰¹ 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. .. m is an integer of 1 or more, and M ^{m +} is an independently m-valent organic cation. ]

In the resist composition of the present embodiment, the component (D01) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure. By using the component (D01) in combination with the components (D02) and (F01) described later, the sensitivity of the resist composition is increased and the roughness of the resist pattern formed by using the resist composition is reduced. , Can be compatible.

-In the anion part formula (d01-1), Rd ⁰¹ 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.

Cyclic group which may have a substituent:
The cyclic group in Rd ⁰¹ is preferably a cyclic hydrocarbon group. The cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromaticity. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

The aromatic hydrocarbon group in Rd ⁰¹ is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, further preferably 5 to 20 carbon atoms, and particularly preferably 6 to 15 carbon atoms. Most preferably, the number of carbon atoms is 6 to 10. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.
Specifically, as the aromatic ring of the aromatic hydrocarbon group in Rd ⁰¹ , benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of carbon atoms constituting these aromatic rings was substituted with a heteroatom. Examples include aromatic heterocycles. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
Specific examples of the aromatic hydrocarbon group in Rd ⁰¹ include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.) and one of the hydrogen atoms in the aromatic ring. Examples thereof include a group substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group and a 2-naphthylethyl group). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom number.

Examples of the cyclic aliphatic hydrocarbon group in Rd ⁰¹ include an aliphatic hydrocarbon group containing a ring in the structure.
As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from the alicyclic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the terminal of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferable. 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 one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among them, the polycycloalkane is a polycycloalkane having a polycyclic skeleton of a crosslinked ring system such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecan; a fused ring system such as a cyclic group having a steroid skeleton. Polycycloalkanes having a polycyclic skeleton of are more preferred.

Among them, as the cyclic aliphatic hydrocarbon group in Rd ⁰¹ , a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane is preferable, and a group obtained by removing one hydrogen atom from a polycycloalkane is more preferable. Preferably, an adamantyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.

The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. , 1 to 4 carbon atoms are more preferable, and 1 to 3 carbon atoms are particularly preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], a trimethylene group [ -(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -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 -etc. Alkyl methylene groups;- 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 ) CH ₃ ) ₂ -CH ₂ -etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include alkylalkylene groups such as alkyltetramethylene 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.

Further, the cyclic hydrocarbon group in Rd ⁰¹ may contain a hetero atom such as a heterocycle. Specifically, the lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), respectively, and the general formulas (a5-r-1) to (a5-r-). Examples thereof include a _—SO2 -containing cyclic group represented by 4) and a heterocyclic group represented by the following chemical formulas (r-hr-1) to (r-hr-16), respectively. * In the formula represents a bond bond to a carbon atom in the formula (d01-1).

The cyclic hydrocarbon group at Rd ⁰¹ may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, a nitro group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are more preferable. The methoxy group and the ethoxy group are most preferable.
As the halogen atom as a substituent, a fluorine atom is preferable.
The alkyl halide group as a substituent includes an alkyl group having 1 to 5 carbon atoms, for example, a part or all of hydrogen atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group. Examples thereof include the group substituted with the halogen atom.
The carbonyl group as a substituent is a group that substitutes the methylene group ( _-CH2- ) constituting the cyclic hydrocarbon group.

Chained alkyl group which may have a substituent:
The chain-like alkyl group in Rd ⁰¹ may be either 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.
The branched 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 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

Chain alkenyl group which may have a substituent:
The chain alkenyl group in Rd ⁰¹ may be either linear or branched.
The linear alkenyl group preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, further preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butynyl group and the like.
The branched alkenyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms, further preferably 3 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group and the like.
Among the above, as the chain alkenyl group, a linear alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.

The chain alkyl or alkenyl group at Rd ⁰¹ may have a substituent. Examples of the substituent include an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a cyclic group in Rd ⁰¹ and the like.

The cyclic group which may have a substituent of Rd ⁰¹ , the chain alkyl group which may have a substituent, or the chain alkenyl group which may have a substituent may be other than those described above. As a cyclic group which may have a substituent or a chain-like alkyl group which may have a substituent, the same group as the acid dissociable group represented by the above formula (a1-r-2) may be used. Can be mentioned.

Among them, Rd ⁰¹ is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane; the above general formulas (a2-r-1) to (a2-r-7), respectively. The lactone-containing cyclic group to be used; the _—SO2 -containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4), respectively, is preferable.
Among these, Rd ⁰¹ is an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like group which may have a substituent. Alkyl groups are preferred. Substituents that these groups may have include hydroxyl groups, oxo groups, alkyl groups, aryl groups, fluorine atoms, fluorinated alkyl groups, and the above general formulas (a2-r-1) to (a2-r-). Examples thereof include a lactone-containing cyclic group represented by 7), an ether bond, an ester bond, or a combination thereof. If the substituents contain ether and / or ester bonds, they may be attached to an alkylene group. For example, the substituent may contain a linking group represented by any of the following formulas (y-al-1) to (y-al-5).

［式中、Ｖ’^１０１は単結合または炭素原子数１～５のアルキレン基であり、Ｖ’^１０２は炭素原子数１～３０の２価の飽和炭化水素基である。］

[In the formula, ^V'101 is a single bond or an alkylene group having 1 to 5 carbon atoms, and ^V'102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms. ]

Preferred examples of the aromatic hydrocarbon group include a polycyclic structure containing a phenyl group, a naphthyl group, and a bicyclooctane skeleton (a polycyclic structure composed of a bicyclooctane skeleton and a ring structure other than the bicyclooctane skeleton). The aromatic hydrocarbon group preferably has a hydroxyl group as a substituent.
The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
The chain-like alkyl group preferably has 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. , Nonyl 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- Examples thereof include branched alkyl groups such as ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

When the chain-like alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the number of carbon atoms of the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8. 1 to 4 are more preferable. The fluorinated alkyl group may contain an atom other than the fluorine atom. Examples of the atom other than the fluorine atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like.

Among them, as Rd ⁰¹ , an aromatic hydrocarbon group which may have a substituent or a chain-like alkyl group which may have a substituent is preferable, and an aromatic hydrocarbon which may have a substituent may be used. A chain fluorinated alkyl group which may have a group or a substituent is more preferable.

Preferred specific examples of the anion portion of the component (D01) are shown below, but the present invention is not limited thereto.

Among the above, the anion portion of the component (D01) is any one of the chemical formulas (an-d01-1) to (an-d01-7) and (an-d01-19) to (an-d01-23). The one represented by is preferable, and the one represented by any of the chemical formulas (an-d01-1) to (an-d01-4) and (an-d01-21) is more preferable.

-In the cation part equation (d01-1), M ^{m +} is an organic cation having an m valence. M ^{m +} is preferably a sulfonium cation or an iodonium cation. m is an integer of 1 or more.

Preferred cation portions ((M ^{m +} ) _{1 / m} ) include organic cations represented by the following general formulas (ca-1) to (ca-5), respectively.

［式中、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もよいアリール基、アルキル基またはアルケニル基を表す。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原子数１～５のアルキル基を表す。Ｒ^２１０は、置換基を有してもよいアリール基、置換基を有してもよいアルキル基、置換基を有してもよいアルケニル基、又は置換基を有してもよいＳＯ_２－含有環式基である。Ｌ^２０１は、－Ｃ（＝Ｏ）－または－Ｃ（＝Ｏ）－Ｏ－を表す。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す。ｘは１または２である。Ｗ^２０１は（ｘ＋１）価の連結基を表す。］

[In the formula, R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² each represent an aryl group, an alkyl group or an alkenyl group which may independently have a substituent. 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. R ²¹⁰ contains an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or SO _2- which may have a substituent. It is a cyclic group. L ²⁰¹ represents -C (= O)-or -C (= O) -O-. Y ²⁰¹ independently represents an arylene group, an alkylene group or an alkenylene group. x is 1 or 2. W ²⁰¹ represents a linking group of (x + 1) valence. ]

In the above general formulas (ca-1) to (ca-5), 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. , Phenyl group and 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.
Substituents that R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² may have include, for example, an alkyl group, a halogen atom, an alkyl halide group, a carbonyl group, a cyano group, an amino group, an aryl group, and the following. Examples thereof include groups represented by the general formulas (ca-r-1) to (ca-r-7) of.

［式中、Ｒ’^２０１は、それぞれ独立に、水素原子、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基である。］

[In the formula, ^R'201 may independently have a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is a good chain alkenyl group. ]

In the formulas (ca-r-1) to (ca-r-7), ^R'201 may independently have a hydrogen atom, a cyclic group which may have a substituent, and a substituent, respectively. A good chain alkyl group or a chain alkenyl group which may have a substituent. 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 in ^R'201 are each described above. The same as Rd ⁰¹ in the formula (d01-1) can be mentioned.

Among them, ^R'201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane; the above general formulas (a2-r-1) to (a2-r-7), respectively. The lactone-containing cyclic group to be used; the _—SO2 -containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4), respectively, is preferable.

In the above general formulas (ca-1) to (ca-5), 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 together with the sulfur atom in the formula. If so, heteroatoms such as sulfur atom, oxygen atom, nitrogen atom, carbonyl group, -SO-, _-SO2- , _-SO3- , -COO-, -CONH- or _-N (RN)-( The _RN may be bonded via a functional group such as (is an alkyl group having 1 to 5 carbon atoms). As the ring to be formed, one ring containing a sulfur atom in its ring skeleton, including the sulfur atom, is preferably a 3- to 10-membered ring, and particularly preferably a 5- to 7-membered ring. preferable. Specific examples of the formed ring include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxatiin ring, and a tetrahydrothiophenium. Rings, tetrahydrothiopyranium rings and the like can be mentioned.

R ²⁰⁸ to R ²⁰⁹ 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 are alkyl groups, they are bonded to each other. May form a ring.

R ²¹⁰ contains an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or SO _2- which may have a substituent. It is a cyclic group.
Examples of the aryl group in 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 in R ²¹⁰ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group in R ²¹⁰ preferably has 2 to 10 carbon atoms.
As the SO ₂ -containing cyclic group which may have a substituent in R ²¹⁰ , "-SO ₂ -containing polycyclic group" is preferable, and it is represented by the above general formula (a5-r-1). Groups are more preferred.

Y ²⁰¹ independently represents an arylene group, an alkylene group or an alkenylene group.
Examples of the arylene group in Y ²⁰¹ include a group obtained by removing one hydrogen atom from the aryl group exemplified as the aromatic hydrocarbon group in R ¹⁰¹ in the above formula (b-1).
Examples of the alkylene group and the alkaneylene group in Y ²⁰¹ include a chain alkyl group in R ¹⁰¹ in the above formula (b-1) and a group obtained by removing one hydrogen atom from the group exemplified as the chain alkenyl group. ..

In the formula (ca-4), x is 1 or 2.
W ²⁰¹ is a (x + 1) valence, i.e., a divalent or trivalent linking group.
As the divalent linking group in W ²⁰¹ , a divalent hydrocarbon group which may have a substituent is preferable, and it has a substituent similar to Ya ²¹ in the above general formula (a2-1). A divalent hydrocarbon group may be exemplified. The divalent linking group in 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 in W ²⁰¹ include a group obtained by removing one hydrogen atom from the divalent linking group in W ²⁰¹ , a group in which the divalent linking group is further bonded to the divalent linking group, and the like. Can be mentioned. As the trivalent linking group in W ²⁰¹ , a group in which two carbonyl groups are bonded to an arylene group is preferable.

Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following chemical formulas (ca-1-1) to (ca-1-70).

［式中、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 the formula, g1, g2, and g3 indicate 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 to 20. ]

［式中、Ｒ”^２０１は水素原子又は置換基であって、該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, R " ²⁰¹ is a hydrogen atom or a substituent, and the substituents are the same as those listed as the substituents that R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² may have. Is.]

Specific examples of the suitable cation represented by the formula (ca-2) include diphenyliodonium cation, bis (4-tert-butylphenyl) iodonium cation and the like.

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

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

Specific examples of suitable cations represented by the above formula (ca-5) include cations represented by the following general formulas (ca-5-1) to (ca-5-3).

Among the above, as the cation portion ((M ^{m +} ) _{1 / m} ), the cation represented by the general formula (ca-1) is preferable, and the formulas (ca-1-1) to (ca-1-70) are used. The cations represented by each of are more preferable, and the cations represented by the above formulas (ca-1-1) to (ca-1-47) are further preferable.

As the component (D01), a compound represented by the following formula (d01-1-1) is preferable.

[In the formula, Rd ⁰¹ is the same as Rd ⁰¹ in the formula (d01-1). R ²⁰¹ to R ²⁰³ are the same as R ²⁰¹ to R ²⁰³ in the above formula (ca-1). ]

In the above formula (d01-1-1), Rd ⁰¹ is preferably an aromatic hydrocarbon group which may have a substituent or a chain alkyl group which may have a substituent, and has a substituent. More preferably, an aromatic hydrocarbon group may be used, or a fluorinated alkyl group which may have a substituent may be used.
In the above formula (d01-1-1), R ²⁰¹ to R ²⁰³ are preferably aryl groups which may independently have a substituent.

Specific examples of the component (D01) are shown below, but the present invention is not limited thereto.

In the resist composition of the present embodiment, the component (D01) may be used alone or in combination of two or more.
The content of the component (D01) in the resist composition of the present embodiment is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and 2 to 10 parts by mass with respect to 100 parts by mass of the component (A1). Parts by mass are even more preferred.
When the content of the component (D01) is at least the lower limit of the above-mentioned preferable range, the roughness of the resist pattern is more likely to be reduced. On the other hand, when it is not more than the upper limit of the above-mentioned preferable range, the sensitivity of the resist composition tends to be well maintained.

(D01) Ingredient manufacturing method:
The method for producing the component (D01) is not particularly limited, and the component (D01) can be produced by a known method.

≪ (D02) component ≫
The component (D02) is a compound represented by the following general formula (d02-1).

［式中、Ｒｄ^０２は、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基である。但し、式中のＲｄ^０２において、式中の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。ｍは、１以上の整数であって、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 ⁰² 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. .. However, in Rd ⁰² in the formula, it is assumed that the fluorine atom is not bonded to the carbon atom adjacent to the S atom in the formula. m is an integer of 1 or more, and M ^{m +} is an independently m-valent organic cation. ]

In the resist composition of the present embodiment, the component (D02) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure. By using the component (D02) in combination with the component (D02) and the component (F01) described later, the sensitivity of the resist composition is increased and the roughness of the resist pattern formed by using the resist composition is reduced. And, can be compatible.

Anion portion In the above formula (d02-1), Rd ⁰² 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 good chain alkenyl group.

Examples of the cyclic group which may have a substituent include the same cyclic group which may have a substituent in Rd ⁰¹ in the above formula (d01-1).
However, it is assumed that the fluorine atom is not bonded (fluorine-substituted) to the carbon atom adjacent to the S atom in Rd ⁰² . As a result, the anion of the component (D02) becomes an appropriate weak acid anion, and the quenching ability is improved.
Rd ⁰² is preferably a chain alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent. The chain-like alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10. The aliphatic cyclic group preferably has 3 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms. As the aliphatic cyclic group, a group obtained by removing one or more hydrogen atoms from adamantan, norbornan, isobornan, tricyclodecane, tetracyclododecane and the like (may have a substituent); one or more from camphor and the like. It is more preferable that the group is a group excluding the hydrogen atom of.
The hydrocarbon group of Rd ⁰² may have a substituent. The substituent may be a substituent (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in Rd ⁰¹ in the above formula (d01-1). Similar things can be mentioned.

Among them, Rd ⁰² is preferably an aliphatic cyclic group which may have a substituent, and more preferably an aliphatic polycyclic group which may have a substituent.

Preferred specific examples of the anion portion of the component (D02) are shown below, but the present invention is not limited thereto.

Among the above, as the anion portion of the component (D02), those represented by any of the chemical formulas (an-d02-1) to (an-d02-19) are preferable, and those represented by the chemical formulas (an-d02-1) to (an-d02-1) are preferable. The one represented by (an-d02-8) is more preferable, and the one represented by the chemical formula (an-d02-1), (an-d02-6), or (an-d02-8) is further preferable.

-In the cation part equation (d02-1), M ^{m +} is an organic cation having an m valence. Examples of M ^{m +} include the same as M ^m + in the above formula (d1-1).

As the cation portion ((M ^{m +} ) _{1 / m} ) of the component (D02), the organic cations represented by the above formulas (ca-1) to (ca-5) are preferable, and the above formula (ca-1) is used. The represented cation is more preferred. Among them, as the cation portion ((M ^{m +} ) _{1 / m} ) of the component (D02), the cations represented by the above formulas (ca-1-1) to (ca-1-70) are preferable, and the above-mentioned formula ((M m +) 1 / m) is preferable. The cations represented by ca-1-1) to (ca-1-47) are more preferable.

As the compound (D02), a compound represented by the following formula (d02-1-1) is preferable.

[In the formula, Rd ⁰² is the same as Rd ⁰² in the above formula (d02-1). R ²⁰¹ to R ²⁰³ are the same as R ²⁰¹ to R ²⁰³ in the above formula (ca-1). ]

In the above formula (d02-1-1), Rd ⁰² is preferably a chain alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent, and is preferably substituted. Aliphatic cyclic groups that may have groups are more preferred.
In the above formula (d02-1-1), R ²⁰¹ to R ²⁰³ are preferably aryl groups which may independently have a substituent.

Specific examples of the component (D02) are shown below, but the present invention is not limited thereto.

In the resist composition of the present embodiment, the component (D02) may be used alone or in combination of two or more.
The content of the component (D02) in the resist composition of the present embodiment is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and 1 to 10 parts by mass with respect to 100 parts by mass of the component (A1). Parts by mass are even more preferred.
When the content of the component (D02) is at least the lower limit of the above-mentioned preferable range, the roughness of the resist pattern is more likely to be reduced. On the other hand, when it is not more than the upper limit of the above-mentioned preferable range, the sensitivity of the resist composition tends to be well maintained.
The mass ratio of the component (D01) to the component (D02) in the resist composition of the present embodiment is not particularly limited, but for example, the component (D01): the component (D02) (mass ratio) is 1: 1 to 5. It can be 1. (D01) component: The (D02) component (mass ratio) is preferably 1.5: 1 to 4: 1, more preferably 2: 1 to 3: 1.
When the mass ratio of the component (D01) to the component (D02) is within the above-mentioned preferable range, the sensitivity of the resist composition resist is likely to be improved, and the roughness of the resist pattern is more likely to be reduced.

(D02) Ingredient manufacturing method:
The method for producing the component (D02) is not particularly limited, and the component (D02) can be produced by a known method.

≪Other (D) component≫
The resist composition of the present embodiment may contain a component (D) other than the component (D01) and the component (D02) as long as the effects of the present invention are not impaired. The component (D) other than the component (D01) and the component (D02) is a photodisintegrating base (D1) that is decomposed by exposure and loses acid diffusion controllability (hereinafter referred to as "(D1) component") ((D01). ) And the nitrogen-containing organic compound (D2) that does not correspond to the component (D1) (hereinafter referred to as "component (D2)") and the like (excluding those corresponding to the component (D01)).

-Component (D1) As the component (D1), a compound represented by the following general formula (d1-3) (hereinafter referred to as "component (d1-3)") can be mentioned.

［式中、Ｒｄ^４は置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基である。Ｙｄ^１は単結合又は２価の連結基である。ｍは１以上の整数であって、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 ⁴ 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. Yd ¹ is a single bond or divalent linking group. m is an integer of 1 or more, and M ^{m +} is an independently m-valent organic cation. ]

-In the anion part formula (d1-3), Rd ³ is 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. Examples of the alkenyl group are the same as those of ^R'201 , and a cyclic group containing a fluorine atom, a chain alkyl group, or a chain alkenyl group is preferable. Of these, a fluorinated alkyl group is preferable, and the same group as the fluorinated alkyl group of Rd ¹ is more preferable.

In formula (d1-3), Rd ⁴ is 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. It is an alkenyl group, and examples thereof include the same group as ^R'201 .
Of these, an alkyl group, an alkoxy group, an alkenyl group, and a cyclic group, which may have a substituent, are preferable.
The alkyl group in Rd ⁴ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, or isobutyl. Examples thereof include a group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. A part of the hydrogen atom of the alkyl group of Rd ⁴ may be substituted with a hydroxyl group, a cyano group or the like.
The alkoxy group in Rd ⁴ is preferably an alkoxy group having 1 to 5 carbon atoms, and specifically, as an alkoxy group having 1 to 5 carbon atoms, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, and the like. Examples thereof include an n-butoxy group and a tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferable.

Examples of the alkenyl group in Rd ⁴ include the same group as the alkenyl group in ^R'201 , 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 an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms as a substituent.

Examples of the cyclic group in Rd ⁴ include the same cyclic group as in ^R'201 , and one or more from cycloalkanes such as cyclopentane, cyclohexane, adamantan, norbornan, isobornan, tricyclodecane, and tetracyclododecane. An alicyclic group excluding the hydrogen atom of the above, or an aromatic group such as a phenyl group or a naphthyl group is preferable. When Rd ⁴ is an alicyclic group, the resist composition is well dissolved in an organic solvent, so that the lithography characteristics are improved. Further, when Rd ⁴ is an aromatic group, the resist composition has excellent light absorption efficiency and good sensitivity and lithography characteristics in lithography using EUV or the like as an exposure light source.

In formula (d1-3), Yd ¹ is a single bond or a divalent linking group.
The divalent linking group in Yd ¹ is not particularly limited, but is divalent including a divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent and a hetero atom. Examples include the linking group of. Each of these contains a divalent hydrocarbon group having a substituent and a hetero atom, which are mentioned in the description of the divalent linking group in Ya ²¹ in the above formula (a2-1). Examples are similar to the valence linking group.
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, and even more preferably a methylene group or an ethylene group.

A preferable specific example of the anion portion of the component (d1-3) is shown below.

Cation part In the formula (d1-3), M ^{m +} is an organic cation having an m valence, which is the same as M ^{m +} in the formula (d01-1).

As the component (d1-3), one type may be used alone, or two or more types may be used in combination.

(D1-3) Ingredient manufacturing method:
The method for producing the component (d1-3) is not particularly limited, and is produced in the same manner as that described in, for example, US2012-0149916.

In the resist composition of the present embodiment, the component (D1) may be used alone or in combination of two or more.
When the resist composition of the present embodiment contains the component (D1), the content of the component (D1) in the resist composition is preferably 10% by mass or less with respect to the total mass of the component (D). It is more preferably 3% by mass or less, and further preferably 3% by mass or less. It is particularly preferable that the resist composition of the present embodiment does not contain the component (D1). By setting the content of the component (D1) to the above-mentioned preferable upper limit value or less, the effect of the present invention can be easily obtained.

-Component (D2) The component (D2) is a nitrogen-containing organic compound component that does not correspond to a photodisintegrating base.
The component (D2) is not particularly limited as long as it acts as an acid diffusion control agent and does not correspond to a photodisintegrating base, and any known component may be used. Of these, aliphatic amines are preferable, and among them, secondary aliphatic amines and tertiary aliphatic amines are more preferable.
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 an amine (alkylamine or alkylalcoholamine) in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or a hydroxyalkyl group having 12 or less carbon atoms, or a cyclic amine.
Specific examples of alkylamines and alkylalcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di. 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 other trialkylamines; diethanolamine, triethanolamine, diisopropanolamine, tri Alkyl alcohol amines such as isopropanolamine, di-n-octanolamine and tri-n-octanolamine can be mentioned. Among these, trialkylamines having 5 to 10 carbon atoms are 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 heteroatom. 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, piperazine and the like.
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.

Other aliphatic amines include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, and tris {2. -(1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2- {2- (2-hydroxy) Ethoxy) ethoxy} ethyl] amine, triethanolamine triacetate and the like can be mentioned, with triethanolamine triacetate being preferred.

Further, as the component (D2), an aromatic amine may be used.
Examples of the aromatic amine include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or a derivative thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine and the like.

As the component (D2), one type may be used alone, or two or more types may be used in combination.
When the resist composition of the present embodiment contains the component (D2), the content of the component (D1) in the resist composition is preferably 10% by mass or less with respect to the total mass of the component (D). It is more preferably 3% by mass or less, and further preferably 3% by mass or less. It is particularly preferable that the resist composition of the present embodiment does not contain the component (D2). By setting the content of the component (D2) to the above-mentioned preferable upper limit value or less, the effect of the present invention can be easily obtained.

<Fluorine additive component (F)>
The resist composition of the present embodiment contains a fluorine additive component (hereinafter referred to as "(F) component"). The component (F) imparts water repellency to the resist film or improves lithography characteristics. The resist composition of the present embodiment contains the component (F01) as the component (F).

(F01) component The (F01) component is a polymer having a structural unit (f01) represented by the following general formula (f01-1) and a structural unit (f02) represented by the following general formula (f02-1). It is a compound.

［式中、Ｒは、それぞれ独立に、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基であり；Ｖｆ^０１は、２価の連結基であり；Ｒｆ^０１は、フッ素原子を含む１価の有機基であり；Ｖｆ^０２は、２価の連結基であり；ｎｆ^０２は、０～２の整数であり；Ｒｆ^０２は、酸解離性基である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, respectively; Vf ⁰¹ is a divalent linking group; Rf ⁰¹ is a monovalent organic group containing a fluorine atom; Vf ⁰² is a divalent linking group; nf ⁰² is an integer of 0 to 2; Rf ⁰² is an acid dissociable group. .. ]

In the resist composition of the present embodiment, the component (F01) acts as a fluorine additive component. By using the component (F01) in combination with the components (D01) and (D02), the sensitivity of the resist composition is increased, and the roughness of the resist pattern formed by using the resist composition is reduced. Can be compatible.

<< Structural unit (f01) >>
The structural unit (f01) is a structural unit represented by the following general formula (f01-1).

［式中、Ｒは、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基であり；Ｖｆ^０１は、２価の連結基であり；Ｒｆ^０１は、フッ素原子を含む１価の有機基である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms; Vf ⁰¹ is a divalent linking group; Rf ⁰¹ is It is a monovalent organic group containing a fluorine atom. ]

In the above formula (f01-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. R is the same as R in the above formula (a1-1). 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 particularly preferable from the viewpoint of industrial availability.

In the above formula (f01-1), Vf ⁰¹ is a divalent linking group. The divalent linking group is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like. The divalent hydrocarbon group which may have a substituent in Vf ⁰¹ and the divalent linking group containing a hetero atom are the same as those mentioned in Ya ^x1 in the above formula (a10-1), respectively. Can be mentioned.

Among them, Vf ⁰¹ is preferably a divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. As the divalent hydrocarbon group, an aliphatic hydrocarbon group is preferable. The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably saturated. The aliphatic hydrocarbon group is preferably linear or branched, and more preferably linear.

The divalent hydrocarbon group at Vf ⁰¹ may have a substituent. Examples of the substituent include a halogen atom, and a fluorine atom is preferable.

As Vf ⁰¹ , an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group or an ethylene group is more preferable.

In the above formula (f01-1), Rf ⁰¹ is a monovalent organic group containing a fluorine atom. Examples of the monovalent organic group containing a fluorine atom include a monovalent hydrocarbon group containing a fluorine atom. The monovalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

An aliphatic hydrocarbon group in Rf ⁰¹ The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

Linear or branched aliphatic hydrocarbon group The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. The number of carbon atoms 1 to 4 is more preferable, and the number of carbon atoms 1 to 3 is particularly preferable. The linear aliphatic hydrocarbon group is preferably a linear alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
The branched aliphatic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and 3 carbon atoms. Especially preferable. As the branched aliphatic hydrocarbon group, a branched alkyl group is preferable, and specifically, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. And so on.

The linear or branched aliphatic hydrocarbon group contains at least one fluorine atom as a substituent. In the linear or branched aliphatic hydrocarbon group, 25% or more of hydrogen atoms in the aliphatic hydrocarbon group are preferably fluorinated, and 50% or more is fluorinated. More preferably, 60% or more is fluorinated. When the above-mentioned preferable upper limit value or more is fluorinated, the hydrophobicity of the resist film at the time of immersion exposure is improved.
The linear or branched aliphatic hydrocarbon group may contain a substituent other than a fluorine atom. Examples of the substituent other than the fluorine atom include a hydroxyl group, a halogen atom other than fluorine (for example, a chlorine atom, a bromine atom, an iodine atom, etc.) and the like.

An aliphatic hydrocarbon group containing a ring in the structure As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group (fat) may contain a substituent containing a hetero atom in the ring structure. A group obtained by removing one hydrogen atom from the group hydrocarbon ring), 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. Examples thereof include a group in which a hydrogen group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. 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 one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically. Examples include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The cyclic aliphatic hydrocarbon group contains at least one fluorine atom as a substituent. The cyclic aliphatic hydrocarbon group preferably has 25% or more of hydrogen atoms in the cyclic hydrocarbon group fluorinated, more preferably 50% or more, and 60% or more. Is more preferably fluorinated.
The cyclic aliphatic hydrocarbon group may contain a substituent other than the fluorine atom. Examples of the substituent other than the fluorine atom include a hydroxyl group, a halogen atom other than fluorine (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group, an alkoxy group, a carbonyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are more preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are more preferable. , A methoxy group and an ethoxy group are more preferable.
Examples of the halogenated alkyl group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
The cyclic aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom as a part of the carbon atom constituting the ring structure. As the substituent containing the heteroatom, —O—, —C (= O) —O—, —S—, —S (= O) _2- , —S (= O) ₂ -O— are preferable.

-Aromatic hydrocarbon group in Rf ⁰¹ The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be a monocyclic type or a polycyclic type. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); an aromatic compound containing two or more aromatic rings. A group obtained by removing one hydrogen atom from (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or the aromatic heterocycle is substituted with an alkylene group (for example, a benzyl group, a phenethyl group, etc.). Examples thereof include 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-arylalkyl group such as 2-naphthylethyl group) and the like. The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2 carbon atoms, and 1 carbon atom. Is particularly preferred.

The aromatic hydrocarbon group contains at least one fluorine atom as a substituent. The aromatic hydrocarbon group preferably has 25% or more of hydrogen atoms in the aromatic hydrocarbon group fluorinated, more preferably 50% or more, and 60% or more of fluorine. It is more preferable that it is made.
The aromatic hydrocarbon group may contain a substituent other than the fluorine atom. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a hydroxyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are more preferable.
Examples of the alkoxy group as the substituent include those exemplified as a substituent for substituting a hydrogen atom of the cyclic aliphatic hydrocarbon group.

As Rf ⁰¹ , an aliphatic hydrocarbon group containing a fluorine atom is preferable, and an alkyl group containing a fluorine atom is more preferable. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms.
Among them, as Rf ⁰¹ , a fluorinated alkyl group having 1 to 6 carbon atoms is preferable, and a trifluoromethyl group, -CH ₂ -CF ₃ , -CH ₂ -CF ₂ -CF ₃ , -CH (CF ₃ ) ₂ , -CH ₂ -CH ₂ -CF ₃ or -CH ₂ -CH ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₃ is more preferable.

The structural unit (f01) is preferably a structural unit represented by the following general formula (f01-1-1).

［式中、Ｒは、前記と同様であり；Ｒｆ^０１２およびＲｆ^０１３は、それぞれ独立に、水素原子、ハロゲン原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基を表し；Ｒｆ^０１１は、フッ素原子を含む有機基を表す。］

[In the formula, R is the same as described above; Rf ⁰¹² and Rf ⁰¹³ are independently hydrogen atom, halogen atom, alkyl group having 1 to 5 carbon atoms or alkyl halide having 1 to 5 carbon atoms, respectively. Represents a group; Rf ⁰¹¹ represents an organic group containing a fluorine atom. ]

In the formula (f01-1-1), R is the same as R in the formula (f01-1-).

In the above formula (f01-1-1), Rf ⁰¹² and Rf ⁰¹³ independently have a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. show. As the halogen atom, a fluorine atom is preferable. As the alkyl group having 1 to 5 carbon atoms, 1 to 3 carbon atoms are preferable, and a methyl group or an ethyl group is more preferable. 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 hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. As the halogen atom, a fluorine atom is preferable. Among them, as Rf ⁰¹² and Rf ⁰¹³ , a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group is preferable.

In the formula (f01-1-1), Rf ⁰¹¹ is an organic group containing a fluorine atom. Rf ⁰¹¹ is the same as Rf ⁰¹ in the above equation (f0-1).

Specific examples of the structural unit (f01) are shown below, but the present invention is not limited thereto. In the formula, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The structural unit (f01) contained in the component (F01) may be one type or two or more types.
The ratio of the constituent units (f01) in the (F01) component is preferably 10 to 95 mol%, preferably 20 to 95 mol%, based on the total (100 mol%) of all the constituent units constituting the (F01) component. It is more preferably 90 mol%, further preferably 30 to 85 mol%, and particularly preferably 40 to 80 mol%.
When the ratio of the structural unit (f01) is set to be equal to or higher than the lower limit of the preferable range, the sensitivity of the resist composition is improved and the lithography characteristics such as roughness are further improved. When the ratio of the structural unit (f01) is not more than the upper limit of the preferable range, the balance with other structural units can be achieved, and various lithography characteristics are improved.

<< Structural unit (f02) >>
The structural unit (f02) is a structural unit represented by the following general formula (f02-1).

［式中、Ｒは、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基であり；Ｖｆ^０２は、２価の連結基であり；ｎｆ^０２は、０～２の整数であり；Ｒｆ^０２は、酸解離性基である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms; Vf ⁰² is a divalent linking group; nf ⁰² is. It is an integer of 0 to 2; Rf ⁰² is an acid dissociative group. ]

In the above formula (f02-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl halide group having 1 to 5 carbon atoms. R is the same as R in the above formula (a1-1). 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 particularly preferable from the viewpoint of industrial availability.

In the above formula (f02-1), Vf ⁰² is a divalent linking group. The divalent linking group is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like. The divalent hydrocarbon group which may have a substituent in Vf ⁰¹ and the divalent linking group containing a hetero atom are the same as those mentioned in Ya ^x1 in the above formula (a10-1), respectively. Can be mentioned.

Among them, Vf ⁰² is preferably a divalent hydrocarbon group which may have an ether bond. The divalent hydrocarbon group which may have an ether bond preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. As the divalent hydrocarbon group, an aliphatic hydrocarbon group is preferable. The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably saturated. The aliphatic hydrocarbon group is preferably linear or branched, and more preferably linear.

As Vf ⁰² , an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group or an ethylene group is more preferable.

In the above equation (f02-1), nf ⁰² is an integer of 0 to 2. nf ⁰² is preferably 0 or 1, more preferably 0.

In the above formula (f02-1), Rf ⁰² is an acid dissociative group. Examples of the acid dissociable group include groups mentioned as the acid dissociative group in the structural unit (a1), and a tertiary alkyl ester type acid dissociative group is preferable, and the formula (a1-r-2) is used. The represented acid dissociative group is more preferred.

Among them, as the acid dissociative group in Rf ⁰² , an acid dissociative group represented by the following general formula (Rf02-1) is preferable.

［式中、Ｒｆ^０２１～Ｒｆ^０２３は、それぞれ独立に、飽和脂肪族炭化水素基であり、Ｒ^０２２及びＲ^０２３は、互いに結合して環を形成してもよい。＊は、前記式（ｆ０２－１）中の酸素原子に結合する結合手である。］

[In the formula, Rf ⁰²² to Rf ⁰²³ are each independently saturated aliphatic hydrocarbon groups, and R ⁰²² and R ⁰² 3 may be bonded to each other to form a ring. * Is a bond that bonds to an oxygen atom in the above formula (f02-1). ]

In the above formula (Rf02-1), Rf ⁰²¹ to Rf ⁰²³ are independently saturated aliphatic hydrocarbon groups.
Examples of the saturated aliphatic hydrocarbon group in Rf ⁰²² to Rf ⁰²³ include a linear or branched alkyl group or a cyclic saturated aliphatic hydrocarbon group.
The linear alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 4 carbon atoms, and particularly preferably 1 or 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

The branched-chain alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group and the like, and an isopropyl group is preferable.

The cyclic saturated aliphatic hydrocarbon group in Rf ⁰²¹ may be a polycyclic group or a monocyclic group.
As the saturated aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The saturated aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms. Examples include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

Rf ⁰²² and Rf ⁰²³ may be combined with each other to form a ring. When Rf ⁰²² and Rf ⁰²³ form a ring, the acid dissociative group represented by the formula (Rf02-1) includes a group represented by the formula (Rf02-1-1).
When Rf ⁰²² and Rf ⁰²³ are independent saturated aliphatic hydrocarbon groups that do not bind to each other, the acid dissociable group represented by the above formula (Rf02-1) is the above-mentioned formula (Rf02-1- The group represented by 2) can be mentioned.

［式中、Ｒｆ^０２４は、直鎖状又は分岐鎖状の炭素原子数１～１２のアルキル基を表す。Ｒ^ｆ０２５は、Ｒｆ^０２４が結合した炭素原子と共に飽和脂肪族環式基を形成する基を示す。
式中、Ｒｆ^０２６及びＲｆ^０２７は、それぞれ独立に、炭素原子数１～１０の１価の鎖状飽和炭化水素基又は水素原子である。Ｒｆ^０２８は、飽和脂肪族炭化水素基である。＊は、前記式（ｆ０２－１）中の酸素原子に結合する結合手を表す。］

[In the formula, Rf ⁰²⁴ represents a linear or branched-chain alkyl group having 1 to 12 carbon atoms. R ^f025 indicates a group forming a saturated aliphatic cyclic group together with the carbon atom to which Rf ⁰²⁴ is bonded.
In the formula, Rf ⁰²⁶ and Rf ⁰²⁷ are independently monovalent chain saturated hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms. Rf ⁰²⁸ is a saturated aliphatic hydrocarbon group. * Represents a bond that binds to an oxygen atom in the above formula (f02-1). ]

In the above formula (Rf02-1-1), Rf ⁰²⁴ is a linear or branched-chain alkyl group having 1 to 12 carbon atoms.

Examples of the linear or branched alkyl group in Rf ⁰²⁴ include the same groups as those mentioned as the linear or branched alkyl group in Rf ⁰²² to Rf ⁰²³ .

In the above formula (Rf02-1-1), the Rf ⁰²⁵ (saturated aliphatic cyclic group formed together with the carbon atom to which Rf ⁰²⁴ is bonded) may be a polycyclic type or a monocyclic type.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, specifically. Examples include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
Among them, a monocyclic saturated alicyclic hydrocarbon group is preferable, specifically, a cyclopentyl group and a cyclohexyl group are more preferable, and a cyclopentyl group is further preferable.

In the above formula (Rf02-1-2), Rf ⁰²⁶ and Rf ⁰²⁷ are independently monovalent chain saturated hydrocarbon groups or hydrogen atoms having 1 to 10 carbon atoms. The monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms may be linear or branched, but linear is preferable. The monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms is preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms 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 decyl group. The group etc. can be mentioned.
Among them, Rf ⁰²⁶ and Rf ⁰²⁷ are preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, further preferably a methyl group and an ethyl group, and particularly preferably a methyl group. preferable.

In the above formula (Rf02-1-2), Rf ⁰²⁸ is a saturated aliphatic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group include a linear or branched alkyl group and a saturated alicyclic hydrocarbon group.

The linear alkyl group in Rf ⁰²⁸ preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and the like. Among these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

The branched-chain alkyl group in Rf ⁰²⁸ preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, a 2,2-dimethylbutyl group and the like, and an isopropyl group is preferable.

The saturated alicyclic hydrocarbon group in Rf ⁰²⁸ may be a polycyclic group or a monocyclic group.
As the aliphatic hydrocarbon group which is a monocyclic group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms. Examples include adamantan, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

Specific examples of the acid dissociative group represented by the formula (Rf02-1-1) include the formulas (r-pr-m1) to (r-pr-m17) and ((r-pr-s1) to. The group represented by (r-pr-s20) can be mentioned.

Specific examples of the acid dissociative group represented by the formula (Rf02-1-2) include the formulas (r-pr-cm1) to (r-pr-cm5) and (r-pr-cs1) to ( Examples thereof include groups represented by r-pr-cs3) and (r-pr-c1) to (r-pr-c3).

Specific examples of the structural unit (f02) are shown below, but the present invention is not limited thereto. In the formula, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The structural unit (f02) contained in the component (F01) may be one type or two or more types.
The ratio of the constituent unit (f02) in the component (F01) is preferably 5 to 60 mol% with respect to the total (100 mol%) of all the constituent units constituting the component (F01). It is more preferably 50 mol%, further preferably 10 to 40 mol%, and particularly preferably 20 to 30 mol%.
When the ratio of the structural unit (f02) is at least the lower limit of the preferable range, the sensitivity of the resist composition is improved, and the lithography characteristics such as roughness are further improved. When the ratio of the structural unit (f02) is not more than the upper limit of the preferable range, the balance with other structural units can be achieved, and various lithography characteristics are improved.

As the component (F01), one type may be used alone, or two or more types may be used in combination.
Examples of the component (F01) include a polymer compound having a structural unit (f01) and a repeating structure of the structural unit (f02). In this case, the molar ratio of the structural unit (f01) to the structural unit (f02) in the polymer compound (constituent unit (f01): structural unit (f02)) is preferably 90:10 to 40:60. , 85:15 to 50:50, more preferably 80:20 to 60:40.

The component (F01) may have other structural units in addition to the structural unit (f01) and the structural unit (f02). Examples of the other structural unit include a structural unit derived from acrylic acid or methacrylic acid.
As the component (F01), a polymer compound having a repeating structure of a structural unit (f01) and a structural unit (f02) is preferable.

The weight average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of the component (F01) is preferably 1000 to 50,000, more preferably 5000 to 40,000, still more preferably 10,000 to 30,000. When the Mw of the component (F01) is not more than the upper limit of the above range, the solubility in the resist solvent becomes good. When the Mw of the component (F01) is at least the lower limit of the above range, the water repellency of the resist film becomes good.
The dispersity (Mw / Mn) of the component (F01) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and even more preferably 1.0 to 2.5.

The content of the component (F01) in the resist composition is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the component (A).

Specific examples of the component (F01) are shown below, but the present invention is not limited thereto. In the formula, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

-Other (F) component The resist composition of the present embodiment may contain (F) component (hereinafter referred to as "(F1) component") other than the (F01) component as long as the effect of the present invention is not impaired. good.
Examples of the component (F1) are described in JP-A-2010-002870, JP-A-2010-032994, JP-A-2010-277043, JP-A-2011-13569, and JP-A-2011-128226. Fluorine-containing polymer compounds can be used.
More specifically, as the component (F1), a polymer having a structural unit (f1) represented by the following general formula (f1-1) (however, excluding those corresponding to the component (F01)) can be mentioned. The polymer is a polymer (homopolymer) consisting only of the structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) and the structural unit (a1). It is preferable that the structural unit (f1) is a copolymer of the structural unit derived from acrylic acid or methacrylic acid and the structural unit (a1).

［式中、Ｒは前記と同様であり、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、炭素原子数１～５のアルキル基又は炭素原子数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０～５の整数であり、Ｒｆ^１０１はフッ素原子を含む有機基である。］

[In the formula, R is the same as described above, and Rf ¹⁰² and Rf ¹⁰³ independently have a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. Represented, Rf ¹⁰² and Rf ¹⁰³ may be the same or different. nf ¹ is an integer of 0 to 5, and Rf ¹⁰¹ is an organic group containing a fluorine atom. ]

In the formula (f1-1), R bonded to the carbon atom at the α-position is the same as described above. As R, a hydrogen atom or a methyl group is preferable.
In the formula (f1-1), the halogen atom of Rf ¹⁰² and Rf ¹⁰³ is preferably a fluorine atom. Examples of the alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include the same as the above-mentioned alkyl group having 1 to 5 carbon atoms of R, and a methyl group or an ethyl group is preferable. As a halogenated alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ , specifically, a group in which a part or all of hydrogen atoms of an alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Can be mentioned. As the halogen atom, a fluorine atom is preferable. Among them, as Rf ¹⁰² and Rf ¹⁰³ , a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group is preferable.
In the formula (f1-1), nf ¹ is an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 1 or 2.

In the 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 the number of carbon atoms is preferably 1 to 20, and the number of carbon atoms is preferably 1 to 15. More preferably, 1 to 10 carbon atoms are particularly preferable.
Further, in the hydrocarbon group containing a fluorine atom, it is preferable that 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more is fluorinated, and 60% or more is fluorinated. Fluorination is particularly preferable because the hydrophobicity of the resist film during immersion exposure is increased.
Among them, as Rf ¹⁰¹ , a fluorinated hydrocarbon group having 1 to 6 carbon atoms is more preferable, and a trifluoromethyl group, -CH ₂ -CF ₃ , -CH ₂ -CF ₂ -CF ₃ , -CH (CF). ₃ ) ₂ , -CH ₂ -CH ₂ -CF ₃ , -CH ₂ -CH ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₃ are particularly preferable.

The weight average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of the component (F1) is preferably 1000 to 50,000, more preferably 5000 to 40,000, and most preferably 10,000 to 30,000. When it is not more than the upper limit of this range, it has sufficient solubility in a solvent for resist to be used as a resist, and when it is more than the lower limit of this range, the water repellency of the resist film is good.
The dispersity (Mw / Mn) of the component (F1) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5.

In the resist composition of the present embodiment, the component (F1) may be used alone or in combination of two or more.
When the resist composition contains the component (F1), the content of the component (F1) is preferably 10% by mass or less, more preferably 5% by mass or less, and 3% by mass with respect to the total mass of the component (F). % Or less is more preferable. It is particularly preferable that the resist composition of the present embodiment does not contain the component (F1). By setting the content of the component (F1) to the above-mentioned preferable upper limit value or less, the effect of the present invention can be easily obtained.

<Other ingredients>
The resist composition of the present embodiment may further contain other components in addition to the above-mentioned component (A), component (D), and component (F). Examples of other components include the components (B), (E), and (S) shown below.

<< Acid generator component (B) >>
The resist composition of the present embodiment may contain an acid generator component (B) (hereinafter referred to as “(B) component”) that generates an acid upon exposure.
The component (B) is not particularly limited, and those previously proposed as an acid generator for a chemically amplified resist composition can be used.
Examples of such an acid generator include onium salt-based acid generators such as iodonium salt and sulfonium salt, oxime sulfonate-based acid generators; bisalkyl or bisarylsulfonyldiazomethanes, and diazomethane-based poly (bissulfonyl) diazomethanes. Acid generators; nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, disulfon-based acid generators, and various other substances can be mentioned.

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). Examples thereof include 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”).

［式中、Ｒ^１０１及びＲ^１０４～Ｒ^１０８は、それぞれ独立に、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基である。Ｒ^１０４とＲ^１０５とは相互に結合して環構造を形成していてもよい。Ｒ^１０２は、炭素原子数１～５のフッ素化アルキル基又はフッ素原子である。Ｙ^１０１は、酸素原子を含む２価の連結基又は単結合である。Ｖ^１０１～Ｖ^１０３は、それぞれ独立に、単結合、アルキレン基又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、単結合又は酸素原子である。Ｌ^１０３～Ｌ^１０５は、それぞれ独立に、単結合、－ＣＯ－又は－ＳＯ_２－である。ｍは１以上の整数であって、Ｍ^ｍ＋はｍ価のオニウムカチオンである。］

[In the formula, R ¹⁰¹ and R ¹⁰⁴ to R ¹⁰⁸ each independently have a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It may be a chain alkenyl group. R ¹⁰⁴ and R ¹⁰⁵ may be coupled to each other to form a ring structure. R ¹⁰² is a fluorinated alkyl group or a fluorine atom having 1 to 5 carbon atoms. Y ¹⁰¹ is a divalent linking group or a single bond 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 single-bonded, -CO- or -SO _2- . m is an integer of 1 or more, and M ^{m +} is an m-valent onium cation. ]

{Anion part}
-In the anion formula (b-1) in the component (b-1), R ¹⁰¹ is 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 which may have.

Cyclic group which may have a substituent:
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. Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromaticity. Further, the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

The aromatic hydrocarbon group in R ¹⁰¹ is a hydrocarbon group having an aromatic ring. The number of carbon atoms of the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, still more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. .. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.
Specifically, as the aromatic ring of the aromatic hydrocarbon group in R ¹⁰¹ , benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of carbon atoms constituting these aromatic rings was substituted with a heteroatom. Examples include aromatic heterocycles. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
Specifically, as the aromatic hydrocarbon group in R ¹⁰¹ , a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.) and one of the hydrogen atoms of the aromatic ring are alkylene. Examples thereof include a group substituted with a group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group and a 2-naphthylethyl group). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

Examples of the cyclic aliphatic hydrocarbon group in R ¹⁰¹ include an aliphatic hydrocarbon group containing a ring in the structure.
As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from the alicyclic hydrocarbon ring) and an alicyclic hydrocarbon group are linear or branched. Examples thereof include a group bonded to the terminal of a chain-shaped aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, and the like.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferable. 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 one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among them, the polycycloalkane is a polycycloalkane having a polycyclic skeleton of a crosslinked ring system such as adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecan; a fused ring system such as a cyclic group having a steroid skeleton. Polycycloalkanes having a polycyclic skeleton of are more preferred.

Among them, as the cyclic aliphatic hydrocarbon group in R ¹⁰¹ , a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane is preferable, and a group obtained by removing one hydrogen atom from a polycycloalkane is more preferable. Preferably, an adamantyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.

The linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms. 1 to 3 are the most preferable. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], a trimethylene group [ -(CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ] and the like can be mentioned.
The branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6, and even more preferably 3 or 4. 3 is the most preferable. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -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 -etc. Alkyl methylene groups;- 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 ) CH ₃ ) ₂ -CH ₂ -etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -etc. Alkyltrimethylene groups; -CH (CH ₃ ) Examples thereof include alkylalkylene groups such as alkyltetramethylene 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.

Further, the cyclic hydrocarbon group in R ¹⁰¹ may contain a hetero atom such as a heterocycle. Specifically, the lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), respectively, and the general formulas (a5-r-1) to (a5-r-). Examples thereof include a _—SO2 -containing cyclic group represented by 4) and a heterocyclic group represented by the chemical formulas (r-hr-1) to (r-hr-16), respectively. In the chemical formulas (r-hr-1) to (r-hr-16), * represents a bond that binds to Y ¹⁰¹ in the formula (b-1).

Examples of the substituent in the cyclic group of R ¹⁰¹ include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, a nitro group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group are more preferable. The methoxy group and the ethoxy group are most preferable.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
The alkyl halide group as a substituent includes an alkyl group having 1 to 5 carbon atoms, for example, a part or all of hydrogen atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group. Examples thereof include the group substituted with the halogen atom.
The carbonyl group as a substituent is a group that substitutes the methylene group ( _-CH2- ) constituting the cyclic hydrocarbon group.

The cyclic hydrocarbon group in R ¹⁰¹ may be a fused cyclic group containing a condensed ring in which an aliphatic hydrocarbon ring and an aromatic ring are condensed. Examples of the fused ring include those obtained by condensing one or more aromatic rings with a polycycloalkane having a polycyclic skeleton of a crosslinked ring system. Specific examples of the crosslinked ring-based polycycloalkane include bicycloalkanes such as bicyclo [2.2.1] heptane (norbornane) and bicyclo [2.2.2] octane. As the fused ring formula, a group containing a fused ring in which two or three aromatic rings are condensed with bicycloalkane is preferable, and two or three aromatic rings are condensed with bicyclo [2.2.2] octane. Groups containing fused rings are more preferred. Specific examples of the fused cyclic group in R ¹⁰¹ include those represented by the following formulas (r-br-1) to (r-br-2). * In the formula represents a bond that binds to Y ¹⁰¹ in the formula (b-1).

Examples of the substituent that the fused cyclic group in R ¹⁰¹ may have include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group and a fat. Examples include a cyclic hydrocarbon group.
Examples of the alkyl group, alkoxy group, halogen atom and alkyl halide group as the substituent of the fused cyclic group include the same as those mentioned as the substituent of the cyclic group in R ¹⁰¹ .
Examples of the aromatic hydrocarbon group as a substituent of the fused ring type group include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.) and a hydrogen atom of the aromatic ring. A group in which one is substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.), the above. Examples thereof include heterocyclic groups represented by the formulas (r-hr-1) to (r-hr-6), respectively.
As the alicyclic hydrocarbon group as a substituent of the fused ring type group, a group obtained by removing one hydrogen atom from a monocycloalkane such as cyclopentane and cyclohexane; adamantan, norbornan, isobornane, tricyclodecane and tetra. A group obtained by removing one hydrogen atom from a polycycloalkane such as cyclododecane; a lactone-containing cyclic group represented by the general formulas (a2-r-1) to (a2-r-7), respectively; the general formula. -SO ₂ -containing cyclic group represented by (a5-r-1) to (a5-r-4); represented by the above formulas (r-hr-7) to (r-hr-16), respectively. Examples thereof include a heterocyclic group.

Chained alkyl group which may have a substituent:
The chain-like alkyl group of R ¹⁰¹ may be either 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.
The branched-chain alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. 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 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

Chain alkenyl group which may have a substituent:
The chain alkenyl group of R ¹⁰¹ may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5, and even more preferably 2 to 4. 3 is particularly preferable. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), a butynyl group and the like. Examples of the branched alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group, a 2-methylpropenyl group and the like.
Among the above, as the chain alkenyl group, a linear alkenyl group is preferable, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.

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

Among the above, 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; represented by the above general formulas (a2-r-1) to (a2-r-7), respectively. A lactone-containing cyclic group; a _—SO2 -containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4), respectively, is preferable.

In formula (b-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, the Y ¹⁰¹ may contain an atom other than the oxygen atom. Examples of the atom other than the oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, a nitrogen atom and the like.
Examples of the divalent linking group containing an oxygen atom include an oxygen atom (ether bond: -O-), an ester bond (-C (= O) -O-), and an oxycarbonyl group (-OC (= O-). )-), Amid bond (-C (= O) -NH-), carbonyl group (-C (= O)-), carbonate bond (-OC (= O) -O-), etc. An oxygen atom-containing linking group of the system; a combination of the oxygen atom-containing linking group of the non-hydrogen system and an alkylene group and the like can be mentioned. A sulfonyl group (-SO _2- ) may be further linked to this combination. Examples of the divalent linking group containing such an oxygen atom include linking groups represented by the general formulas (y-al-1) to (y-al-7). In the general formulas (y-al-1) to (y-al-7), it is the general formulas (y-al-1) to bond with R ¹⁰¹ in the formula (b-1). It is ^V'101 in (y-al-7).

The divalent saturated hydrocarbon group in ^V'102 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and 1 to 5 carbon atoms. It is more preferable that it is an alkylene group of.

The alkylene group in ^V'101 and ^V'102 may be a linear alkylene group or a branched chain alkylene group, and a linear alkylene group is preferable.
Specific examples of the alkylene group in ^V'101 and ^V'102 are methylene groups [-CH ₂ -];-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 -etc. Alkyl methylene groups; 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 ) Alkylethylene groups 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 ) Alkyltrimethylene groups such as CH _2- ; Tetramethylene groups [-CH ₂ CH ₂ CH ₂ CH _2- ]; -CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ Alkyltetramethylene groups such as CH _2- ; pentamethylene groups [-CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ] and the like can be mentioned.
Further, a part of the methylene group 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 a cyclic aliphatic hydrocarbon group of ^Ra'3 in the above formula (a1-r-1) (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group). ), A divalent group obtained by further removing one hydrogen atom is preferable, and a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group is more preferable.

As Y ¹⁰¹ , a divalent linking group containing an ester bond or a divalent linking group containing an ether bond is preferable, and they are represented by the above formulas (y-al-1) to (y-al-5), respectively. Linking groups are more preferred.

In formula (b-1), V ¹⁰¹ is a single bond, an alkylene group or a fluorinated alkylene group. The alkylene group and the fluorinated alkylene group in V ¹⁰¹ preferably have 1 to 4 carbon atoms. Examples of the fluorinated alkylene group in V ¹⁰¹ include a group in which a part or all of the hydrogen atom of the alkylene group in V ¹⁰¹ is replaced with a fluorine atom. Among them, V ¹⁰¹ is preferably a single bond or a fluorinated alkylene group having 1 to 4 carbon atoms.

In formula (b-1), R ¹⁰² is 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 portion represented by the above formula (b-1) include fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anion and perfluorobutane sulfonate anion when Y ¹⁰¹ has a single bond. When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, an anion represented by any of the following formulas (an-1) to (an-3) can be mentioned.

［式中、Ｒ”^１０１は、置換基を有してもよい脂肪族環式基、上記の化学式（ｒ－ｈｒ－１）～（ｒ－ｈｒ－６）でそれぞれ表される１価の複素環式基、前記式（ｒ－ｂｒ－１）又（ｒ－ｂｒ－２）で表される縮合環式基、又は置換基を有してもよい鎖状のアルキル基である。Ｒ”^１０２は、置換基を有してもよい脂肪族環式基、前記式（ｒ－ｂｒ－１）又（ｒ－ｂｒ－２）で表される縮合環式基、前記一般式（ａ２－ｒ－１）、（ａ２－ｒ－３）～（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－含有環式基である。Ｒ”^１０３は、置換基を有してもよい芳香族環式基、置換基を有してもよい脂肪族環式基、又は置換基を有してもよい鎖状のアルケニル基である。Ｖ”^１０１は、単結合、炭素原子数１～４のアルキレン基、又は炭素原子数１～４のフッ素化アルキレン基である。Ｒ^１０２は、フッ素原子又は炭素原子数１～５のフッ素化アルキル基である。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０～２０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, and a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6), respectively. It is a cyclic group, a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), or a chain alkyl group which may have a substituent. R " ¹⁰² . Is an aliphatic cyclic group which may have a substituent, a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), and the above general formula (a2-r-). 1), lactone-containing cyclic groups represented by (a2-r-3) to (a2-r-7), respectively, or the general formulas (a5-r-1) to (a5-r-4), respectively. Represented-SO ₂ -containing cyclic group. 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 single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. v "is an integer of 0 to 3 independently, q" is an integer of 0 to 20 independently, and n "is an integer of 0 or 1."

The aliphatic cyclic group which may have a substituent of R " ¹⁰¹ , R" ¹⁰² and R " ¹⁰³ is a group exemplified as a cyclic aliphatic hydrocarbon group in R ¹⁰¹ in the above formula (b-1). As the substituent, the same group as the substituent which may replace the cyclic aliphatic hydrocarbon group in R ¹⁰¹ in the above formula (b-1) can be mentioned.

The aromatic cyclic group which may have a substituent in R " ¹⁰³ may be the group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R ¹⁰¹ in the above formula (b-1). Preferred. Examples of the substituent include the same substituents which may replace the aromatic hydrocarbon group in R ¹⁰¹ in the above formula (b-1).

The chain-like alkyl group which may have a substituent in R " ¹⁰¹ is preferably the group exemplified as the chain-like alkyl group in R ¹⁰¹ in the above formula (b-1).
The chain alkenyl group which may have a substituent in R " ¹⁰³ is preferably the group exemplified as the chain alkenyl group in R ¹⁰¹ in the above formula (b-1).

-In the anion formula (b-2) in the component (b-2), R ¹⁰⁴ and R ¹⁰⁵ independently have a cyclic group which may have a substituent and a chain which may have a substituent. Alkyl group of the above, or a chain alkenyl group which may have a substituent, respectively, and the same as R ¹⁰¹ in the formula (b-1) can be mentioned. However, R ¹⁰⁴ and R ¹⁰⁵ may be coupled to each other to form a ring.
R ¹⁰⁴ and R ¹⁰⁵ are preferably a chain-like alkyl group which may have a substituent, and are a linear or branched alkyl group or a linear or branched fluorinated alkyl group. Is more preferable.
The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and even more preferably 1 to 3 carbon atoms. The carbon atom number of the chain-shaped alkyl group of R ¹⁰⁴ and R ¹⁰⁵ is preferably as small as possible because the solubility in the resist solvent is good within the range of the carbon atom number. Further, in the chain-like alkyl groups of R ¹⁰⁴ and R ¹⁰⁵ , the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and the stronger the acid strength, and the higher the energy resistance to high-energy light and electron beams of 250 nm or less. It is preferable because it improves transparency. The ratio of fluorine atoms in the chain-shaped alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are substituted with fluorine atoms. It is a perfluoroalkyl group.
In formula (b-2), V ¹⁰² and V ¹⁰³ are each independently a single bond, an alkylene group, or a fluorinated alkylene group, and each of them is the same as V ¹⁰¹ in formula (b-1). Can be mentioned.
In formula (b-2), L ¹⁰¹ and L ¹⁰² are independently single bonds or oxygen atoms, respectively.

-In the anion formula (b-3) in the component (b-3), R ¹⁰⁶ to R ¹⁰⁸ are each independently a cyclic group which may have a substituent and a chain which may have a substituent. Is a chain alkenyl group which may have an alkyl group or a substituent, and examples thereof include the same group as R ¹⁰¹ in the formula (b-1).
In formula (b-3), L ¹⁰³ to L ¹⁰⁵ are independently single-bonded, -CO- or -SO _2- .

Among the above, as the anion portion of the component (B), the anion in the component (b-1) is preferable. Among these, the anion represented by any of the above general formulas (an-1) to (an-3) is more preferable, and it is represented by either the general formula (an-1) or (an-2). Anions are more preferred, and anions represented by the general formula (an-2) are particularly preferred.

{Cation part}
In the formula (b-1), the formula (b-2), and the formula (b-3), M ^{m +} represents an m-valent onium cation. Of these, sulfonium cations and iodonium cations are preferable.
m is an integer of 1 or more.

Preferred cation portions ((M ^{m +} ) _{1 / m} ) include organic cations represented by the above formulas (ca-1) to (ca-5), respectively. Among them, the cation portion ((M ^{m +} ) _{1 / m} ) is preferably a cation represented by the general formula (ca-1).

In the resist composition of the present embodiment, the component (B) may be used alone or in combination of two or more.
When the resist composition contains the component (B), the content of the component (B) in the resist composition is preferably less than 50 parts by mass with respect to 100 parts by mass of the component (A), preferably 1 to 40 parts by mass. Is more preferable, and 3 to 25 parts by mass is further preferable.
By setting the content of the component (B) to the above-mentioned preferable range, pattern formation is sufficiently performed. Further, when each component of the resist composition is dissolved in an organic solvent, a uniform solution can be easily obtained, and the storage stability of the resist composition is improved, which is preferable.

<< At least one compound (E) selected from the group consisting of an organic carboxylic acid and a phosphorus oxo acid and a derivative thereof >>
The resist composition of the present embodiment contains organic carboxylic acid, phosphorus oxo acid and its derivatives as optional components for the purpose of preventing sensitivity deterioration, improving the resist pattern shape, stability over time, and the like. Can contain at least one compound (E) selected from the group (hereinafter referred to as "component (E)").
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 the oxo acid of phosphorus include phosphoric acid, phosphonic acid, phosphinic acid and the like, and among these, phosphonic acid is particularly preferable.
Examples of the derivative of phosphorus oxo acid include an ester in which the hydrogen atom of the oxo acid is replaced with a hydrocarbon group, and examples of the hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and the number of carbon atoms. Examples thereof include 6 to 15 aryl groups.
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 phosphonic acid derivative include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester.
Examples of the derivative of phosphinic acid include phosphinic acid ester and phenylphosphinic acid.
In the resist composition of the present embodiment, the component (E) may be used alone or in combination of two or more.
When the resist composition contains the component (E), the content of the component (E) is usually used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A1).

<< Organic solvent component (S) >>
The resist composition of the present embodiment can be produced by dissolving a resist material in an organic solvent component (hereinafter referred to as "(S) component").
The component (S) may be any component as long as it can dissolve each component to be used to form a uniform solution, and any conventionally known solvent for the chemically amplified resist composition may be appropriately used. It can be selected and used.
Examples of the component (S) include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; ethylene glycol, diethylene glycol and propylene glycol. , Polyhydric alcohols such as dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, said polyhydric alcohols or said ester bond. Derivatives of polyhydric alcohols such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monoalkyl ethers such as monobutyl ethers, or compounds having an ether bond such as monophenyl ethers [among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred]; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate. , Esters such as methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethylbenzyl ether, cresylmethyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, Examples thereof include aromatic organic solvents such as xylene, simene and mesityrene, dimethylsulfoxide (DMSO) and the like.
In the resist composition of the present embodiment, the component (S) may be used alone or as a mixed solvent of two or more kinds. Of these, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferable.

Further, as the component (S), a mixed solvent in which PGMEA and a polar solvent are mixed 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 even more preferably 3: 7 to 7 :. It is 3. Further, a mixed solvent of PGMEA, PGME and cyclohexanone is also preferable.
In addition, as the component (S), a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferable. In this case, the mass ratio of the former to the latter is preferably 70:30 to 95: 5 as the mixing ratio.
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 component (S) is used so that the solid content concentration of the resist composition is in the range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass.

The resist composition of the present embodiment further contains an additive that is more miscible, for example, an additional resin for improving the performance of the resist film, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, and an antihalation agent. , Dyes and the like can be appropriately added and contained.

In the resist composition of the present embodiment, after dissolving the resist material in the component (S), impurities and the like may be removed by using a polyimide porous film, a polyamide-imide porous film, or the like. For example, the resist composition may be filtered using a filter made of a polyimide porous membrane, a filter made of a polyamide-imide porous membrane, a filter made of a polyimide porous membrane, a polyamide-imide porous membrane, or the like. Examples of the polyimide porous film and the polyamide-imide porous film include those described in JP-A-2016-155121.

The resist composition of the present embodiment described above contains the component (D01), the component (D02), and the component (F01) in addition to the component (A).
By containing the component (D01), the diffusion of acid is appropriately controlled in the unexposed portion. On the other hand, the inclusion of the component (D02) promotes deprotection in the exposed portion. Further, by containing the component (F01) having the structural unit (f01) and the structural unit (f02), the solubility of the component (F01) in the developing solution in the exposed portion is improved. Due to these actions, according to the resist composition of the present embodiment, both the sensitivity and the LWR can be improved.

(Resist pattern forming method)
The resist pattern forming method according to the second aspect of the present invention is a step of forming a resist film using the resist composition according to the first aspect of the present invention described above on a support, and the resist film is exposed. It is a method including a step and a step of developing the resist film after the exposure to form a resist pattern.
As an embodiment of such a resist pattern forming method, for example, a resist pattern forming method performed as follows can be mentioned.

First, the resist composition of the above-described embodiment is applied onto a support with a spinner or the like, and a bake (post-apply bake (PAB)) treatment is preferably performed for 40 to 120 seconds under temperature conditions of, for example, 80 to 150 ° C. Is applied for 60 to 90 seconds to form a resist film.
Next, using an exposure apparatus such as a KrF exposure apparatus, an ArF exposure apparatus, an electron beam drawing apparatus, and an EUV exposure apparatus, the resist film is passed through a mask (mask pattern) on which a predetermined pattern is formed. After performing selective exposure by exposure or drawing by direct irradiation of an electron beam without a mask pattern, baking (post-exposure baking (PEB)) processing is performed for 40 to 120 seconds under temperature conditions of, for example, 80 to 150 ° C. , Preferably for 60-90 seconds.
Next, the resist film is developed. In the case of the alkaline developing process, the developing process is performed using an alkaline developing solution, and in the case of the solvent developing process, a developing solution containing an organic solvent (organic developing solution) is used.

After the development treatment, a rinsing treatment is preferably performed. In the case of the alkaline development process, the rinsing treatment is preferably a water rinse using pure water, and in the case of the solvent development process, it is preferable to use a rinsing solution containing an organic solvent.
In the case of the solvent development process, after the development treatment or the rinsing treatment, a treatment for removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be performed.
Dry after development or rinsing. In some cases, a baking process (post-baking) may be performed after the development process.
In this way, the resist pattern can be formed.

The support is not particularly limited, and conventionally known ones can be used, and examples thereof include a substrate for electronic components and a support having a predetermined wiring pattern formed therein. More specifically, a silicon wafer, a metal substrate such as copper, chromium, iron, or aluminum, a glass substrate, or the like can be mentioned. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold and the like can be used.
Further, the support may be one in which an inorganic and / or organic film is provided on the substrate as described above. 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 the multilayer resist method.
Here, in the multilayer resist method, at least one layer of an organic film (lower layer organic film) and at least one layer of a resist film (upper layer resist film) are provided on a substrate, and a resist pattern formed on the upper layer resist film is used as a mask. It is a method of patterning an lower organic film, and is said to be able to form a pattern with a high aspect ratio. That is, according to the multilayer resist method, since the required thickness can be secured by the lower organic film, the resist film can be thinned and a fine pattern having a high aspect ratio can be formed.
The multilayer 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 can be divided into a method of forming a multilayer structure having three or more layers provided with (metal thin film, etc.) (three-layer resist method).

The wavelength used for exposure is not particularly limited, and may be ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV ₍ extreme ultraviolet rays), VUV (vacuum ultraviolet rays), EB (electron beam), X-rays, soft X-rays, 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 useful for ArF excimer laser. That is, the resist pattern forming method of the present embodiment is a particularly useful method when the step of exposing the resist film includes an operation of exposing the resist film to an ArF excimer laser.

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

Examples of the alkaline developer used in the developing process in the alkaline developing process include a 0.1 to 10% by mass tetramethylammonium hydroxide (TMAH) aqueous solution.
The organic solvent contained in the organic developer used in the developing process in the solvent developing process may be any known organic solvent as long as it can dissolve the component (A) (component (A) before exposure). It can be selected as appropriate. Specific examples thereof include ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, polar solvents such as ether solvents, hydrocarbon solvents and the like.
The ketone solvent is an organic solvent containing CC (= O) -C in its structure. The ester solvent is an organic solvent containing CC (= O) -OC in its structure. The alcohol solvent is an organic solvent containing an alcoholic hydroxyl group in its structure. The "alcoholic hydroxyl group" means a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. The nitrile-based solvent is an organic solvent containing a nitrile group in its structure. The amide-based solvent is an organic solvent containing an amide group in its structure. The ether solvent is an organic solvent containing COC in its structure.
Among the organic solvents, there are organic solvents containing a plurality of functional groups that characterize each of the above solvents in the structure, but in that case, the organic solvent corresponds to any solvent type containing the functional groups of the organic solvent. It shall be. For example, diethylene glycol monomethyl ether shall fall under any of the alcohol-based solvents and ether-based solvents in the above classification.
The hydrocarbon-based solvent is a hydrocarbon solvent which is composed of a hydrocarbon which may be halogenated and has no substituent other than a halogen atom. As the halogen atom, a fluorine atom is preferable.
Among the above, the polar solvent is preferable, and the ketone solvent, the ester solvent, the nitrile solvent and the like are preferable as the organic solvent contained in the organic developer.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, phenylacetone and methylethylketone. , Methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, γ-butyrolactone, methylamylketone (2-heptanone) and the like. Among these, as the ketone solvent, methylamylketone (2-heptanone) is preferable.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy acetate, ethyl ethoxyacetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol. Monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate , 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxy Butyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxy Pentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formic acid, ethyl forerate, butyl forerate, propyl forrate, ethyl lactate, butyl lactate, propyl lactate, carbonic acid. Ethyl, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, 2- Methyl hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate and the like can be mentioned. Be done. Among these, butyl acetate is preferable as the ester solvent.

Examples of the nitrile-based solvent include acetonitrile, propionitrile, valeronitrile, butyronitrile and the like.

A known additive can be added to the organic developer, if necessary. Examples of the additive include a surfactant. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used. As the surfactant, a nonionic surfactant is preferable, and a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant is more preferable.
When the surfactant is blended, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0.% With respect to the total amount of the organic developer. 5% by mass is more preferable.

The developing process can be carried out by a known developing method. For example, a method of immersing a support in a developing solution for a certain period of time (dip method), a method of raising the developing solution on the surface of the support by surface tension and allowing it to stand still for a certain period of time. (Paddle method), spraying the developer on the surface of the support (spray method), spreading the developer on the support rotating at a constant speed while scanning the developer spray nozzle. Examples include a method of continuing (dynamic dispense method).

As the organic solvent contained in the rinse solution used for the rinse treatment after the development process in the solvent development process, for example, among the organic solvents listed as the organic solvents used in the organic developer, those that do not easily dissolve the resist pattern are appropriately selected. Can be used. Usually, at least one solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent is used. Among these, at least one selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent and an amide solvent is preferable, and at least one selected from an alcohol solvent and an ester solvent is preferable. More preferably, an alcohol solvent is particularly preferable.
The alcohol solvent used in the rinsing solution is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched or cyclic. Specific examples thereof include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol and the like. Be done. Among these, 1-hexanol, 2-heptanol and 2-hexanol are preferable, and 1-hexanol and 2-hexanol are more preferable.
Any one of these organic solvents may be used alone, or two or more thereof may be used in combination. Further, it may be mixed with an organic solvent other than the above or water and used. However, in consideration of development characteristics, the blending amount of water in the rinsing liquid is preferably 30% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, and 3% by mass, based on the total amount of the rinsing liquid. % Or less is particularly preferable.
A known additive can be added to the rinse solution, if necessary. Examples of the additive include a surfactant. Examples of the surfactant include the same as described above, and a nonionic surfactant is preferable, and a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant is more preferable.
When the surfactant is blended, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, preferably 0.01 to 0.5% by mass, based on the total amount of the rinse liquid. % Is more preferable.

The rinsing treatment (cleaning treatment) using the rinsing liquid can be carried out by a known rinsing method. Examples of the rinsing treatment method include a method of continuously spraying the rinsing liquid on a support rotating at a constant speed (rotary coating method), a method of immersing the support in the rinsing liquid for a certain period of time (dip method), and the like. Examples thereof include a method of spraying a rinse liquid on the surface of the support (spray method).

According to the resist pattern forming method of the present embodiment described above, since the resist composition of the above-described embodiment is used, it is possible to form a resist pattern having high sensitivity and reduced roughness. ..

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

<Preparation of resist composition>
(Examples 1 to 6, Comparative Examples 1 to 8)
Each component shown in Table 1 was mixed and dissolved to prepare a resist composition of each example.

In Table 1, each abbreviation has the following meaning. The value in [] is the blending amount (part by mass).
(A) -1: A polymer compound represented by the following chemical formula (A-1). The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 7100, and the molecular weight dispersion (Mw / Mn) is 1.63. ¹³ The copolymerization composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m / n = 40/50/10.
(A) -2: A polymer compound represented by the following chemical formula (A-2). The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 6400, and the molecular weight dispersion (Mw / Mn) is 1.59. ¹³ The copolymerization composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m = 50/50.

(D01) -1 to (D01) -2: Compounds represented by the following chemical formulas (D01-1) to (D01-2).
(D02) -1 to (D02) -3: Compounds represented by the following chemical formulas (D02-1) to (D02-3).
(D2) -1: A compound represented by the following chemical formula (D2-1).

(F01) -1: A polymer compound represented by the following chemical formula (F01-1). The weight average molecular weight (Mw) in terms of standard polystyrene obtained by GPC measurement is 26000, and the molecular weight dispersion (Mw / Mn) is 1.50. ¹³ The copolymerization composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m = 80/20.
(F01) -2: A polymer compound represented by the following chemical formula (F01-2). The weight average molecular weight (Mw) in terms of standard polystyrene obtained by GPC measurement is 25,000, and the molecular weight dispersion (Mw / Mn) is 1.50. ¹³ The copolymerization composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m = 80/20.
(F1) -1: A polymer compound represented by the following chemical formula (F1-1). The weight average molecular weight (Mw) in terms of standard polystyrene obtained by GPC measurement is 25,000, and the molecular weight dispersion (Mw / Mn) is 1.49. ¹³ The copolymerization composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m = 80/20.
(F1) -2: A polymer compound represented by the following chemical formula (F1-2). The weight average molecular weight (Mw) in terms of standard polystyrene obtained by GPC measurement is 27,000, and the molecular weight dispersion (Mw / Mn) is 1.51. ¹³ The copolymerization composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by C-NMR is l / m = 80/20.

(B) -1: An acid generator composed of a compound represented by the following chemical formula (B-1).

(S) -1: Mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / cyclohexanone = 1200/780/980 (mass ratio).

<Formation of resist pattern>
The organic antireflection film composition "ARC29A" (manufactured by Brewer Science Co., Ltd.) is applied onto a 12-inch silicon wafer using a spinner, and is baked on a hot plate at 205 ° C. for 60 seconds to dry. An organic antireflection film having a film thickness of 98 nm was formed.
Next, the resist composition of each example is applied onto the organic antireflection film using a spinner, prebaked (PAB) at 90 ° C. for 60 seconds on a hot plate, and dried to obtain a film thickness. An 80 nm resist film was formed. Then, a top coat was applied onto the resist film using a spinner, and a hot plate was baked at 90 ° C. for 60 seconds.
Photomask (manufactured by ASML; NA (numerical aperture) = 1.35, Dipole, Sigma 0.97-0.78, immersion medium: ultrapure water] for immersion ArF exposure device ArF excimer laser (193 nm) was selectively irradiated via 6% halftone). Then, PEB treatment was performed at 95 ° C. for 60 seconds.
Next, alkaline development was performed at 23 ° C. with a 2.38 mass% TMAH aqueous solution (trade name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 10 seconds, and then a water rinse for 15 seconds using pure water. Was performed, and the product was shaken off and dried. As a result, in each example, a line-and-space pattern (hereinafter referred to as “LS pattern”) having a line width of 40 nm and a pitch of 80 nm (mask size of 40 nm) was formed.

[Evaluation of Optimal Exposure (Eop)]
The optimum exposure amount Eop (μC / cm ² ) in which the LS pattern of the target size is formed was determined by the above <resist pattern formation>. This is shown in Table 2 as "Eop (μC / cm ² )".

[Evaluation of LWR (Linewise Roughness)]
For the LS pattern formed in the above <Formation of resist pattern>, 3σ, which is a scale indicating LWR, was obtained. This is shown in Table 2 as "LWR (nm)".
"3σ" is a standard deviation obtained from the measurement results of 400 line positions measured in the longitudinal direction of the line using a scanning electron microscope (acceleration voltage 300V, trade name: S-9380, manufactured by Hitachi High-Technologies Corporation). It shows a triple value (3σ) (unit: nm) of (σ). The smaller the value of 3σ, the smaller the roughness of the side wall of the line, which means that an LS pattern having a more uniform width was obtained.

As shown in Table 2, it was confirmed that the resist composition of the example was able to form a resist pattern having better sensitivity and better LWR than the resist composition of the comparative example.

Claims (4)

A resist composition that generates an acid upon exposure and whose solubility in a developing solution changes due to the action of the acid.
Substrate component (A) whose solubility in a developing solution changes due to the action of acid, and
The compound (D01) represented by the following general formula (d01-1) and
The compound (D02) represented by the following general formula (d02-1) and
A polymer compound (F01) having a structural unit (f01) represented by the following general formula (f01-1) and a structural unit (f02) represented by the following general formula (f02-1),
A resist composition containing.

[In the formula, Rd ⁰¹ and Rd ⁰² may 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. However, in Rd ⁰² in the formula (d01-2), it is assumed that the fluorine atom is not bonded to the carbon atom adjacent to the S atom in the formula (d01-2). m is an integer of 1 or more independently, and M ^{m +} is an organic cation having an m valence independently. ]

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, respectively; Vf ⁰¹ is a divalent linking group; Rf ⁰¹ is a monovalent organic group containing a fluorine atom; Vf ⁰² is a divalent linking group; nf ⁰² is an integer of 0 to 2; Rf ⁰² is an acid dissociable group. .. ] The resist composition according to claim 1, further comprising an acid generator component (B) that generates an acid upon exposure. The resist composition according to claim 1 or 2, wherein Rf ⁰² in the general formula (f02-1) is a group represented by the following general formula (Rf02-1).

[In the formula, Rf ⁰²² to Rf ⁰²³ are each independently saturated aliphatic hydrocarbon groups, and R ⁰²² and R ⁰² 3 may be bonded to each other to form a ring. * Is a bond that bonds to an oxygen atom in the above formula (f02-1). ] A step of forming a resist film using the resist composition according to any one of claims 1 to 3 on a support, a step of exposing the resist film, and a step of developing the exposed resist film. A resist pattern forming method comprising a step of forming a resist pattern.