JP2013003512A - Resist composition, and resist pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist composition and a resist pattern forming method in which dimensional changes due to the effect of time passage are suppressed and lithography properties and resist pattern shapes are excellent.SOLUTION: A resist composition contains a compound (G) having a monovalent group represented by the general formula (g1) or (g2), and a compound (H) having a monovalent group represented by the general formula (h1) or (h2).

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 and developed to form a resist pattern having a predetermined shape on the resist film. The process to perform is performed. A resist material in which the exposed portion of the resist film changes to a property that dissolves in the developer is referred to as a positive type, and a resist material that changes to a property in which the exposed portion does not dissolve in the developer is referred to as a negative type.
In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has been rapidly progressing due to advances in lithography technology.
As a technique for miniaturization, the exposure light source is generally shortened in wavelength (increased energy). Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used, but at present, mass production of semiconductor elements using a KrF excimer laser or an ArF excimer laser has started. Further, studies have been made on EUV (extreme ultraviolet), EB (electron beam), X-rays, and the like having a shorter wavelength (higher energy) than these excimer lasers.
Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern with fine dimensions.
Conventionally, as a resist material satisfying such requirements, a chemically amplified resist composition containing an acid generator component that generates an acid upon exposure and a base material component whose solubility in a developing solution is changed by the action of the acid. Is used.

As a base material component used in the chemically amplified resist composition, a resin (base resin) is generally used.
For example, as a chemically amplified resist composition for forming a positive resist pattern in an alkali development process using an alkali developer as a developer, an acid generator component and solubility in an alkali developer due to the action of an acid are included. What contains the resin component which increases is generally used. When a resist film formed using such a resist composition is selectively exposed at the time of resist pattern formation, an acid is generated from the acid generator component in the exposed portion, and the alkali developer of the resin component is generated by the action of the acid. As a result, the exposed area becomes soluble in an alkaline developer. Therefore, by performing alkali development, a positive pattern in which an unexposed portion remains as a pattern is formed.
As the resin component, one that increases the polarity of the resin by the action of an acid is generally used. As the polarity increases, solubility in an alkaline developer increases while solubility in an organic solvent decreases. Therefore, when a solvent development process using an organic solvent-containing developer (organic developer) is applied instead of an alkali development process, the solubility in the organic developer is relatively reduced in the exposed area. In the solvent development process, the unexposed portion of the resist film is dissolved and removed by the organic developer, and a negative resist pattern is formed in which the exposed portion remains as a pattern. Such a solvent development process for forming a negative resist pattern is sometimes referred to as a negative development process (see, for example, Patent Document 1).

At present, as a base resin of a chemically amplified resist composition used in ArF excimer laser lithography and the like, it has a structural unit derived from (meth) acrylic acid ester in its main chain because of its excellent transparency near 193 nm. Resins (acrylic resins) and the like are generally used (see, for example, Patent Document 2).
The base resin has a plurality of structural units in order to improve lithography properties and the like. For example, in the case of a resin component in which the polarity of the resin is increased by the action of the acid, it usually has a structural unit having an acid-decomposable group that is decomposed by the action of the acid generated from the acid generator component and increases in polarity. Those having a structural unit having a polar group such as a hydroxyl group and a structural unit having a lactone structure are used.
Here, “(meth) acrylic acid ester” means one or both of an acrylic acid ester having a hydrogen atom bonded to the α-position and a methacrylic acid ester having a methyl group bonded to the α-position. “(Meth) acrylate” means one or both of an acrylate having a hydrogen atom bonded to the α-position and a methacrylate having a methyl group bonded to the α-position. “(Meth) acrylic acid” means one or both of acrylic acid having a hydrogen atom bonded to the α-position and methacrylic acid having a methyl group bonded to the α-position.

  Various acid generators used in chemically amplified resist compositions have been proposed so far, such as onium salt acid generators, oxime sulfonate acid generators, diazomethane acid generators, nitro acid generators, and nitro acid generators. Benzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators and the like are known.

The resist material includes a resin having a structural unit having an acid-decomposable group, and a general formula (i): R ¹⁰¹ -R ¹⁰² -N ^-- S (= O) ₂ -R ¹⁰³ Z ⁺ [wherein R ¹⁰¹ is a hydrogen atom, part or all of the hydrogen atoms are fluorine atoms, hydroxyl groups, —OR ¹⁰⁰ groups, —OCOR ¹⁰⁰ groups, or —COOR ¹⁰⁰ groups (provided that R ¹⁰⁰ is a straight chain having 1 to 10 carbon atoms) Or a branched monovalent hydrocarbon group, or a monovalent hydrocarbon group having a cyclic or cyclic partial structure having 3 to 20 carbon atoms) which may be substituted with 1 to 10 carbon atoms. A linear or branched monovalent hydrocarbon group or a monovalent hydrocarbon group having a cyclic or cyclic partial structure having 3 to 20 carbon atoms, R ¹⁰² represents a single bond or —O— (C═O ) -Group, R ¹⁰³ represents hydrogen A linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms or a cyclic or cyclic partial structure having 3 to 20 carbon atoms, which may be partially or wholly substituted with fluorine atoms. And Z ⁺ represents an onium cation. ] (Hereinafter referred to as “compound (i)”) and a radiation-sensitive resin composition are disclosed (see Patent Document 3).
The compound (i) in the unexposed portion of the resist film has an action of suppressing an acid diffusion phenomenon by performing an ion exchange reaction with an acid generated from an acid generator or the like, and the compound (i) in the exposed portion is decomposed. By doing so, the basicity with respect to the acid generated from an acid generator or the like is lost. Thereby, according to the radiation sensitive resin composition described in patent document 3, it is supposed that the improvement of a lithography characteristic, a resist pattern shape, etc. will be aimed at.

JP 2008-292975 A JP 2003-241385 A International Publication No. 2010/147079 Pamphlet

However, in the radiation-sensitive resin composition described in Patent Document 3, there is a problem that the resist pattern dimensions formed before and after storage are different by preparing the resin composition and storing it for a certain period of time. is there.
On the other hand, the resist pattern is increasingly miniaturized, and the resist material is required to have better lithography characteristics and a resist pattern shape than ever.
The present invention has been made in view of the above circumstances, and provides a resist composition and a resist pattern forming method that are excellent in lithography characteristics and resist pattern shape while suppressing dimensional fluctuation due to the influence of time. Let it be an issue.

In order to solve the above problems, the present invention employs the following configuration.
That is, the first aspect of the present invention includes a compound (G) having a monovalent group represented by the following general formula (g1) or a monovalent group represented by the general formula (g2), and the following: A resist composition comprising a monovalent group represented by general formula (h1) or a compound (H) having a monovalent group represented by general formula (h2).

［式（ｇ１）中、Ｒ^２は単結合又は−Ｃ（＝Ｏ）−Ｏ−基である。但し、Ｒ^２が単結合の場合、式中のＮ⁻が−Ｃ（＝Ｏ）−基に結合するものは（Ｇ）成分には含まれないものとする。Ｒ^３はフッ素原子で置換されていてもよい、炭素数１〜１０の直鎖状若しくは分岐鎖状の１価の炭化水素基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基である。Ｍ^＋はそれぞれ独立に有機カチオンである。］

[In the formula (g1), R ² represents a single bond or a —C (═O) —O— group. However, if R ² is a single bond, N in the formula ^- is -C (= O) - those that bind to groups and are not included in the component (G). R ³ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. M ⁺ is each independently an organic cation. ]

［式（ｈ１）中、Ｒ^６は単結合又は−Ｃ（＝Ｏ）−Ｏ−基である。Ｒ^７はフッ素原子で置換されていてもよい、炭素数１〜１０の直鎖状若しくは分岐鎖状の１価の炭化水素基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基である。］

[In the formula (h1), R ⁶ represents a single bond or a —C (═O) —O— group. R ⁷ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. ]

  According to a second aspect of the present invention, a resist film is formed on a support using the resist composition of the first aspect, the resist film is exposed, and the resist film is developed to form a resist. It is a resist pattern formation method including the process of forming a pattern.

In the present specification and claims, “exposure” is a concept including general irradiation of radiation.
“Structural unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
“Aliphatic” is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups.
The “alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group.
“Halogenated alkyl group” is a group in which some or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms. “Halogenated alkylene group” is in which some or all of the hydrogen atoms in the alkylene group are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
A “fluorinated alkyl group” is a group in which some or all of the hydrogen atoms in the alkyl group are substituted with fluorine atoms. A “fluorinated alkylene group” is a group in which some or all of the hydrogen atoms in the alkylene group are substituted with fluorine atoms. Group.

  ADVANTAGE OF THE INVENTION According to this invention, while being able to suppress the dimensional variation by the influence of time, the resist composition excellent in the lithography characteristic and the resist pattern shape and the resist pattern formation method can be provided.

≪Resist composition≫
The resist composition of the present invention comprises a compound (G) having a monovalent group represented by the general formula (g1) or a monovalent group represented by the general formula (g2) (hereinafter referred to as “(G) component”). And a compound (H) having a monovalent group represented by the general formula (h1) or a monovalent group represented by the general formula (h2) (hereinafter referred to as “component (H)”). Also).
(G) component and (H) component in this invention can be used as an additive mix | blended with a base material component or a base material component, respectively.
Here, the “base component” is an organic compound having a film forming ability and is a main component constituting a resist film, and preferably refers to an organic compound having a molecular weight of 500 or more. When the molecular weight of the organic compound is 500 or more, the film-forming ability is improved and a nano-level resist pattern is easily formed.
Organic compounds used as the base material component are roughly classified into non-polymers and polymers.
As the non-polymer, those having a molecular weight of 500 or more and less than 4000 are usually used. In the present specification, the “low molecular compound” refers to a non-polymer having a molecular weight of 500 or more and less than 4000.
As the polymer, those having a molecular weight of 1000 or more are usually used. In the present specification and claims, the term “resin” refers to a polymer having a molecular weight of 1000 or more. As the molecular weight of the polymer, a polystyrene-reduced mass average molecular weight by GPC (gel permeation chromatography) is used.

When the component (G) and the component (H) are used as additives added together with the base material component, the resist composition of the present invention is developed by the action of an acid in addition to the components (G) and (H). A base material component (A) (hereinafter also referred to as “component (A)”) whose solubility in the liquid changes, and an acid generator component (B) that generates acid upon exposure (hereinafter also referred to as “component (B)”). (Hereinafter, this resist composition is referred to as “first embodiment”).
When one or both of the component (G) and the component (H) is used as the substrate component (component (A)), the resist composition of the present invention includes (G) as the substrate component (component (A)). Component containing component (H) as additive and component (B) (this resist composition is hereinafter referred to as “second embodiment”); as a base component (component (A)) (H) component, (G) component as additive, and (B) component (this resist composition is hereinafter referred to as “third embodiment”); base material component ((A (G) component as component)), (H) component as substrate component (component (A)), and component (B) (hereinafter referred to as “fourth embodiment”). ").

When each resist film is formed using the resist composition of the first to fourth embodiments, and the resist film is selectively exposed, an acid is generated from the component (B) in the exposed portion, While the solubility of the component (A) in the developer changes due to the action of the acid, the solubility of the component (A) in the developer does not change in the unexposed area. Therefore, between the exposed area and the unexposed area. A difference in solubility in the developer occurs. Therefore, when the resist film is developed, when the resist composition is positive, the exposed portion is dissolved and removed to form a positive resist pattern, and when the resist composition is negative, the unexposed portion is dissolved. This is removed to form a negative resist pattern.
At that time, the (G) component in the unexposed portion of the resist film performs an ion exchange reaction with the acid generated from the (B) component and suppresses the acid diffusion phenomenon, and the (G) component in the exposed portion is By decomposing by exposure, the basicity with respect to the acid generated from the component (B) is lost. Thereby, improvement of lithography characteristics, resist pattern shape, etc. is achieved.
The component (H) mainly contributes to improvement in storage stability of the resist composition with time.

The resist composition of the present invention is not limited to the first to fourth embodiments described above,
A copolymer having a structural unit derived from the component (G) and a structural unit derived from the component (H) in the same copolymer as the base material component (component (A)); (This resist composition is hereinafter referred to as “fifth embodiment”); (G) component as additive, (H) component as additive, and acid can be generated by exposure ( A) containing the component (hereinafter, this resist composition is referred to as “sixth embodiment”) and the like.

In this specification, a resist composition in which an exposed portion is dissolved and removed to form a positive resist pattern is referred to as a positive resist composition, and a resist composition that forms a negative resist pattern in which an unexposed portion is dissolved and removed. Is referred to as a negative resist composition.
The resist composition of the present invention may be a positive resist composition or a negative resist composition. In addition, the resist composition of the present invention may be used for an alkali development process using an alkali developer for development processing at the time of forming a resist pattern, and a developer (organic developer) containing an organic solvent is used for the development processing. It may be for the solvent development process used.

When the resist composition of the present invention is a resist composition that forms a negative resist pattern in an alkali development process (or forms a positive resist pattern in a solvent development process), the component (A) is preferably A substrate component soluble in an alkali developer (hereinafter referred to as “alkali-soluble substrate component”) is used, and a crosslinking agent component is further blended. As the alkali-soluble base component, a resin (alkali-soluble resin) is usually used.
The alkali-soluble substrate component usually has an alkali-soluble group such as a hydroxyl group, a carboxy group, or an amino group, and the cross-linking agent component includes an alkali-soluble group such as a methylol group or an alkoxymethyl group by the action of an acid. Those having a reactive group capable of reacting with are used. Therefore, when a resist film is formed using such a resist composition and selective exposure is performed on the resist film, for example, an acid is generated from the component (B) in the exposed portion, and alkali-soluble due to the action of the acid. Cross-linking occurs between the base component and the cross-linking agent component, resulting in a decrease in alkali-soluble groups of the alkali-soluble base component and a concomitant decrease in polarity and increase in molecular weight. As a result, solubility in an alkali developer is increased. Decrease (increase in solubility in organic developer). Therefore, in the formation of a resist pattern, when a resist film obtained by coating the resist composition on a support is selectively exposed, the exposed portion is hardly soluble in an alkali developer (to an organic developer). On the other hand, the unexposed area remains soluble (almost insoluble in the organic developer) while remaining undissolved in the alkali developer, so that a negative resist pattern can be formed by developing with an alkali developer. . At this time, if an organic developer is used as the developer, a positive resist pattern can be formed.
As the crosslinking agent component, for example, it is usually preferable to use an amino crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group, a melamine crosslinking agent, or the like because a good resist pattern with less swelling can be formed. It is preferable that the compounding quantity of a crosslinking agent component is 1-50 mass parts with respect to 100 mass parts of alkali-soluble resin.
In addition, when the alkali-soluble substrate component has self-crosslinkability (for example, when the alkali-soluble substrate component has a group capable of reacting with an alkali-soluble group by the action of an acid), the crosslinking agent component is not necessarily blended. Also good.

When the resist composition of the present invention is a resist composition that forms a positive resist pattern in an alkali development process and a negative resist pattern in a solvent development process, the component (A) is preferably an acid A base material component (hereinafter also referred to as “(A0) component”) whose polarity is increased by action is used. Since the polarity of the component (A0) changes before and after exposure, by using the component (A0), a good development contrast can be obtained not only in the alkali development process but also in the solvent development process.
That is, when applying an alkali development process, the component (A0) is hardly soluble in an alkali developer before exposure, and when an acid is generated from the component (B) by exposure, for example, the polarity of the component is reduced by the action of the acid. Increases the solubility in an alkaline developer. Therefore, in the formation of a resist pattern, when a resist film obtained by applying the resist composition on a support is selectively exposed, the exposed portion changes from slightly soluble to soluble in an alkaline developer. Since the unexposed portion remains hardly soluble in alkali and does not change, a positive resist pattern can be formed by alkali development. On the other hand, when the solvent development process is applied, the component (A0) is highly soluble in an organic developer before exposure. For example, when an acid is generated from the component (B) by exposure, the (A0) component is polar due to the action of the acid. Becomes higher and the solubility in an organic developer decreases. Therefore, in the formation of the resist pattern, when the resist film obtained by applying the resist composition on the support is selectively exposed, the exposed portion changes from soluble to poorly soluble in an organic developer. On the other hand, since the unexposed portion remains soluble and does not change, by developing with an organic developer, a contrast can be provided between the exposed portion and the unexposed portion, and a negative resist pattern can be formed.

<(G) component>
The component (G) is a compound having a monovalent group represented by the following general formula (g1) or a monovalent group represented by the general formula (g2).

［式（ｇ１）中、Ｒ^２は単結合又は−Ｃ（＝Ｏ）−Ｏ−基である。但し、Ｒ^２が単結合の場合、式中のＮ⁻が−Ｃ（＝Ｏ）−基に結合するものは（Ｇ）成分には含まれないものとする。Ｒ^３はフッ素原子で置換されていてもよい、炭素数１〜１０の直鎖状若しくは分岐鎖状の１価の炭化水素基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基である。Ｍ^＋はそれぞれ独立に有機カチオンである。］

[In the formula (g1), R ² represents a single bond or a —C (═O) —O— group. However, if R ² is a single bond, N in the formula ^- is -C (= O) - those that bind to groups and are not included in the component (G). R ³ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. M ⁺ is each independently an organic cation. ]

In Formula (g1), R ² is a single bond or a —C (═O) —O— group, and preferably a single bond. However, when ^{R 2} is a single bond, the component (G), N in the formula ^- is -C (= O) - those bonded to the group ^{(-N - -C (= O)} - has a group ) Is not included.
The linear or branched monovalent hydrocarbon group for R ³ has 1 to 10 carbon atoms, preferably 1 to 5 and more preferably 1 to 3. Examples of the linear or branched monovalent hydrocarbon group in R ³ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl. Group, tert-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
The cyclic monovalent hydrocarbon group for R ³ has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms. The cyclic monovalent hydrocarbon group for R ³ is a group obtained by removing one or more hydrogen atoms from a monocycloalkane; one or more polycycloalkanes such as bicycloalkane, tricycloalkane, tetracycloalkane, etc. Examples include a group excluding a hydrogen atom. Specifically, a group in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane, cyclohexane or cyclooctane; one from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane Examples include groups in which the above hydrogen atoms have been removed.
As the monovalent hydrocarbon group having a cyclic partial structure in R ³ , a group in which a cyclic hydrocarbon is bonded to the end of a linear or branched hydrocarbon group, a cyclic hydrocarbon is a linear group Or the group etc. which intervene in the middle of the branched hydrocarbon group are mentioned. The cyclic partial structure has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, a group obtained by removing one or more hydrogen atoms from the above-mentioned monocycloalkane, and one or more groups from polycycloalkane. Examples include a group excluding a hydrogen atom.
In R ³ , a linear or branched monovalent hydrocarbon group, a cyclic monovalent hydrocarbon group, and a monovalent hydrocarbon group having a cyclic partial structure are each in the hydrocarbon group. Part or all of the hydrogen atoms may be substituted with fluorine atoms or may not be substituted. The substituent may be substituted with a substituent other than a fluorine atom, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorinated alkyl group having 1 to 5 carbon atoms, and an oxygen atom (= O). Can be mentioned.

In the formulas (g1) and (g2), M ⁺ independently represents an organic cation.
The organic cation of M ⁺ is not particularly limited, and among them, an organic cation known as a cation part of an onium salt acid generator compounded in a conventional resist composition is preferable.
As such a cation moiety, a sulfonium ion or an iodonium ion is preferable, and a sulfonium ion is particularly preferable.

Preferable examples of the organic cation of M ⁺ include organic cations represented by the following general formula (g-c1) or general formula (g-c2).

［式（ｇ−ｃ１）中、Ｒ^１”〜Ｒ^３”はそれぞれ独立に置換基を有していてもよいアリール基、アルキル基、又はアルケニル基を表す。Ｒ^１”〜Ｒ^３”のうち、いずれか二つが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。式（ｇ−ｃ２）中、Ｒ^５”〜Ｒ^６”はそれぞれ独立に置換基を有していてもよいアリール基、アルキル基又はアルケニル基を表す。］

[In formula (g-c1), R ¹ ″ to R ³ ″ each independently represents an aryl group, an alkyl group, or an alkenyl group which may have a substituent. Any two of R ¹ ″ to R ³ ″ may be bonded to each other to form a ring together with the sulfur atom in the formula. In formula (g-c2), R ⁵ ″ to R ⁶ ″ each independently represents an aryl group, alkyl group or alkenyl group which may have a substituent. ]

In the formula (g-c1), R ¹ ″ to R ³ ″ each independently represents an aryl group, an alkyl group, or an alkenyl group that may have a substituent. Any two of R ¹ ″ to R ³ ″ may be bonded to each other to form a ring together with the sulfur atom in the formula.
Moreover, it is preferable that at least one of R ¹ ″ to R ³ ″ is an aryl group, and two or more of R ¹ ″ to R ³ ″ since the lithography characteristics and the resist pattern shape are further improved. Is more preferably an aryl group, and it is particularly preferred that all of R ¹ ″ to R ³ ″ are aryl groups.

As the aryl group for R ¹ ″ to R ³ ″, an unsubstituted aryl group having 6 to 20 carbon atoms; some or all of the hydrogen atoms of the unsubstituted aryl group are alkyl groups, alkoxy groups, halogen atoms, hydroxyl groups , An oxo group (═O), an aryl group, an alkoxyalkyloxy group, an alkoxycarbonylalkyloxy group, —C (═O) —O—R ⁶ ′, —O—C (═O) —R ⁷ ′, —O And a substituted aryl group substituted with —R ⁸ ′ and the like. R ⁶ ′, R ⁷ ′ and R ⁸ ′ are each a linear, branched or cyclic saturated hydrocarbon group having 1 to 25 carbon atoms, or a C 2 to 5 carbon atoms. It is a linear or branched aliphatic unsaturated hydrocarbon group.
In R ¹ ″ to R ³ ″, the unsubstituted aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.
As the alkyl group as a substituent in the substituted aryl group of R ¹ ″ to R ³ ″, 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, a tert-butyl group Most preferably.
As the alkoxy group as a substituent in the substituted aryl group, 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, or a tert-butoxy group. Most preferably it is.
The halogen atom as a substituent in the substituted aryl group is preferably a fluorine atom.
Examples of the aryl group as a substituent in the substituted aryl group include the same aryl groups as those described above for R ¹ ″ to R ³ ″, preferably an aryl group having 6 to 20 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Group is more preferable, and phenyl group and naphthyl group are more preferable.

As the alkoxyalkyloxy group in the substituted aryl group, for example,
General formula: -O-C ( ^R47 ) ( ^R48 ) -O- ^R49
[Wherein, R ⁴⁷ and R ⁴⁸ each independently represent a hydrogen atom or a linear or branched alkyl group, and R ⁴⁹ represents an alkyl group. ] Is represented.
In R ⁴⁷ and R ⁴⁸ , the alkyl group preferably has 1 to 5 carbon atoms, may be linear or branched, and is preferably an ethyl group or a methyl group, and most preferably a methyl group.
At least one of R ⁴⁷ and R ⁴⁸ is preferably a hydrogen atom. In particular, it is more preferable that one is a hydrogen atom and the other is a hydrogen atom or a methyl group.
The alkyl group for R ⁴⁹ preferably has 1 to 15 carbon atoms and may be linear, branched or cyclic.
The linear or branched alkyl group for R ⁴⁹ preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group. Can be mentioned.
The cyclic alkyl group for R ⁴⁹ preferably has 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, etc., which may or may not be substituted with an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group, etc. And a group obtained by removing one or more hydrogen atoms from the polycycloalkane. Examples of the monocycloalkane include cyclopentane and cyclohexane. Examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferable.

As the alkoxycarbonylalkyloxy group in the substituted aryl group, for example,
General formula: —O—R ⁵⁵ —C (═O) —O—R ⁵⁶
[Wherein, R ⁵⁵ represents a linear or branched alkylene group, and R ⁵⁶ represents a tertiary alkyl group. ] Is represented.
The linear or branched alkylene group for R ⁵⁵ preferably has 1 to 5 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, or a 1,1-dimethylethylene group. Etc.
As the tertiary alkyl group for R ⁵⁶ , 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl -1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, 1- (1-adamantyl) -1-methylethyl group, 1- (1-adamantyl) -1-methylpropyl group, 1- (1-adamantyl) -1-methylbutyl group, 1- (1-adamantyl) -1-methylpentyl group; 1- (1-cyclopentyl) -1-methylethyl group, 1- (1-cyclopentyl) -1-methylpropyl group, 1- (1-cyclopentyl) -1-methylbutyl group, 1- (1-cyclopentyl) -1-methylpentyl group; 1- (1-cyclohexyl) -1-methylethyl Group, 1- (1-cyclohexyl) -1-methylpropyl group, 1- (1-cyclohexyl) -1-methylbutyl group, 1- (1-cyclohexyl) -1-methylpentyl group, tert-butyl group, tert -Pentyl group, tert-hexyl group and the like.
Moreover, the general ^formula: the ^{R 56} in the -O-R 55 -C (= O ) -O-R 56, also include groups replaced by ^{R 56} '. R ⁵⁶ ′ is a hydrogen atom, an alkyl group, a fluorinated alkyl group, or an aliphatic cyclic group that may contain a hetero atom.
^Examples of the alkyl group for R ⁵⁶ ′ include the same alkyl groups as those described above for R ⁴⁹ .
^Examples of the fluorinated alkyl group for R ⁵⁶ ′ include groups in which some or all of the hydrogen atoms within the alkyl group for R ⁴⁹ have been substituted with fluorine atoms.
Examples of the aliphatic cyclic group which may contain a hetero atom in R ⁵⁶ ′ include an aliphatic cyclic group containing no hetero atom, an aliphatic cyclic group containing a hetero atom in the ring structure, and an aliphatic cyclic group. Examples include those in which a hydrogen atom in the group is substituted with a heteroatom.
Regarding R ⁵⁶ ′, the aliphatic cyclic group containing no hetero atom includes a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, and the like. Can be mentioned. Examples of the monocycloalkane include cyclopentane and cyclohexane. Examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferable.
As for R ⁵⁶ ′, specific examples of the aliphatic cyclic group containing a hetero atom in the ring structure include formulas (L1) to (L6) and (S1) exemplified in the description of the component (B) described later. ) To (S4) and the like.
As for R ⁵⁶ ′, the hydrogen atom in the aliphatic cyclic group is specifically substituted with a hetero atom, specifically, the hydrogen atom in the aliphatic cyclic group is substituted with an oxygen atom (═O), etc. Is mentioned.

^{-C (= O) -O-R} 6 ', -O-C (= O) -R 7', 'R 6 ^{in' -O-R 8, R 7} ', R 8' are each carbon atoms 1 to 25 linear, branched or cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a linear or branched aliphatic unsaturated hydrocarbon group having 2 to 5 carbon atoms. .
The linear or branched saturated hydrocarbon group has 1 to 25 carbon atoms, preferably 1 to 15 carbon atoms, and more preferably 4 to 10 carbon atoms.
Examples of the linear saturated hydrocarbon group 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, a nonyl group, and a decyl group.
Examples of the branched saturated hydrocarbon group excluding the tertiary alkyl group include, 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, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like can be mentioned.
The linear or branched saturated hydrocarbon group may have a substituent. Examples of the substituent include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (═O), a cyano group, and a carboxy group.
As the alkoxy group as a substituent of the linear or branched saturated hydrocarbon group, 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 preferable, and a methoxy group and an ethoxy group are most preferable.
Examples of the halogen atom as a substituent of the linear or branched saturated hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
As the halogenated alkyl group as a substituent of the linear or branched saturated hydrocarbon group, part or all of the hydrogen atoms of the linear or branched saturated hydrocarbon group are the halogen atoms. And a group substituted with.
The cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in R ⁶ ′, R ⁷ ′, and R ⁸ ′ may be either a polycyclic group or a monocyclic group. A group in which one hydrogen atom has been removed from a polycycloalkane such as bicycloalkane, tricycloalkane, tetracycloalkane, and the like. More specifically, one hydrogen atom was removed from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Group and the like.
The cyclic saturated hydrocarbon group may have a substituent. For example, part of the carbon atoms constituting the ring of the cyclic alkyl group may be substituted with a heteroatom, or the hydrogen atom bonded to the ring of the cyclic alkyl group may be substituted with a substituent. Good.
Examples of the former include one or more hydrogen atoms from a heterocycloalkane in which a part of the carbon atoms constituting the ring of the monocycloalkane or polycycloalkane is substituted with a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Examples include groups other than atoms. The ring structure may have an ester bond (—C (═O) —O—). Specifically, a lactone-containing monocyclic group such as a group obtained by removing one hydrogen atom from γ-butyrolactone, or a group obtained by removing one hydrogen atom from a bicycloalkane, tricycloalkane, or tetracycloalkane having a lactone ring. And other lactone-containing polycyclic groups.
Examples of the substituent in the latter example include the same as those described above as the substituent that the linear or branched alkyl group may have, a lower alkyl group, and the like.
R ⁶ ′, R ⁷ ′, and R ⁸ ′ may be a combination of a linear or branched alkyl group and a cyclic alkyl group.
A combination of a linear or branched alkyl group and a cyclic alkyl group includes a group in which a cyclic alkyl group is bonded as a substituent to a linear or branched alkyl group, and a substituent to the cyclic alkyl group. And a group having a linear or branched alkyl group bonded thereto.
Examples of the linear aliphatic unsaturated hydrocarbon group for R ⁶ ′, R ⁷ ′, and R ⁸ ′ include a vinyl group, a propenyl group (allyl group), and a butynyl group.
Examples of the branched aliphatic unsaturated hydrocarbon group for R ⁶ ′, R ⁷ ′, and R ⁸ ′ include a 1-methylpropenyl group and a 2-methylpropenyl group.
The linear or branched aliphatic unsaturated hydrocarbon group may have a substituent. Examples of the substituent include the same as those described as the substituent that the linear or branched alkyl group may have.
Among R ⁷ ′ and R ⁸ ′, among them, the lithography characteristics and the resist pattern shape are good, so that the linear or branched saturated hydrocarbon group having 1 to 15 carbon atoms, or the carbon number 3-20 cyclic saturated hydrocarbon groups are preferred.

The aryl groups for R ¹ ″ to R ³ ″ are each preferably a phenyl group or a naphthyl group.

Examples of the alkyl group for R ¹ ″ to R ³ ″ include a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. Especially, it is preferable that it is C1-C5 from the point which is excellent in resolution. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, and a decyl group. A methyl group is preferable because it is excellent in resolution and can be synthesized at low cost.

As an alkenyl group of R < ¹ >"-R< ³ >", it is preferable that it is C2-C10, for example, 2-5 are more preferable, and 2-4 are more preferable. Specific examples include a vinyl group, a propenyl group (allyl group), a butynyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group.

When any two of R ¹ ″ to R ³ ″ are bonded to each other to form a ring together with the sulfur atom in the formula, it is preferable that a 3 to 10 membered ring including the sulfur atom is formed, It is particularly preferable to form a 5- to 7-membered ring.
When any two of R ¹ ″ to R ³ ″ are bonded to each other to form a ring together with the sulfur atom in the formula, the remaining one is preferably an aryl group. Examples of the aryl group include the same aryl groups as R ¹ ″ to R ³ ″.

  Specific examples of the cation moiety in the compound represented by the formula (g-c1) include, for example, triphenylsulfonium, (3,5-dimethylphenyl) diphenylsulfonium, (4- (2-adamantoxymethyloxy)- 3,5-dimethylphenyl) diphenylsulfonium, (4- (2-adamantoxymethyloxy) phenyl) diphenylsulfonium, (4- (tert-butoxycarbonylmethyloxy) phenyl) diphenylsulfonium, (4- (tert-butoxycarbonyl) Methyloxy) -3,5-dimethylphenyl) diphenylsulfonium, (4- (2-methyl-2-adamantyloxycarbonylmethyloxy) phenyl) diphenylsulfonium, (4- (2-methyl-2-adamantyloxycarbonylmethyl) (Oxy) -3,5-dimethylphenyl) diphenylsulfonium, tri (4-methylphenyl) sulfonium, dimethyl (4-hydroxynaphthyl) sulfonium, monophenyldimethylsulfonium, diphenylmonomethylsulfonium, (4-methylphenyl) diphenylsulfonium, 4-methoxyphenyl) diphenylsulfonium, tri (4-tert-butyl) phenylsulfonium, diphenyl (1- (4-methoxy) naphthyl) sulfonium, di (1-naphthyl) phenylsulfonium, 1-phenyltetrahydrothiophenium, 1 -(4-methylphenyl) tetrahydrothiophenium, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium, 1- (4-methoxynaphthalen-1-yl Tetrahydrothiophenium, 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium, 1-phenyltetrahydrothiopyranium, 1 -(4-hydroxyphenyl) tetrahydrothiopyranium, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiopyranium, 1- (4-methylphenyl) tetrahydrothiopyranium and the like can be mentioned.

  Specific examples of the cation moiety in the compound represented by the formula (g-c1) include those shown below.

［式中、ｇ１は繰返し数を示し、１〜５の整数である。］

[Wherein g1 represents the number of repetitions and is an integer of 1 to 5. ]

［式中、ｇ２、ｇ３は繰返し数を示し、ｇ２は０〜２０の整数であり、ｇ３は０〜２０の整数である。］

[Wherein g2 and g3 represent the number of repetitions, g2 is an integer of 0 to 20, and g3 is an integer of 0 to 20. ]

In the formula (g-c2), R ⁵ ″ and R ⁶ ″ each independently represents an aryl group, an alkyl group or an alkenyl group which may have a substituent.
Among R ⁵ "~R ^6", it is preferable that at least one is an aryl ^group, and particularly preferably none of R 5 "~R ^6" are aryl groups.
As the aryl group for R ⁵ ″ to R ⁶ ″, the same as the aryl groups for R ¹ ″ to R ³ ″ can be used.
Examples of the alkyl group for R ⁵ ″ to R ⁶ ″ include the same as the alkyl group for R ¹ ″ to R ³ ″.
Examples of the alkenyl group for R ⁵ ″ to R ⁶ ″ include the same alkenyl groups for R ¹ ″ to R ³ ″.
Among these, it is most preferable that all of R ⁵ ″ to R ⁶ ″ are phenyl groups.
Specific examples of the cation moiety represented by the formula (g-c2) include diphenyliodonium and bis (4-tert-butylphenyl) iodonium.

Moreover, as a suitable thing of the organic cation of M ^<+>, the cation represented by the following general formula (g-c3) or general formula (g-c4) is mentioned, for example.

［式中、Ｒ^８１〜Ｒ^８６はそれぞれ独立してアルキル基、アセチル基、アルコキシ基、カルボキシ基、水酸基またはヒドロキシアルキル基であり；ｎ_１〜ｎ_５はそれぞれ独立して０〜３の整数であり、ｎ_６は０〜２の整数である。］

[Wherein R ^{81 to} R ⁸⁶ are each independently an alkyl group, acetyl group, alkoxy group, carboxy group, hydroxyl group or hydroxyalkyl group; n _{1 to} n ₅ are each independently an integer of 0 to 3; There, _{n 6} is an integer of 0-2. ]

In R ^{81 to} R ⁸⁶ , the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group, and a methyl group, an ethyl group, a propyl group, an isopropyl group, n A butyl group or a tert-butyl group is particularly preferable.
The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a linear or branched alkoxy group, and particularly preferably a methoxy group or an ethoxy group.
The hydroxyalkyl group is preferably a group in which one or more hydrogen atoms in the alkyl group are substituted with a hydroxy group, and examples thereof include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
When the symbols n _{1 to} n ₆ attached to R ^{81 to} R ⁸⁶ are integers of 2 or more, the plurality of R ^{81 to} R ⁸⁶ may be the same or different.
n ₁ is preferably 0 to 2, more preferably 0 or 1, and still more preferably 0.
n ₂ and n ₃ are preferably each independently 0 or 1, more preferably 0.
n ₄ is preferably 0 to 2, more preferably 0 or 1.
n ₅ is preferably 0 or 1, more preferably 0.
n ₆ is preferably 0 or 1, more preferably 1.

  Preferable examples of the cation represented by the formula (g-c3) or the formula (g-c4) include those shown below.

Moreover, as a suitable thing of the organic cation of M ^<+>, the cation represented by the following general formula (g-c5) or general formula (g-c6) is mentioned, for example.

In formulas (g-c5) and (g-c6), R ⁹ and R ¹⁰ are each independently a phenyl group, a naphthyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group which may have a substituent. Group, hydroxyl group. Examples of the substituent include a substituent in the substituted aryl group exemplified in the description of the aryl group of R ¹ ″ to R ³ ″ (an alkyl group, an alkoxy group, an alkoxyalkyloxy group, an alkoxycarbonylalkyloxy group, a halogen atom). Atom, hydroxyl group, oxo group (═O), aryl group, —C (═O) —O—R ⁶ ′, —O—C (═O) —R ⁷ ′, —O—R ⁸ ′, the above general formula ^{: -O-R 55 -C (=} O) based on ^{R 56} is replaced by ^{R 56} 'in the ^{-O-R 56,} etc.) to be similar.
R ⁴ ′ is an alkylene group having 1 to 5 carbon atoms.
u is an integer of 1 to 3, and 1 or 2 is most preferable.
Preferable examples of the cation represented by the formula (b-7) or the formula (b-8) include those shown below. In the formula, R ^C represents a substituent (alkyl group, alkoxy group, alkoxyalkyloxy group, alkoxycarbonylalkyloxy group, halogen atom, hydroxyl group, oxo group (═O) exemplified in the description of the substituted aryl group. An aryl group, —C (═O) —O—R ⁶ ′, —O—C (═O) —R ⁷ ′, —O—R ⁸ ′).

Among these, as the organic cation of M ⁺ , when blended in a resist composition, better lithography characteristics and a resist pattern shape can be easily obtained. Therefore, the organic cation represented by the general formula (g-c1) is used. Most preferred are cations.

Specifically, as the component (G), the compound (Gm-1) represented by the following general formula (g1-1), the compound (Gm-2) represented by the general formula (g2-1), and the general formula Examples thereof include low-molecular compound components such as the compound (Gm-3) represented by (g1-2) and the compound (Gm-4) represented by the general formula (g2-2).
Further, as the component (G), a resin component having a structural unit (g ′) derived from at least one compound selected from the group consisting of the compound (Gm-1) and the compound (Gm-2), etc. Also mentioned.

［式（ｇ１−１）中、Ｒ^Ｐ１は下記の一般式（Ｉ）又は一般式（ＩＩ）のいずれかで表される１価の基である。Ｒ^２は単結合又は−Ｃ（＝Ｏ）−Ｏ−基である。但し、Ｒ^２が単結合の場合、式中のＮ⁻が−Ｃ（＝Ｏ）−基に結合するものは（Ｇ）成分には含まれないものとする。Ｒ^３はフッ素原子で置換されていてもよい、炭素数１〜１０の直鎖状若しくは分岐鎖状の１価の炭化水素基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基である。式（ｇ２−１）中、Ｒ^Ｐ２は下記一般式（Ｉ）〜（ＩＩＩ）のいずれかで表される１価の基である。Ｘはそれぞれ独立に単結合又は２価の連結基を示す。Ｍ^＋はそれぞれ独立に有機カチオンである。］

[In formula (g1-1), R ^P1 is a monovalent group represented by any of the following general formula (I) or general formula (II). R ² is a single bond or a —C (═O) —O— group. However, if R ² is a single bond, N in the formula ^- is -C (= O) - those that bind to groups and are not included in the component (G). R ³ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. In formula (g2-1), R ^P2 is a monovalent group represented by any of the following general formulas (I) to (III). X each independently represents a single bond or a divalent linking group. M ⁺ is each independently an organic cation. ]

［式（Ｉ）〜（ＩＩＩ）中、Ｒ^ａは水素原子、炭素数１〜５のアルキル基、又は炭素数１〜５のハロゲン化アルキル基であり、Ｒ^ｎは水素原子又は炭素数１〜５のアルキル基である。］

[In formulas (I) to (III), R ^a is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and R ⁿ is a hydrogen atom or 1 to 5 carbon atoms. 5 alkyl groups. ]

［式（ｇ１−２）中、Ｒ^１はフッ素原子、ヒドロキシ基、−Ｏ−Ｒ^１０基、−ＮＨ−Ｃ（＝Ｏ）−Ｒ^１０基、−Ｏ−Ｃ（＝Ｏ）−Ｒ^１０基、又は−Ｃ（＝Ｏ）−Ｏ−Ｒ^１０基（但し、Ｒ^１０は炭素数１〜１０の直鎖状若しくは分岐鎖状の１価のアルキル基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基を示す。）で置換されていてもよい、炭素数１〜２０の直鎖状若しくは分岐鎖状の１価の炭化水素基、炭素数３〜２０の環状の１価の炭化水素基、炭素数３〜２０の環状の部分構造を有する１価の炭化水素基、又は水素原子である。Ｒ^２は単結合又は−Ｃ（＝Ｏ）−Ｏ−基である。但し、Ｒ^２が単結合の場合、式中のＮ⁻が−Ｃ（＝Ｏ）−基に結合するものは（Ｇ）成分には含まれないものとする。Ｒ^３はフッ素原子で置換されていてもよい、炭素数１〜１０の直鎖状若しくは分岐鎖状の１価の炭化水素基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基である。式（ｇ２−２）中、Ｒ^４はフッ素原子、ヒドロキシ基、−Ｏ−Ｒ^１０基、−Ｏ−Ｃ（＝Ｏ）−Ｒ^１０基、又は−Ｃ（＝Ｏ）−Ｏ−Ｒ^１０基（但し、Ｒ^１０は炭素数１〜１０の直鎖状若しくは分岐鎖状の１価のアルキル基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基を示す。）で置換されていてもよい、炭素数１〜２０の直鎖状若しくは分岐鎖状の１価のアルキル基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基である。Ｍ^＋はそれぞれ独立に有機カチオンである。］

[In Formula (g1-2), R ¹ is a fluorine atom, a hydroxy group, —O—R ¹⁰ group, —NH—C (═O) —R ¹⁰ group, —O—C (═O) —R ¹⁰ group. Or -C (= O) -O-R ¹⁰ group (where R ¹⁰ is a linear or branched monovalent alkyl group having 1 to ¹⁰ carbon atoms, or cyclic monovalent group having 3 to 20 carbon atoms) Or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, which may be substituted with a linear or branched chain group having 1 to 20 carbon atoms. A monovalent hydrocarbon group, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom. R ² is a single bond or a —C (═O) —O— group. However, if R ² is a single bond, N in the formula ^- is -C (= O) - those that bind to groups and are not included in the component (G). R ³ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. In formula (g2-2), R ⁴ represents a fluorine atom, a hydroxy group, —O—R ¹⁰ group, —O—C (═O) —R ¹⁰ group, or —C (═O) —O—R ¹⁰ group. (However, R ¹⁰ is a linear or branched monovalent alkyl group having 1 to ¹⁰ carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. A monovalent hydrocarbon group having a partial structure.) Which may be substituted with a linear or branched monovalent alkyl group having 1 to 20 carbon atoms or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. M ⁺ is each independently an organic cation. ]

[Compound (Gm-1)]
The compound (Gm-1) is a compound represented by the general formula (g1-1).
In formula (g1-1), R ^P1 is a monovalent group represented by any one of the above general formula (I) or general formula (II).
In formulas (I) and (II), R ^a is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms in ^Ra is preferably a linear or branched alkyl group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, or an isobutyl group. Tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. Halogenated alkyl group of 1 to 5 carbon atoms in R ^a will, a part or all of the hydrogen atoms of the "alkyl group having 1 to 5 carbon atoms in R ^a", are substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. As R ^a , a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms is more preferable, and a hydrogen atom or a methyl group is particularly preferable in terms of industrial availability.
Wherein (II), ^{R n} is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In formula (g1-1), X represents a single bond or a divalent linking group.
The divalent linking group in X is not particularly limited, and preferred examples include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.
The hydrocarbon group having “substituent” means that part or all of the hydrogen atoms in the hydrocarbon group are substituted with a substituent (a group or atom other than a hydrogen atom).
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.
The aliphatic hydrocarbon group as the divalent hydrocarbon group in X may be saturated or unsaturated, and is usually preferably saturated.
More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. 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 preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (═O).

Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic 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 those described above.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
The alicyclic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

The aromatic hydrocarbon group as the divalent hydrocarbon group in X 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, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. . However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring of the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; a part of carbon atoms constituting the aromatic hydrocarbon ring is hetero Aromatic heterocycles substituted with atoms; and the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.
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) ) In which one of the hydrogen atoms is substituted with an alkylene group (for example, arylalkyl such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) Group in which one hydrogen atom is further removed from the aryl group in the group); and the like. The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
The aromatic hydrocarbon group may or may not have a substituent. For example, a hydrogen atom bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxygen atom (═O).
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group. Most preferred is an ethoxy group.
Examples of the halogen atom as a substituent for the aromatic hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms.

The hetero atom in the “divalent linking group containing a hetero atom” of X is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
As the divalent linking group containing a hetero atom, —O—, —C (═O) —O—, —C (═O) —, —O—C (═O) —O—, —C (= O) —NH—, —NH— (H may be substituted with a substituent such as an alkyl group, an acyl group, etc.), —S—, —S (═O) ₂ —, —S (═O) _{2 -O -, - NH-C} (= O) -, = N-, the formula ^{-Y 21 -O-Y 22 -,} - [Y 21 -C (= O) -O] m '-Y 22 - Or a group represented by —Y ²¹ —O—C (═O) —Y ²² —, wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group optionally having a substituent. O is an oxygen atom, and m ′ is an integer of 0 to 3. ] Etc. are mentioned.
When X is —NH—, H may be substituted with a substituent such as an alkyl group or an aryl group (aromatic group). The substituent (alkyl group, aryl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Formula ^{-Y 21 -O-Y 22 -,} - [Y 21 -C (= O) -O] m '-Y 22 - or ^{-Y 21 -O-C (= O} ) -Y 22 - ^{In, Y 21} And Y ²² are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same groups as those described above as the “divalent hydrocarbon group optionally having substituent (s)” in X.
Y ²¹ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. preferable.
Y ²² is preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, 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, 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) —O—Y ²² —. The group is particularly preferred. Among these, a group represented by the formula — (CH ₂ ) _{a ′} —C (═O) —O— (CH ₂ ) _{b ′} — is preferable. In the formula, a ′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1. b ′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1.
Examples of the divalent linking group containing a hetero atom, a linear group containing an oxygen atom as a hetero atom, for example, a group containing an ether bond or an ester bond, are preferred, the formula -Y 21 ^-O-Y 22 ^-, A group represented by — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² — or —Y ²¹ —O—C (═O) —Y ²² — is more preferable.

  Among these, the divalent linking group for X is particularly preferably a linear or branched alkylene group, a divalent alicyclic hydrocarbon group, or a divalent linking group containing a hetero atom. . Among these, a linear or branched alkylene group and a divalent alicyclic hydrocarbon group are preferable, and a linear alkylene group and a divalent alicyclic hydrocarbon group are more preferable.

Wherein ^(g1-1), R 2, ^{R 3} and ^{M +} is, the formula (g1) is ^R 2, ^{R 3} and ^{M +} respectively similar in.

  Specific examples of the compound (Gm-1) are shown below.

[Compound (Gm-2)]
The compound (Gm-2) is a compound represented by the above general formula (g2-1).
In formula (g2-1), R ^P2 is a monovalent group represented by any one of the general formulas (I) to (III). R ^a and R ⁿ are the same as described above.
Wherein (g2-1), X and ^{M +} are the same as the formula (g1-1) X and ^{M +} respectively in. When ^RP2 is a monovalent group represented by the general formula (III), the divalent linking group in X is preferably a divalent aromatic hydrocarbon group which may have a substituent. An arylene group is more preferable.

  Below, the specific example of a compound (Gm-2) is illustrated.

[Compound (Gm-3)]
The compound (Gm-3) is a compound represented by the general formula (g1-2).
In formula (g1-2), R ¹ represents a fluorine atom, a hydroxy group, —O—R ¹⁰ group, —NH—C (═O) —R ¹⁰ group, —O—C (═O) —R ¹⁰ group. Or -C (= O) -O-R ¹⁰ group (where R ¹⁰ is a linear or branched monovalent alkyl group having 1 to ¹⁰ carbon atoms, or cyclic monovalent group having 3 to 20 carbon atoms) Or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, which may be substituted with a linear or branched chain group having 1 to 20 carbon atoms. A monovalent hydrocarbon group, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom.
The linear or branched monovalent alkyl group for R ¹⁰ has 1 to 10 carbon atoms, preferably 1 to 5 and more preferably 1 to 3. As the linear or branched monovalent alkyl group in R ¹⁰ , methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group Tert-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.
In R ¹⁰ , a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms and a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms are represented by R ³ in the formula (g1), This is the same as a monovalent hydrocarbon group having a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms and a cyclic partial structure having 3 to 20 carbon atoms.

The linear or branched monovalent hydrocarbon group for R ¹ has 1 to 20 carbon atoms, preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 5. However, the carbon number does not include the carbon number in the substituent.
Examples of the linear or branched monovalent hydrocarbon group in R ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl. Group, tert-butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, undecyl group, dodecyl group, tridecyl group I-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, i-hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.
A cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms and a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms in R ¹ are represented by R ³ in the formula (g1), Examples thereof are the same as those of a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms and a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. In addition, the cyclic hydrocarbon group may be an aromatic hydrocarbon group. The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 5 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic hydrocarbon group include a hydrogen atom from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. One aryl group removed; arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group; the aryl group or arylalkyl group A group in which one or more hydrogen atoms have been removed. The number of carbon atoms in the alkyl chain in the arylalkyl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

The aromatic hydrocarbon group is a fluorine atom, a hydroxy group, -O-R ¹⁰ group, -NH-C (= O) -R ¹⁰ group, -O-C (= O) -R ¹⁰ group, or -C. In addition to the (= O) -O-R ¹⁰ group, it may have a substituent. For example, a part of carbon atoms constituting the aromatic ring of the aromatic hydrocarbon group may be substituted with a hetero atom, and the hydrogen atom bonded to the aromatic ring of the aromatic hydrocarbon group is substituted with the substituent. May be.
Examples of the former include heteroaryl groups in which some of the carbon atoms constituting the ring of the aryl group are substituted with heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and aromatic hydrocarbons in the arylalkyl groups. Examples include heteroarylalkyl groups in which some of the carbon atoms constituting the ring are substituted with the above heteroatoms.
Examples of the substituent of the aromatic hydrocarbon group in the latter example include an alkyl group, a halogen atom other than a fluorine atom, a halogenated alkyl group, and an oxygen atom (═O).
The alkyl group as a substituent of the aromatic hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. preferable.
Examples of the halogen atom as a substituent for the aromatic hydrocarbon group include a chlorine atom, a bromine atom, and an iodine atom. Examples of the halogenated alkyl group as the substituent for the aromatic hydrocarbon group include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with chlorine, bromine or iodine atoms.

Wherein ^(g1-2), R 2, ^{R 3} and ^{M +} is, the formula (g1) is ^R 2, ^{R 3} and ^{M +} respectively similar in.

  Below, the specific example of a compound (Gm-3) is illustrated.

[Compound (Gm-4)]
The compound (Gm-4) is a compound represented by the general formula (g2-2).
In formula (g2-2), R ⁴ represents a fluorine atom, a hydroxy group, —O—R ¹⁰ group, —O—C (═O) —R ¹⁰ group, or —C (═O) —O—R ^10. A group wherein R ¹⁰ is a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms A monovalent hydrocarbon group having a partial structure of 1), a linear or branched monovalent alkyl group having 1 to 20 carbon atoms and a cyclic group having 3 to 20 carbon atoms. Or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, which is the same as R ¹ in the formula (g1-2).
Wherein (G2-2), ^{M +} is the same as ^{M +} in the formula (g1).

  Below, the specific example of a compound (Gm-4) is illustrated.

The low molecular compound components such as the compound (Gm-1), the compound (Gm-2), the compound (Gm-3) and the compound (Gm-4) described above are added together with the base material component in the resist composition. It can be used as an agent.
In the resist composition, the component (G) as an additive may be used alone or in combination of two or more.
The component (G) as an additive includes at least one compound selected from the group consisting of the compound (Gm-1), the compound (Gm-2), the compound (Gm-3), and the compound (Gm-4). It is preferable.
In the resist composition, the content of the component (G) as an additive is preferably 0.5 to 20 parts by mass, and 1.0 to 15 parts by mass with respect to 100 parts by mass of the base component of the resist composition. More preferred is 1.5 to 10 parts by mass.
Since the content of the component (G) is within the above range, the effect of acid diffusion control is further enhanced, and the contrast between the unexposed area and the exposed area is improved, so that the lithography characteristics or the resist pattern shape is further improved. It becomes good.

[Resin Component Having Structural Unit (g ′)]
The structural unit (g ′) is a structural unit derived from at least one compound selected from the group consisting of the compound (Gm-1) and the compound (Gm-2).
Hereinafter, among the structural units (g ′), the structural unit derived from the compound (Gm-1) is the structural unit (g′1), and the structural unit derived from the compound (Gm-2) is the structural unit (g ′). Also called 2).
The “structural unit derived from the compound (Gm-1)” and the “structural unit derived from the compound (Gm-2)” as used herein are configured by cleavage of the ethylenic double bond of each compound. Means a structural unit.

・ Structural unit (g'1)
The structural unit (g′1) is a structural unit represented by the following general formula (Gm-1-I) or general formula (Gm-1-II).

［式中、Ｒ^ａ，Ｒ^ｎ、Ｒ^２、Ｒ^３、Ｘ及びＭ^＋はそれぞれ前記と同様である。］

[Wherein, R ^a , R ⁿ , R ² , R ³ , X and M ⁺ are the same as defined above. ]

In the formula (Gm-1-I), R ^a is preferably ^a hydrogen atom or a methyl group.
X is preferably a linear, branched or cyclic alkylene group, and more preferably a linear or cyclic alkylene group.
R ² is preferably a single bond.
R ³ is preferably a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and is a linear or branched chain having 1 to 10 carbon atoms or It is more preferably a branched monovalent fluorinated alkyl group.
M ⁺ is preferably an organic cation represented by the general formula (g-c1).

In the formula (Gm-1-II), R ^a is preferably ^a hydrogen atom or a methyl group.
R ⁿ is preferably a hydrogen atom or a methyl group.
X is preferably a linear, branched or cyclic alkylene group, and more preferably a linear or cyclic alkylene group. R ² is preferably a single bond.
R ³ is preferably a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and is a linear or branched chain having 1 to 10 carbon atoms or It is more preferably a branched monovalent fluorinated alkyl group.
M ⁺ is preferably an organic cation represented by the general formula (g-c1).

Specific examples of the structural unit (g′1) are illustrated below. In the following formula, R ^a ′ represents a hydrogen atom, a methyl group or a trifluoromethyl group.

・ Unit (g'2)
The structural unit (g′2) is a structural unit represented by the following general formula (Gm-2-I), general formula (Gm-2-II), or general formula (Gm-2-III).

［式中、Ｒ^ａ，Ｒ^ｎ、Ｘ及びＭ^＋はそれぞれ前記と同様である。］

[Wherein, R ^a , R ⁿ , X and M ⁺ are the same as defined above. ]

In the formula (Gm-2-I), R ^a is preferably ^a hydrogen atom or a methyl group.
X is preferably a linear, branched or cyclic alkylene group, and more preferably a linear or cyclic alkylene group.
M ⁺ is preferably an organic cation represented by the general formula (g-c1).

In the formula (Gm-2-II), R ^a is preferably ^a hydrogen atom or a methyl group.
R ⁿ is preferably a hydrogen atom or a methyl group.
X is preferably a linear, branched or cyclic alkylene group, and more preferably a linear or cyclic alkylene group.
M ⁺ is preferably an organic cation represented by the general formula (g-c1).

In the formula (Gm-2-III), R ^a is preferably ^a hydrogen atom or a methyl group. X is preferably a single bond or an arylene group which may have a substituent, and more preferably a single bond.
M ⁺ is preferably an organic cation represented by the general formula (g-c1).

Specific examples of the structural unit (g′2) are illustrated below. In the following formula, R ^a ′ represents a hydrogen atom, a methyl group or a trifluoromethyl group. m ″ is 0 or 1.

The structural unit (g ′) contained in the resin component may be used alone or in combination of two or more.
In the resin component having the structural unit (g ′), the proportion of the structural unit (g ′) is preferably 0.5 to 30 mol%, and 1 to 15 mol% with respect to all the structural units constituting the resin component. More preferably, 1-10 mol% is further more preferable.
By making the proportion of the structural unit (g ′) within the above range, the effect of acid diffusion control is further enhanced, and the contrast between the unexposed part and the exposed part is improved, so that the lithography characteristics or the resist pattern shape is improved. Better.

-Other structural unit The resin component which has a structural unit (g ') may have other structural units other than a structural unit (g').
Such other structural unit is not particularly limited as long as it is a structural unit that is not classified into the structural unit (g ′) described above, such as for ArF excimer laser, for KrF excimer laser (preferably for ArF excimer laser), Many things conventionally known as what is used for resin for resists can be used.
Such other structural unit is a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and the acid decomposition whose polarity is increased by the action of an acid It is preferable to have a structural unit (structural unit (a1) described later) containing a sex group. In particular, the copolymer having the structural unit (a1) and the above-described structural unit (g ′) can be used as a base component (component (A)) of the resist composition.

In the resist composition of the present invention, the resin component having the structural unit (g ′) is a copolymer having the structural unit (g ′) and the structural unit (a1), that is, the base material component ((A)). The component (G) is preferred as the component.
In addition to the structural unit (g ′) and the structural unit (a1), the resin component having the structural unit (g ′) as the base material component (component (A)) was further bonded to the α-position carbon atom. A structural unit derived from an acrylate ester optionally substituted with a hydrogen atom, a structural unit (a0) containing a —SO ₂ — containing cyclic group, and hydrogen bonded to the α-position carbon atom A structural unit derived from an acrylate ester optionally substituted with a substituent having at least one structural unit selected from the group consisting of the structural unit (a2) containing a lactone-containing cyclic group Is preferred.
In addition to the structural unit (g ′) and the structural unit (a1), the resin component having the structural unit (g ′) as the base material component (component (A)) or the structural unit (a0) and In addition to at least one of the structural unit (a2), the structural unit (a1), and the structural unit (g ′), the hydrogen atom bonded to the α-position carbon atom may be further substituted with a substituent. A structural unit derived from an ester and having a structural unit (a3) containing a polar group-containing aliphatic hydrocarbon group is preferred.
Details of the structural units (a1) to (a3) and (a0) will be described later.

  In the resist composition, the resin component having the structural unit (g ′) may be used alone or in combination of two or more.

<(H) component>
The component (H) is a compound having a monovalent group represented by the following general formula (h1) or a monovalent group represented by the general formula (h2).

［式（ｈ１）中、Ｒ^６は単結合又は−Ｃ（＝Ｏ）−Ｏ−基である。Ｒ^７はフッ素原子で置換されていてもよい、炭素数１〜１０の直鎖状若しくは分岐鎖状の１価の炭化水素基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基である。］

[In the formula (h1), R ⁶ represents a single bond or a —C (═O) —O— group. R ⁷ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. ]

In the formula (h1), R ⁶ is a single bond or a —C (═O) —O— group, and preferably a single bond.
In R ⁷ , a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic partial structure having 3 to 20 carbon atoms The monovalent hydrocarbon group having a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms or a cyclic group having 3 to 20 carbon atoms in R ³ in the formula (g1). The same applies to a monovalent hydrocarbon group and a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms.

Specifically, as the component (H), a compound (Hm-1) represented by the following general formula (h1-1), a compound (Hm-2) represented by the general formula (h2-1), a general formula Low molecular compound components such as the compound (Hm-3) represented by (h1-2) and the compound (Hm-4) represented by the general formula (h2-2) can be mentioned.
The component (H) includes a resin component having a structural unit (h ′) derived from at least one compound selected from the group consisting of the compound (Hm-1) and the compound (Hm-2). Also mentioned.

［式（ｈ１−１）中、Ｒ^Ｐ１は前記の一般式（Ｉ）又は一般式（ＩＩ）のいずれかで表される１価の基である。Ｒ^６は単結合又は−Ｃ（＝Ｏ）−Ｏ−基である。Ｒ^７はフッ素原子で置換されていてもよい、炭素数１〜１０の直鎖状若しくは分岐鎖状の１価の炭化水素基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基である。式（ｈ２−１）中、Ｒ^Ｐ２は前記一般式（Ｉ）〜（ＩＩＩ）のいずれかで表される１価の基である。Ｘはそれぞれ独立に単結合又は２価の連結基を示す。］

[In formula (h1-1), R ^P1 is a monovalent group represented by either the general formula (I) or the general formula (II). R ⁶ is a single bond or a —C (═O) —O— group. R ⁷ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. In the formula (h2-1), R ^P2 is a monovalent group represented by any one of the general formulas (I) to (III). X each independently represents a single bond or a divalent linking group. ]

［式（ｈ１−２）中、Ｒ^５はフッ素原子、ヒドロキシ基、−Ｏ−Ｒ^１０基、−ＮＨ−Ｃ（＝Ｏ）−Ｒ^１０基、−Ｏ−Ｃ（＝Ｏ）−Ｒ^１０基、又は−Ｃ（＝Ｏ）−Ｏ−Ｒ^１０基（但し、Ｒ^１０は炭素数１〜１０の直鎖状若しくは分岐鎖状の１価のアルキル基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基を示す。）で置換されていてもよい、炭素数１〜２０の直鎖状若しくは分岐鎖状の１価の炭化水素基、炭素数３〜２０の環状の１価の炭化水素基、炭素数３〜２０の環状の部分構造を有する１価の炭化水素基、又は水素原子である。Ｒ^６は単結合又は−Ｃ（＝Ｏ）−Ｏ−基である。Ｒ^７はフッ素原子で置換されていてもよい、炭素数１〜１０の直鎖状若しくは分岐鎖状の１価の炭化水素基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基である。式（ｈ２−２）中、Ｒ^８はフッ素原子、ヒドロキシ基、−Ｏ−Ｒ^１０基、−Ｏ−Ｃ（＝Ｏ）−Ｒ^１０基、又は−Ｃ（＝Ｏ）−Ｏ−Ｒ^１０基（但し、Ｒ^１０は炭素数１〜１０の直鎖状若しくは分岐鎖状の１価のアルキル基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基を示す。）で置換されていてもよい、炭素数１〜２０の直鎖状若しくは分岐鎖状の１価のアルキル基、炭素数３〜２０の環状の１価の炭化水素基、又は炭素数３〜２０の環状の部分構造を有する１価の炭化水素基である。］

[In the formula (h1-2), R ⁵ represents a fluorine atom, a hydroxy group, —O—R ¹⁰ group, —NH—C (═O) —R ¹⁰ group, —O—C (═O) —R ¹⁰ group. Or -C (= O) -O-R ¹⁰ group (where R ¹⁰ is a linear or branched monovalent alkyl group having 1 to ¹⁰ carbon atoms, or cyclic monovalent group having 3 to 20 carbon atoms) Or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, which may be substituted with a linear or branched chain group having 1 to 20 carbon atoms. A monovalent hydrocarbon group, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom. R ⁶ is a single bond or a —C (═O) —O— group. R ⁷ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. In the formula (h2-2), R ⁸ is a fluorine atom, a hydroxy group, —O—R ¹⁰ group, —O—C (═O) —R ¹⁰ group, or —C (═O) —O—R ¹⁰ group. (However, R ¹⁰ is a linear or branched monovalent alkyl group having 1 to ¹⁰ carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. A monovalent hydrocarbon group having a partial structure.) Which may be substituted with a linear or branched monovalent alkyl group having 1 to 20 carbon atoms or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. ]

[Compound (Hm-1)]
The compound (Hm-1) is a compound represented by the general formula (h1-1).
In the formula (h1-1), R ^P1 is a monovalent group represented by either the general formula (I) or the general formula (II).
In formula (h1-1), R ⁶ , R ⁷ and X are the same as R ² , R ³ and X in formula (g1-1), respectively.
As a specific example of the compound (Hm-1), as shown below as an example, “—N ⁻ —” in the anion moiety of the compound mentioned in the compound (Gm-1) is replaced with “—NH—”. And the like.

[Compound (Hm-2)]
The compound (Hm-2) is a compound represented by the general formula (h2-1).
In formula (h2-1), R ^P2 is a monovalent group represented by any one of the general formulas (I) to (III).
In formula (h2-1), X is the same as X in the formula (g2-1).
Specific examples of the compound (Hm-2) include compounds in which “—COO ⁻ ” in the anion moiety of the compound mentioned in the compound (Gm-2) is replaced with “—COOH”.

[Compound (Hm-3)]
The compound (Hm-3) is a compound represented by the general formula (h1-2).
In formula (h1-2), R ⁵ is a fluorine atom, a hydroxy group, —O—R ¹⁰ group, —NH—C (═O) —R ¹⁰ group, —O—C (═O) —R ¹⁰ group. Or -C (= O) -O-R ¹⁰ group (where R ¹⁰ is a linear or branched monovalent alkyl group having 1 to ¹⁰ carbon atoms, or cyclic monovalent group having 3 to 20 carbon atoms) Or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, which may be substituted with a linear or branched chain group having 1 to 20 carbon atoms. A monovalent hydrocarbon group, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom, The same as R ^{1 in} g1-2).
Wherein (H1-2), ^{R 6} and ^{R 7} are each similar to the ^{R 6} and ^{R 7} in the formula (h1-1).
As specific examples of the compound (Hm-3), as shown below as an example, “—N ⁻ —” in the anion moiety of the compound exemplified in the compound (Gm-3) is represented by “—NH—. And the like.

[Compound (Hm-4)]
The compound (Hm-4) is a compound represented by the general formula (h2-2).
In formula (h2-2), R ⁸ represents a fluorine atom, a hydroxy group, —O—R ¹⁰ group, —O—C (═O) —R ¹⁰ group, or —C (═O) —O—R ^10. A group wherein R ¹⁰ is a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms A monovalent hydrocarbon group having a partial structure of 1), a linear or branched monovalent alkyl group having 1 to 20 carbon atoms and a cyclic group having 3 to 20 carbon atoms. Or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, which is the same as R ⁵ in the formula (h1-2).
Hereinafter, specific examples of the compound (Hm-4), as shown below as an example, the anion moiety of the compounds listed in the compound (Gm-4) "-COO ^-" to "-COOH" Examples include substituted compounds.

The low molecular compound components such as the compound (Hm-1), the compound (Hm-2), the compound (Hm-3) and the compound (Hm-4) described above are added together with the base material component in the resist composition. It can be used as an agent.
In the resist composition, the component (H) as the additive may be used alone or in combination of two or more.
The component (H) as an additive includes at least one compound selected from the group consisting of the compound (Hm-1), the compound (Hm-2), the compound (Hm-3), and the compound (Hm-4). It is preferable.
In the resist composition, the content of the component (H) as an additive is preferably 0.1 to 15 parts by mass, and 0.3 to 7 parts by mass with respect to 100 parts by mass of the base component of the resist composition. More preferably, 0.5-5 mass parts is especially preferable.
When the content of the component (H) is within the above range, the dimensional variation of the resist pattern due to the influence of time is further suppressed.

[Resin component having structural unit (h ′)]
The structural unit (h ′) is a structural unit derived from at least one compound selected from the group consisting of the compound (Hm-1) and the compound (Hm-2).
Hereinafter, among the structural units (h ′), the structural unit derived from the compound (Hm-1) is the structural unit (h′1), and the structural unit derived from the compound (Hm-2) is the structural unit (h ′). Also called 2).
The “structural unit derived from the compound (Hm-1)” and the “structural unit derived from the compound (Hm-2)” as used herein are configured by cleavage of the ethylenic double bond of each compound. Means a structural unit.

・ Unit (h'1)
The structural unit (h′1) is a structural unit represented by the following general formula (Hm-1-I) or general formula (Hm-1-II).

［式中、Ｒ^ａ，Ｒ^ｎ、Ｒ^６、Ｒ^７及びＸはそれぞれ前記と同様である。］

[Wherein, R ^a , R ⁿ , R ⁶ , R ⁷ and X are the same as defined above. ]

In the formula (Hm-1-I), R ^a is preferably ^a hydrogen atom or a methyl group.
X is preferably a linear, branched or cyclic alkylene group, and more preferably a linear or cyclic alkylene group.
R ⁶ is preferably a single bond.
R ⁷ is preferably a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and a linear or branched group having 1 to 10 carbon atoms or It is more preferably a branched monovalent fluorinated alkyl group.

In the formula (Hm-1-II), R ^a is preferably ^a hydrogen atom or a methyl group.
R ⁿ is preferably a hydrogen atom or a methyl group.
X is preferably a linear, branched or cyclic alkylene group, and more preferably a linear or cyclic alkylene group.
R ⁶ is preferably a single bond.
R ⁷ is preferably a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and a linear or branched group having 1 to 10 carbon atoms or It is more preferably a branched monovalent fluorinated alkyl group.

Specific examples of the structural unit (h′1) are illustrated below. In the following formula, R ^a ′ represents a hydrogen atom, a methyl group or a trifluoromethyl group.

・ Unit (h'2)
The structural unit (h′2) is a structural unit represented by the following general formula (Hm-2-I), general formula (Hm-2-II), or general formula (Hm-2-III).

［式中、Ｒ^ａ，Ｒ^ｎ及びＸはそれぞれ前記と同様である。］

[Wherein, R ^a , R ⁿ and X are the same as defined above. ]

In the formula (Hm-2-I), R ^a is preferably ^a hydrogen atom or a methyl group.
X is preferably a linear, branched or cyclic alkylene group, and more preferably a linear or cyclic alkylene group.

In the formula (Hm-2-II), R ^a is preferably ^a hydrogen atom or a methyl group.
R ⁿ is preferably a hydrogen atom or a methyl group.
X is preferably a linear, branched or cyclic alkylene group, and more preferably a linear or cyclic alkylene group.

In the formula (Hm-2-III), R ^a is preferably ^a hydrogen atom or a methyl group. X is preferably a single bond or an arylene group which may have a substituent, and more preferably a single bond.

Specific examples of the structural unit (h′2) are illustrated below. In the following formula, R ^a ′ represents a hydrogen atom, a methyl group or a trifluoromethyl group. m ″ is 0 or 1.

The structural unit (h ′) contained in the resin component may be used alone or in combination of two or more.
In the resin component having the structural unit (h ′), the proportion of the structural unit (h ′) is preferably 0.5 to 30 mol%, and 1 to 15 mol% with respect to all the structural units constituting the resin component. More preferred is 1.5 to 10 mol%. .
By setting the proportion of the structural unit (h ′) to be equal to or higher than the lower limit value, the dimensional variation of the resist pattern due to the influence of time is further suppressed. On the other hand, by setting the proportion of the structural unit (h ′) to the upper limit value or less, the dissolution contrast of the developer (particularly alkali developer) is improved, and the lithography properties such as resolution and pattern shape are improved.

-Other structural unit The resin component which has structural unit (h ') may have other structural units other than structural unit (h').
Such other structural unit is not particularly limited as long as it is a structural unit that is not classified into the structural unit (h ′) described above, such as for ArF excimer laser, for KrF excimer laser (preferably for ArF excimer laser), etc. Many things conventionally known as what is used for resin for resists can be used.
As such other structural unit, it is preferable to have a structural unit (a1) described later. In particular, the copolymer having the structural unit (a1) and the above-described structural unit (h ′) can be used as a base component (component (A)) of the resist composition.

In the resist composition of the present invention, the resin component having the structural unit (h ′) is a copolymer having the structural unit (h ′) and the structural unit (a1), that is, the base material component ((A)). (H) component as component) is preferable.
The resin component having the structural unit (h ′) is selected from the group consisting of the structural unit (a0) and the structural unit (a2) in addition to the structural unit (h ′) and the structural unit (a1). What has at least 1 type of structural unit is preferable.
In addition to the structural unit (h ′) and the structural unit (a1), the resin component having the structural unit (h ′) or at least one of the structural unit (a0) and the structural unit (a2) and the structural unit ( What has the said structural unit (a3) further in addition to a1) and a structural unit (h ') is preferable.

  In the resist composition, the resin component having the structural unit (h ′) may be used alone or in combination of two or more.

The above-mentioned “resin component having the structural unit (g ′)” and “resin component having the structural unit (h ′)” are structural units derived from the component (G) in the same copolymer ( A copolymer having a structural unit (g ′)) and a structural unit derived from the component (H) (structural unit (h ′)) is also included.
In the copolymer having the structural unit (g ′) and the structural unit (h ′), the proportion of the structural unit (g ′) is 0.5 to 30 with respect to all the structural units constituting the copolymer. Mol% is preferable, 1-15 mol% is more preferable, 1-10 mol% is more preferable, and the ratio of a structural unit (h ') is 0.5-0.5 with respect to all the structural units which comprise the said copolymer. 30 mol% is preferable, 1-15 mol% is more preferable, and 1-10 mol% is further more preferable.
By setting the proportion of the structural unit (g ′) within the above range, the effect of acid diffusion control is further enhanced, and the lithography characteristics or resist pattern shape is improved.
By setting the proportion of the structural unit (h ′) to be equal to or higher than the lower limit value, the dimensional variation of the resist pattern due to the influence of time is further suppressed. On the other hand, by setting the proportion of the structural unit (h ′) to the upper limit value or less, the dissolution contrast of the developer (particularly alkali developer) is improved, and the lithography properties such as resolution and pattern shape are improved.

In the resist composition of the present invention, the content of the compound (H) is preferably equal to or greater than the content of the compound (G). Thereby, when the resist composition is prepared and stored for a certain period, the dimensional fluctuation due to the influence of time is suppressed.
In the present invention, when the compound (H) or the compound (G) is a low molecular compound component, the “amount of contained material” means the mole of the compound blended in the resist composition based on 100 parts by mass of the base component. (Mol) means number.
When the compound (H) or the compound (G) is a resin component as a base component, the “content amount” is the number of moles calculated by the following procedures (1) to (3).
Procedure (1): About resin used for a resist composition, carbon 13 nuclear magnetic resonance spectrum (600 MHz — ¹³ C-NMR) indicates the copolymer composition ratio of the resin (ratio of each structural unit in the structural formula (molar ratio)). Ask for. Thereby, the ratio (molar ratio) of the structural unit (h ′) or the structural unit (g ′) is determined.
Procedure (2): From the molar ratio determined in the procedure (1), the mass ratio of the structural unit (h ′) or the structural unit (g ′) was determined, and the total resin component was defined as 100 (parts by mass). The ratio (mass ratio) of each structural unit is determined.
Procedure (3): The ratio (mass ratio) of the structural units determined in Procedure (2) is regarded as the mass of the compound (H) or the compound (G), and from this, the mole of the compound (H) or the compound (G) Calculate the number of (mol).

<(A) component>
In the resist composition of the present invention, as the component (A), it is preferable to use a base material component ((A0) component) whose polarity is increased by the action of an acid. That is, the resist composition of the present invention is preferably a chemically amplified resist composition that becomes positive in the alkali development process and negative in the solvent development process.
The component (A0) may be a resin component whose polarity is increased by the action of an acid, a low molecular compound component whose polarity is increased by the action of an acid, or a mixture thereof. .
The component (A0) is preferably a resin component whose polarity is increased by the action of an acid, and particularly derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. And a polymer (A1) having a structural unit (a1) containing an acid-decomposable group whose polarity is increased by the action of an acid (hereinafter also referred to as “component (A1)”). preferable.
In addition to the structural unit (a1), the component (A1) is a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent. A structural unit derived from a structural unit (a0) containing a —SO ₂ — containing cyclic group, and an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and a lactone What has at least 1 type of structural unit selected from the group which consists of a structural unit (a2) containing a containing cyclic group is preferable.
In addition to the structural unit (a1), the component (A1) or at least one of the structural unit (a0) and the structural unit (a2) and the structural unit (a1) are A structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom of which may be substituted with a substituent and having a structural unit (a3) containing a polar group-containing aliphatic hydrocarbon group is preferred. .
In addition, as the component (A1), in addition to the structural unit (a1), a copolymer (the component (G) as a base material component) having the structural unit (g ′) described above is also suitable. As mentioned.
As the component (A1), in addition to the structural unit (a1), a copolymer having the structural unit (h ′) described above (component (H) as a base material component) is also suitable. Can be mentioned.

Here, in the present specification and claims, the “structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
“Acrylic acid ester” is a compound in which the hydrogen atom at the carboxy group terminal of acrylic acid (CH ₂ ═CH—COOH) is substituted with an organic group.
In the acrylate ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent that replaces the hydrogen atom bonded to the α-position carbon atom is an atom or group other than a hydrogen atom, such as an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a hydroxy group. An alkyl group etc. are mentioned. The α-position carbon atom of the acrylate ester is a carbon atom to which a carbonyl group is bonded unless otherwise specified.
Hereinafter, an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent may be referred to as an α-substituted acrylate ester. Further, the acrylate ester and the α-substituted acrylate ester may be collectively referred to as “(α-substituted) acrylate ester”.
In the α-substituted acrylate ester, the alkyl group as a substituent at the α-position is preferably a linear or branched alkyl group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- Examples thereof include a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
Specific examples of the halogenated alkyl group as the substituent at the α-position include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as the substituent at the α-position” are substituted with a halogen atom. It is done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
Bonded to the α-position of the α-substituted acrylate ester is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. An alkyl group or a fluorinated alkyl group having 1 to 5 carbon atoms is more preferred, and a hydrogen atom or a methyl group is most preferred from the viewpoint of industrial availability.

[Structural unit (a1)]
The structural unit (a1) is a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and has an acid-decomposability that increases polarity by the action of an acid. A structural unit containing a group.

The “acid-decomposable group” is an acid-decomposable group that can cleave at least part of the bonds in the structure of the acid-decomposable group by the action of an acid generated from the component (B) upon exposure.
Examples of the acid-decomposable group whose polarity increases by the action of an acid include a group that decomposes by the action of an acid to generate a polar group.
Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, a sulfo group (—SO ₃ H), and the like. Among these, a polar group containing —OH in the structure (hereinafter sometimes referred to as “OH-containing polar group”) is preferable, a carboxy group or a hydroxyl group is preferable, and a carboxy group is particularly preferable.
More specifically, examples of the acid-decomposable group include a group in which the polar group is protected with an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).
An “acid-dissociable group” is an acid that can cleave at least a bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group by the action of an acid generated from, for example, the component (B) upon exposure. It is a group having dissociation properties. The acid-dissociable group constituting the acid-decomposable group must be a group having a lower polarity than the polar group generated by dissociation of the acid-dissociable group. Is dissociated, a polar group having a polarity higher than that of the acid dissociable group is generated to increase the polarity. As a result, the polarity of the entire component (A1) increases. As the polarity increases, the solubility in the developer changes relatively. When the developer is an alkaline developer, the solubility increases. On the other hand, the developer contains an organic solvent (organic type). In the case of a developer, the solubility decreases.

The acid-dissociable group is not particularly limited, and those that have been proposed as acid-dissociable groups for base resins for chemically amplified resists can be used. In general, a group that forms a cyclic or chain tertiary alkyl ester with a carboxy group in (meth) acrylic acid or the like; an acetal-type acid dissociable group such as an alkoxyalkyl group is widely known.
Here, the “tertiary alkyl ester” is an ester formed by replacing a hydrogen atom of a carboxy group with a chain or cyclic alkyl group, and the carbonyloxy group (—C (═O The structure in which the tertiary carbon atom of the chain or cyclic alkyl group is bonded to the terminal oxygen atom of) -O-). In this tertiary alkyl ester, when an acid acts, a bond is cut between an oxygen atom and a tertiary carbon atom to form a carboxy group.
The chain or cyclic alkyl group may have a substituent.
Hereinafter, a group that is acid dissociable by constituting a carboxy group and a tertiary alkyl ester is referred to as a “tertiary alkyl ester type acid dissociable group” for convenience.

Examples of the tertiary alkyl ester type acid dissociable group include an aliphatic branched acid dissociable group and an acid dissociable group containing an aliphatic cyclic group.
Here, “aliphatic branched” means having a branched structure having no aromaticity. The structure of the “aliphatic branched acid dissociable group” is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. The “hydrocarbon group” may be either saturated or unsaturated, but is usually preferably saturated.
Examples of the aliphatic branched acid dissociable group include a group represented by —C (R ⁷¹ ) (R ⁷² ) (R ⁷³ ). ^Wherein, R 71 ^{to R 73} each independently represents a linear alkyl group of 1 to 5 carbon atoms. The group represented by —C (R ⁷¹ ) (R ⁷² ) (R ⁷³ ) preferably has 4 to 8 carbon atoms, specifically, a tert-butyl group or a 2-methyl-2-butyl group. , 2-methyl-2-pentyl group, 3-methyl-3-pentyl group and the like. A tert-butyl group is particularly preferable.

The “aliphatic cyclic group” means a monocyclic group or a polycyclic group having no aromaticity.
The aliphatic cyclic group in the “acid-dissociable group containing an aliphatic cyclic group” may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O), and the like. Is mentioned.
The basic ring structure excluding the substituent of the aliphatic cyclic group is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. The hydrocarbon group may be either saturated or unsaturated, but is usually preferably saturated.
3-30 are preferable, as for carbon number which comprises this basic ring, 3-20 are more preferable, 5-15 are further more preferable, and 5-12 are especially preferable.
The aliphatic cyclic group may be monocyclic or polycyclic.
Examples of the aliphatic cyclic group include one or more hydrogens from a monocycloalkane which may or may not be substituted with an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group. A group in which one or more hydrogen atoms have been removed from a polycycloalkane such as bicycloalkane, tricycloalkane, or tetracycloalkane; More specifically, a group in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; one or more polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. An alicyclic hydrocarbon group such as a group excluding a hydrogen atom is exemplified. Moreover, a part of carbon atoms constituting the ring of these alicyclic hydrocarbon groups may be substituted with an ether group (—O—).

Examples of the acid dissociable group containing an aliphatic cyclic group include:
(I) On the ring skeleton of a monovalent aliphatic cyclic group, the substituent ( An atom or group other than a hydrogen atom) to form a tertiary carbon atom;
(Ii) a group having a monovalent aliphatic cyclic group and a branched alkylene having a tertiary carbon atom bonded thereto.
In the group (i), examples of the substituent bonded to the carbon atom bonded to the atom adjacent to the acid dissociable group on the ring skeleton of the aliphatic cyclic group include an alkyl group. Examples of the alkyl group include those similar to R ¹⁴ in formulas (1-1) to (1-9) described later.
Specific examples of the group (i) include groups represented by the following general formulas (1-1) to (1-9).
Specific examples of the group (ii) include groups represented by the following general formulas (2-1) to (2-6).

［式中、Ｒ^１４はアルキル基であり、ｇは０〜８の整数である。］

[Wherein, R ¹⁴ represents an alkyl group, and g represents an integer of 0 to 8. ]

［式中、Ｒ^１５およびＲ^１６は、それぞれ独立してアルキル基である。］

[Wherein, R ¹⁵ and R ¹⁶ each independently represents an alkyl group. ]

In formulas (1-1) to (1-9), the alkyl group of R ¹⁴ may be linear, branched or cyclic, and is preferably linear or branched.
The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and still more preferably 1 or 2. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. 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 alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group and the like, and isopropyl group is most preferable.
g is preferably an integer of 0 to 3, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
In formulas (2-1) to (2-6), examples of the alkyl group for R ^{15 to} R ¹⁶ include the same alkyl groups as those described above for R ¹⁴ .
In the formulas (1-1) to (1-9) and (2-1) to (2-6), a part of the carbon atoms constituting the ring is substituted with an etheric oxygen atom (—O—). May be.
In formulas (1-1) to (1-9) and (2-1) to (2-6), a hydrogen atom bonded to a carbon atom constituting the ring may be substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, and a fluorinated alkyl group.

The “acetal-type acid dissociable group” is generally bonded to an oxygen atom by substituting a hydrogen atom at the terminal of an OH-containing polar group such as a carboxy group or a hydroxyl group. When an acid is generated by exposure, this acid acts to break the bond between the acetal type acid dissociable group and the oxygen atom to which the acetal type acid dissociable group is bonded. OH-containing polar groups are formed.
Examples of the acetal type acid dissociable group include a group represented by the following general formula (p1).

［式中、Ｒ^１’，Ｒ^２’はそれぞれ独立して水素原子または炭素数１〜５のアルキル基を表し、ｎは０〜３の整数を表し、Ｙは炭素数１〜５のアルキル基または脂肪族環式基を表す。］

[Wherein, R ¹ 'and R ² ' each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n represents an integer of 0 to 3, and Y represents an alkyl group having 1 to 5 carbon atoms. Or represents an aliphatic cyclic group. ]

In formula (p1), n is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 0.
Examples of the alkyl group for R ¹ ′ and R ² ′ include the same alkyl groups listed as the substituents that may be bonded to the α-position carbon atom in the description of the α-substituted acrylate ester. A methyl group or an ethyl group is preferred, and a methyl group is most preferred.
In the present invention, it is preferable that at least one of R ¹ ′ and R ² ′ is a hydrogen atom. That is, the acid dissociable group (p1) is preferably a group represented by the following general formula (p1-1).

［式中、Ｒ^１’、ｎ、Ｙは上記と同じである。］

[Wherein R ¹ ′, n and Y are the same as described above. ]

Examples of the alkyl group for Y include the same alkyl groups as those described above for the substituent that may be bonded to the carbon atom at the α-position in the description of the α-substituted acrylate ester.
The aliphatic cyclic group for Y can be appropriately selected from monocyclic or polycyclic aliphatic cyclic groups that have been proposed in a number of conventional ArF resists. For example, the above “aliphatic ring” Examples thereof are the same as the aliphatic cyclic groups mentioned in “Acid-dissociable groups containing formula groups”.

  Examples of the acetal type acid dissociable group also include a group represented by the following general formula (p2).

［式中、Ｒ^１７、Ｒ^１８はそれぞれ独立して直鎖状若しくは分岐鎖状のアルキル基または水素原子であり；Ｒ^１９は直鎖状、分岐鎖状若しくは環状のアルキル基である。または、Ｒ^１７およびＲ^１９がそれぞれ独立に直鎖状若しくは分岐鎖状のアルキレン基であって、Ｒ^１７とＲ^１９とが結合して環を形成していてもよい。］

[Wherein, R ¹⁷ and R ¹⁸ each independently represents a linear or branched alkyl group or a hydrogen atom; and R ¹⁹ represents a linear, branched or cyclic alkyl group. Alternatively, R ¹⁷ and R ¹⁹ may each independently be a linear or branched alkylene group, and R ¹⁷ and R ¹⁹ may be bonded to form a ring. ]

In R ¹⁷ and R ¹⁸ , the alkyl group preferably has 1 to 15 carbon atoms, may be linear or branched, and is preferably an ethyl group or a methyl group, and most preferably a methyl group.
In particular, it is preferable that one of R ¹⁷ and R ¹⁸ is a hydrogen atom and the other is a methyl group.
R ¹⁹ is a linear, branched or cyclic alkyl group, preferably having 1 to 15 carbon atoms, and may be any of linear, branched or cyclic.
When R ¹⁹ is linear or branched, it preferably has 1 to 5 carbon atoms, more preferably an ethyl group or a methyl group, and most preferably an ethyl group.
When R ¹⁹ is cyclic, it preferably has 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, one or more polycycloalkanes such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. And the like, in which a hydrogen atom is removed. Specific examples include monocycloalkanes such as cyclopentane and cyclohexane, and groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferable.
In the formula (p2), R ¹⁷ and R ¹⁹ are each independently a linear or branched alkylene group (preferably an alkylene group having 1 to 5 carbon atoms), and R ¹⁹ and R ¹⁷ And may be combined.
In this case, a cyclic group is formed by R ¹⁷ , R ¹⁹ , the oxygen atom to which R ¹⁹ is bonded, and the carbon atom to which the oxygen atom and R ¹⁷ are bonded. The cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

  More specifically, examples of the structural unit (a1) include structural units represented by general formula (a1-0-1) shown below, structural units represented by general formula (a1-0-2) shown below, and the like. .

［式中、Ｒは水素原子、炭素数１〜５のアルキル基または炭素数１〜５のハロゲン化アルキル基であり；Ｘ^１は酸解離性基であり；Ｙ^２は２価の連結基であり；Ｘ^２は酸解離性基である。］

Wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; X ¹ is an acid dissociable group; Y ² is a divalent linking group. Yes; X ² is an acid-dissociable group. ]

In general formula (a1-0-1), the alkyl group and the halogenated alkyl group of R are each exemplified as the substituent which may be bonded to the carbon atom at the α-position in the description of the α-substituted acrylic ester. And the same alkyl groups and halogenated alkyl groups. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, and most preferably a hydrogen atom or a methyl group.
X ¹ is not particularly limited as long as it is an acid dissociable group, and examples thereof include the above-described tertiary alkyl ester type acid dissociable groups, acetal type acid dissociable groups, and the like. An ester type acid dissociable group is preferred.
In general formula (a1-0-2), R is the same as defined above.
X ² is the same as X ¹ in formula (a1-0-1).

Examples of the divalent linking group of Y ^2, but are not limited to, divalent hydrocarbon group which may have a substituent group, and a divalent linking group containing a hetero atom as preferred.
The hydrocarbon group having “substituent” means that part or all of the hydrogen atoms in the hydrocarbon group are substituted with a substituent (a group or atom other than a hydrogen atom).
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.
The aliphatic hydrocarbon group as the divalent hydrocarbon group in Y ² may be saturated or unsaturated, and is usually preferably saturated.
More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. 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 preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (═O).

Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic 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 those described above.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
The alicyclic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring.
The aromatic hydrocarbon group as the divalent hydrocarbon group in Y ² preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, and 6 to 6 carbon atoms. 15 is particularly preferable, and 6 to 10 is most preferable. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring of the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; a part of carbon atoms constituting the aromatic hydrocarbon ring is hetero Aromatic heterocycles substituted with atoms; and the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.
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) ) In which one of the hydrogen atoms is substituted with an alkylene group (for example, arylalkyl such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) Group in which one hydrogen atom is further removed from the aryl group in the group); and the like. The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
The aromatic hydrocarbon group may or may not have a substituent. For example, a hydrogen atom bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxygen atom (═O).
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group. Most preferred is an ethoxy group.
Examples of the halogen atom as a substituent for the aromatic hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms.

The hetero atom in the “divalent linking group containing a hetero atom” of Y ² is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
As the divalent linking group containing a hetero atom, —O—, —C (═O) —O—, —C (═O) —, —O—C (═O) —O—, —C (= O) —NH—, —NH— (H may be substituted with a substituent such as an alkyl group, an acyl group, etc.), —S—, —S (═O) ₂ —, —S (═O) _{2 -O -, - NH-C} (= O) -, = N-, the formula ^{-Y 21 -O-Y 22 -,} - [Y 21 -C (= O) -O] m '-Y 22 - Or a group represented by —Y ²¹ —O—C (═O) —Y ²² —, wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group optionally having a substituent. O is an oxygen atom, and m ′ is an integer of 0 to 3. ] Etc. are mentioned.
When Y ² is —NH—, H may be substituted with a substituent such as an alkyl group or an aryl group (aromatic group). The substituent (alkyl group, aryl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
Formula ^{-Y 21 -O-Y 22 -,} - [Y 21 -C (= O) -O] m '-Y 22 - or ^{-Y 21 -O-C (= O} ) -Y 22 - ^{In, Y 21} And Y ²² are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same groups as those described above as the “divalent hydrocarbon group which may have a substituent” for Y ² .
Y ²¹ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group. preferable.
Y ²² is preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, 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, 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) —O—Y ²² —. The group is particularly preferred. Among these, a group represented by the formula — (CH ₂ ) _{a ′} —C (═O) —O— (CH ₂ ) _{b ′} — is preferable. In the formula, a ′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1. b ′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1.
Examples of the divalent linking group containing a hetero atom, a linear group containing an oxygen atom as a hetero atom, for example, a group containing an ether bond or an ester bond, are preferred, the formula -Y 21 ^-O-Y 22 ^-, A group represented by — [Y ²¹ —C (═O) —O] _{m ′} —Y ²² — or —Y ²¹ —O—C (═O) —Y ²² — is more preferable.

Among the above, as the divalent linking group for Y ² , in particular, a linear or branched alkylene group, a divalent alicyclic hydrocarbon group, or a divalent linking group containing a hetero atom is included. preferable. Among these, a linear or branched alkylene group or a divalent linking group containing a hetero atom is preferable.

  More specifically, examples of the structural unit (a1) include structural units represented by the following general formulas (a1-1) to (a1-4).

［式中、Ｒ、Ｒ^１’、Ｒ^２’、ｎ、ＹおよびＹ^２はそれぞれ前記と同じであり、Ｘ’は第３級アルキルエステル型酸解離性基を表す。］’

[Wherein, R, R ¹ ′, R ² ′, n, Y and Y ² are the same as defined above, and X ′ represents a tertiary alkyl ester-type acid dissociable group. ] '

In the formula, X ′ is the same as the tertiary alkyl ester-type acid dissociable group.
^{R 1 ', R 2',} n, as the Y, respectively, ^{R 1} in the general formula listed in the description of "acetal-type acid dissociable group" described above ^{(p1) ', R 2'} , n, similarly to the Y Can be mentioned.
The Y ^2, the same groups as those described above for ^{Y 2} in the general formula (a1-0-2).
Specific examples of the structural units represented by the general formulas (a1-1) to (a1-4) are shown below.
In the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

In the present invention, as the structural unit (a1), a structural unit represented by the following general formula (a1-0-11), a structural unit represented by the following general formula (a1-0-12), and the following general formula ( a1-0-13), a structural unit represented by the following general formula (a1-0-14), a structural unit represented by the following general formula (a1-0-15), and the following general unit It is preferable to have at least one selected from the group consisting of structural units represented by formula (a1-0-2).
Especially, the structural unit represented by the following general formula (a1-0-11), the structural unit represented by the following general formula (a1-0-12), and the following general formula (a1-0-13) And at least one selected from the group consisting of structural units represented by the following general formula (a1-0-14) and structural units represented by the following general formula (a1-0-15) It is more preferable.

［式中、Ｒは水素原子、炭素数１〜５のアルキル基または炭素数１〜５のハロゲン化アルキル基であり、Ｒ^２１はアルキル基であり；Ｒ^２２は、当該Ｒ^２２が結合した炭素原子と共に脂肪族単環式基を形成する基であり；Ｒ^２３は分岐鎖状のアルキル基であり；Ｒ^２４は、当該Ｒ^２４が結合した炭素原子と共に脂肪族多環式基を形成する基であり；Ｒ^２５は炭素数１〜５の直鎖状のアルキル基である。Ｒ^１５およびＲ^１６は、それぞれ独立してアルキル基である。Ｙ^２は２価の連結基であり、Ｘ^２は酸解離性基である。］

Wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, R ²¹ is an alkyl group; R ²² is a carbon to which R ²² is bonded. A group that forms an aliphatic monocyclic group together with an atom; R ²³ is a branched alkyl group; and R ²⁴ is a group that forms an aliphatic polycyclic group together with the carbon atom to which R ²⁴ is bonded. R ²⁵ is a linear alkyl group having 1 to 5 carbon atoms. R ¹⁵ and R ¹⁶ are each independently an alkyl group. Y ² is a divalent linking group, and X ² is an acid dissociable group. ]

In each formula, the description of R, Y ² and X ² is the same as described above.
In formula (a1-0-11), examples of the alkyl group for R ²¹ include the same alkyl groups as those described above for R ¹⁴ in formulas (1-1) to (1-9). Group or isopropyl group is preferred.
R ²² is, the aliphatic monocyclic group formed together with the carbon atom to which R ²² is bonded, the same aliphatic cyclic groups as those in the aforementioned tertiary alkyl ester-type acid dissociable groups, a monocyclic group The thing similar to what is is mentioned. Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane is preferably a 3- to 11-membered ring, more preferably a 3- to 8-membered ring, further preferably a 4- to 6-membered ring, and particularly preferably a 5- or 6-membered ring.
In the monocycloalkane, a part of carbon atoms constituting the ring may or may not be substituted with an ether group (—O—).
Moreover, this monocycloalkane may have a C1-C5 alkyl group, a fluorine atom, or a C1-C5 fluorinated alkyl group as a substituent.
Examples of R ²² constituting such an aliphatic monocyclic group include a linear alkylene group in which an ether group (—O—) may be interposed between carbon atoms.

Specific examples of the structural unit represented by the formula (a1-0-11) include the formulas (a1-1-16) to (a1-1-23), (a1-1-27), and (a1-1 -31). Among these, the formulas (a1-1-16) to (a1-1-17), (a1-1-20) to (a1-1-23), (a1-1-27), (a1-1-1- The structural unit represented by the following (a1-1-02) including the structural units represented by 31), (a1-1-32), and (a1-1-33) is preferable. Moreover, the structural unit represented by the following (a1-1-02 ′) is also preferable.
In each formula, h is an integer of 1 to 4, and 1 or 2 is preferable.

［式中、Ｒ、Ｒ^２１はそれぞれ前記と同じであり、ｈは１〜４の整数である。］

[Wherein, R and R ²¹ are the same as defined above, and h is an integer of 1 to 4, respectively. ]

In formula (a1-0-12), as the branched alkyl group for R ²³ , the branched alkyl group described for the alkyl group for R ¹⁴ in formulas (1-1) to (1-9) above. Examples thereof are the same as those described above, and an isopropyl group is most preferable.
R ²⁴ is, the aliphatic polycyclic group formed together with the carbon atom to which R ²⁴ is bonded, the same aliphatic cyclic groups as those in the aforementioned tertiary alkyl ester-type acid dissociable group, polycyclic group The thing similar to what is is mentioned.
Specific examples of the structural unit represented by the formula (a1-0-12) include those represented by the formulas (a1-1-26) and (a1-1-28) to (a1-1-30). Units are listed.
As the structural unit represented by the formula (a1-0-12), those in which R ²⁴ is an aliphatic polycyclic group formed together with the carbon atom to which R ²⁴ is bonded are preferably a 2-adamantyl group, The structural unit represented by the formula (a1-1-26) is preferable.

In formula (a1-0-13), R and R ²⁴ are the same as defined above.
Examples of the linear alkyl group for R ²⁵ include the same linear alkyl groups as those described above for the alkyl group for R ^{14 in} the formulas (1-1) to (1-9), and methyl Most preferred are groups or ethyl groups.
Specific examples of the structural unit represented by the formula (a1-0-13) include formulas (a1-1-1) to (a1-1-2) exemplified as specific examples of the general formula (a1-1). ), Structural units represented by (a1-1-7) to (a1-1-15).
As the structural unit represented by the formula (a1-0-13), those in which R ²⁴ is an aliphatic polycyclic group formed together with the carbon atom to which R ²⁴ is bonded are preferably a 2-adamantyl group, The structural unit represented by the formula (a1-1-1) or (a1-1-2) is preferable.

In formula (a1-0-14), R and R ²² are the same as defined above. R ¹⁵ and ^{R 16} are the same as ^{R 15} and ^{R 16} in each of the general formulas (2-1) to (2-6).
Specific examples of the structural unit represented by the formula (a1-0-14) include the formulas (a1-1-35) and (a1-1-36) exemplified as specific examples of the general formula (a1-1). ).

In formula (a1-0-15), R and R ²⁴ are the same as defined above. R ¹⁵ and ^{R 16} are the same as ^{R 15} and ^{R 16} in each of the general formulas (2-1) to (2-6).
Specific examples of the structural unit represented by formula (a1-0-15) include formulas (a1-1-4) to (a1-1-6) exemplified as specific examples of general formula (a1-1). ) And (a1-1-34).

Examples of the structural unit represented by the formula (a1-0-2) include the structural unit represented by the formula (a1-3) or (a1-4), and particularly represented by the formula (a1-3). Are preferred.
As the structural unit represented by the formula (a1-0-2), in particular, Y ^{2 in} the formula is the aforementioned —Y ²¹ —O—Y ²² — or —Y ²¹ —C (═O) —O—Y ^22. Those represented by-are preferred.
Preferred examples of the structural unit include a structural unit represented by the following general formula (a1-3-01); a structural unit represented by the following general formula (a1-3-02); 3-03) and the like.

［式中、Ｒは前記と同じであり、Ｒ^１３は水素原子またはメチル基であり、Ｒ^１４はアルキル基であり、ｅは１〜１０の整数であり、ｎ’は０〜３の整数である。］

[Wherein, R is the same as above, R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is an alkyl group, e is an integer of 1 to 10, and n ′ is an integer of 0 to 3] is there. ]

［式中、Ｒは前記と同じであり、Ｙ^２’およびＹ^２”はそれぞれ独立して２価の連結基であり、Ｘ’は酸解離性基であり、ｗは０〜３の整数である。］

[Wherein, R is the same as defined above, Y ² ′ and Y ² ″ are each independently a divalent linking group, X ′ is an acid-dissociable group, and w is an integer of 0 to 3] is there.]

In formulas (a1-3-01) to (a1-3-02), R ¹³ is preferably a hydrogen atom.
R ¹⁴ is the same as ^{R 14} in the formula (1-1) to (1-9).
e is preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and most preferably 1 or 2.
n ′ is preferably 1 or 2, and most preferably 2.
Specific examples of the structural unit represented by the formula (a1-3-01) include structural units represented by the formulas (a1-3-25) to (a1-3-26).
Specific examples of the structural unit represented by the formula (a1-3-02) include structural units represented by the formulas (a1-3-27) to (a1-3-28).

In formula (a1-3-03), examples of the divalent linking group for Y ² ′ and Y ² ″ include the same groups as those described above for Y ² in formula (a1-3).
Y ² ′ is preferably a divalent hydrocarbon group which may have a substituent, more preferably a linear aliphatic hydrocarbon group, and even more preferably a linear alkylene group. Among these, a linear alkylene group having 1 to 5 carbon atoms is preferable, and a methylene group and an ethylene group are most preferable.
Y ² ″ is preferably a divalent hydrocarbon group which may have a substituent, more preferably a linear aliphatic hydrocarbon group, and still more preferably a linear alkylene group. A linear alkylene group of 1 to 5 is preferable, and a methylene group and an ethylene group are most preferable.
Examples of the acid dissociable group in X ′ include the same groups as described above, and are preferably tertiary alkyl ester-type acid dissociable groups. In addition, a group in which a substituent is bonded to a carbon atom bonded to an atom adjacent to the acid dissociable group to form a tertiary carbon atom is more preferable. Preferred are the groups
w is an integer of 0 to 3, and w is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1.
As the structural unit represented by the formula (a1-3-03), a structural unit represented by the following general formula (a1-3-03-1) or (a1-3-03-2) is preferable. The structural unit represented by the formula (a1-3-03-1) is preferable.

［式中、ＲおよびＲ^１４はそれぞれ前記と同じであり、ａ’は１〜１０の整数であり、ｂ’は１〜１０の整数であり、ｔは０〜３の整数である。］

[Wherein, R and R ¹⁴ are the same as defined above, a ′ is an integer of 1 to 10, b ′ is an integer of 1 to 10, and t is an integer of 0 to 3, respectively. ]

In formulas (a1-3-03-1) to (a1-3-03-2), a ′ is the same as described above, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and 1 or 2 is particularly preferred.
b ′ is the same as described above, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and particularly preferably 1 or 2.
t is preferably an integer of 1 to 3, and 1 or 2 is particularly preferable.
Specific examples of the structural unit represented by formula (a1-3-03-1) or (a1-3-03-2) include those represented by formulas (a1-3-29) to (a1-3-32). The structural unit represented is mentioned.

As the structural unit (a1) contained in the component (A1), 1 type of structural unit may be used, or 2 or more types may be used.
In the component (A1), the proportion of the structural unit (a1) is preferably from 15 to 70 mol%, more preferably from 15 to 60 mol%, more preferably from 20 to 55 mol%, based on all the structural units constituting the component (A1). Is more preferable.
By setting the proportion of the structural unit (a1) to the lower limit value or more, a pattern can be easily obtained when a resist composition is formed, and the lithography properties such as sensitivity, resolution, and LWR are also improved. Moreover, it becomes easy to balance with another structural unit by setting it as an upper limit or less.

[Structural unit (a0)]
The structural unit (a0) is a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent, and includes a —SO ₂ — containing cyclic group Unit.
The structural unit (a0) contains a —SO ₂ — containing cyclic group, thereby improving the adhesion of the resist film formed using the resist composition containing the component (A1) to the substrate. Further, it contributes to the improvement of lithography characteristics such as sensitivity, resolution, exposure margin (EL margin), LWR (line width roughness), LER (line edge roughness), mask reproducibility and the like.

Here _- as "-SO 2 containing cyclic group", -SO 2 _- within the ring skeleton thereof shows a cyclic group containing a ring containing, in particular, -SO 2 _- in the sulfur atom (S ) Is a cyclic group that forms part of the ring skeleton of the cyclic group.
-SO 2 _- In-containing cyclic group, within the ring skeleton thereof -SO 2 _- in a ring containing as the first ring, when in the case of the ring only having a single cyclic group, yet another ring structure Is referred to as a polycyclic group regardless of its structure.
The —SO ₂ — containing cyclic group may be monocyclic or polycyclic.
The —SO ₂ — containing cyclic group is particularly a cyclic group containing —O—SO ₂ — in the ring skeleton, that is, a ring skeleton in which —O—S— in —O—SO ₂ — is a cyclic group. It is preferable that it is a sultone ring which forms a part of.
The —SO ₂ — containing cyclic group preferably has 3 to 30 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and particularly preferably 4 to 12 carbon atoms. . However, the carbon number is the number of carbon atoms constituting the ring skeleton, and does not include the carbon number in the substituent.
The —SO ₂ — containing cyclic group may be an —SO ₂ — containing aliphatic cyclic group or an —SO ₂ — containing aromatic cyclic group. Preferably -SO ₂ - containing aliphatic cyclic group.
The —SO ₂ -containing aliphatic cyclic group includes at least a hydrogen atom from an aliphatic hydrocarbon ring in which a part of carbon atoms constituting the ring skeleton is substituted with —SO ₂ — or —O—SO ₂ —. One group is excluded. More specifically, a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which —CH ₂ — constituting the ring skeleton is substituted with —SO ₂ —, —CH ₂ — constituting the ring And a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which CH ₂ — is substituted with —O—SO ₂ —.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms are removed from a monocycloalkane having 3 to 6 carbon atoms. Examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group in which two hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane. , Tricyclodecane, tetracyclododecane and the like.

The —SO ₂ — containing cyclic group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (═O), —COOR ″, —OC (═O) R ″ (R ″ represents a hydrogen atom or an alkyl group). Group), a hydroxyalkyl group, a cyano group, and the like.
The alkyl group as the substituent is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples 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.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, the group couple | bonded with the oxygen atom (-O-) to the alkyl group quoted as the alkyl group as the said substituent is mentioned.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group for the substituent include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms.
Examples of the halogenated alkyl group as the substituent include a group in which part or all of the hydrogen atoms of the alkyl group mentioned as the alkyl group as the substituent are substituted with the halogen atom. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.
R ″ in —COOR ″ and —OC (═O) R ″ is preferably a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms.
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 particularly preferably a methyl group or an ethyl group. preferable.
When R ″ is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, a fluorine atom Or a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane, which may or may not be substituted with a fluorinated alkyl group More specifically, one or more hydrogen atoms are removed from a monocycloalkane such as cyclopentane or cyclohexane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Group and the like.
As the hydroxyalkyl group as the substituent, those having 1 to 6 carbon atoms are preferable. Specifically, at least one hydrogen atom of the alkyl group mentioned as the alkyl group as the substituent is substituted with a hydroxyl group. Group.
More specifically, examples of the —SO ₂ -containing cyclic group include groups represented by the following general formulas (3-1) to (3-4).

［式中、Ａ’は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｚは０〜２の整数であり、Ｒ^６はアルキル基、アルコキシ基、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり、Ｒ”は水素原子またはアルキル基である。］

[In the formula, A ′ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, z is an integer of 0 to 2, and R ⁶ is an alkyl group. , An alkoxy group, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group, and R ″ is a hydrogen atom or an alkyl group.]

In the general formulas (3-1) to (3-4), A ′ represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (—O—) or a sulfur atom (—S—), An oxygen atom or a sulfur atom.
The alkylene group having 1 to 5 carbon atoms in A ′ is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.
When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include a group in which —O— or —S— is interposed between the terminal or carbon atoms of the alkylene group, such as —O—CH _{2. -, - CH 2 -O-CH} 2 -, - S-CH 2 -, - CH 2 -S-CH 2 - , and the like.
A ′ is preferably an alkylene group having 1 to 5 carbon atoms or —O—, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.
z may be any of 0 to 2, and is most preferably 0.
When z is 2, the plurality of R ⁶ may be the same or different.
As the alkyl group, alkoxy group, halogenated alkyl group, —COOR ″, —OC (═O) R ″, and hydroxyalkyl group in R ⁶ , the —SO ₂ — containing cyclic group has the above-mentioned, respectively. And the same alkyl groups, alkoxy groups, halogenated alkyl groups, —COOR ″, —OC (═O) R ″, and hydroxyalkyl groups as those which may be substituted.
Below, the specific cyclic group represented by the said general formula (3-1)-(3-4) is illustrated. In the formula, “Ac” represents an acetyl group.

Among the above, the —SO ₂ -containing cyclic group is preferably a group represented by the general formula (3-1), and the chemical formulas (3-1-1), (3-1-18), ( It is more preferable to use at least one selected from the group consisting of groups represented by any of 3-3-1) and (3-4-1), and represented by the chemical formula (3-1-1). Are most preferred.

  More specifically, examples of the structural unit (a0) include structural units represented by general formula (a0-0) shown below.

［式中、Ｒは水素原子、炭素数１〜５のアルキル基または炭素数１〜５のハロゲン化アルキル基であり、Ｒ^３０は−ＳＯ_２−含有環式基であり、Ｒ^２９’は単結合または２価の連結基である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, R ³⁰ is a —SO ₂ — containing cyclic group, and R ²⁹ ′ is a single atom. It is a bond or a divalent linking group. ]

In formula (a0-0), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- Examples thereof include a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
The halogenated alkyl group in R is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and is most preferably a hydrogen atom or a methyl group in terms of industrial availability.

In formula (a0-0), R ³⁰ is the same as the —SO ₂ — containing cyclic group mentioned above.
R ²⁹ ′ may be either a single bond or a divalent linking group. Since it is excellent in the effect of this invention, it is preferable that it is a bivalent coupling group.
Examples of the divalent linking group for R ²⁹ ′ include those listed as the divalent linking group for Y ² in the general formula (a1-0-2) given in the description of the structural unit (a1). The same thing is mentioned.
The divalent linking group for R ²⁹ ′ is preferably an alkylene group, a divalent alicyclic hydrocarbon group, or a divalent linking group containing a hetero atom. Among these, those containing an alkylene group and an ester bond (—C (═O) —O—) are preferable.
The alkylene group is preferably a linear or branched alkylene group. Specifically, the same as the linear alkylene group and the branched alkylene group mentioned as the aliphatic hydrocarbon group for Y ² can be used.
As the divalent linking group containing an ester bond, in particular, the general formula: —R ²⁰ —C (═O) —O— [wherein R ²⁰ is a divalent linking group. ] Is preferable. That is, the structural unit (a0) is preferably a structural unit represented by the following general formula (a0-0-1).

［式中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基であり、Ｒ^２０は２価の連結基であり、Ｒ^３０は−ＳＯ_２−含有環式基である。］

[Wherein, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, R ²⁰ is a divalent linking group, and R ³⁰ is —SO ₂ — containing] It is a cyclic group. ]

R ²⁰ is not particularly limited, and examples thereof include those similar to those exemplified as the divalent linking group for R ²⁹ ′ in the general formula (a0-0).
The divalent linking group for R ²⁰ is preferably a linear or branched alkylene group, a divalent alicyclic hydrocarbon group, or a divalent linking group containing a hetero atom.
Examples of the linear or branched alkylene group, divalent alicyclic hydrocarbon group, and divalent linking group containing a hetero atom include the linear groups mentioned above as preferred for R ²⁹ ′. Or the thing similar to the branched alkylene group, the bivalent alicyclic hydrocarbon group, and the bivalent coupling group containing a hetero atom is mentioned.
Among these, a linear or branched alkylene group or a divalent linking group containing an oxygen atom as a hetero atom is preferable.
As the linear alkylene group, a methylene group or an ethylene group is preferable, and a methylene group is particularly preferable.
As the branched alkylene group, an alkylmethylene group or an alkylethylene group is preferable, and —CH (CH ₃ ) —, —C (CH ₃ ) ₂ — or —C (CH ₃ ) ₂ CH ₂ — is particularly preferable.
Examples of the divalent linking group containing an oxygen atom, is preferably a divalent linking group containing an ether bond or an ester bond, the formula ^-Y 21 ^{-O-Y 22} -, wherein ^- [Y 21 -C (= O ^{_{) -O] m '- Y 22}} - or the formula ^{-Y 21 -O-C (= O} ) -Y 22 - group represented by is more preferable. Y ²¹ , Y ²² and m ′ are the same as described above.
Among them, a group represented by the formula —Y ²¹ —O—C (═O) —Y ²² — is preferable, and a group represented by the formula — (CH ₂ ) _c —O—C (═O) — (CH ₂ ) _d — The groups represented are particularly preferred. c is an integer of 1 to 5, an integer of 1 to 3 is preferable, and 1 or 2 is more preferable. d is an integer of 1 to 5, an integer of 1 to 3 is preferable, and 1 or 2 is more preferable.

  As the structural unit (a0), a structural unit represented by general formula (a0-0-11) or (a0-0-12) shown below is preferable, and a structural unit represented by formula (a0-0-12) is preferable. Units are more preferred.

［式中、Ｒ、Ａ’、Ｒ^６、ｚおよびＲ^２０はそれぞれ前記と同じである。］

[Wherein, R, A ′, R ⁶ , z and R ²⁰ are the same as defined above. ]

In formula (a0-0-11), A ′ is preferably a methylene group, an ethylene group, an oxygen atom (—O—) or a sulfur atom (—S—).
R ²⁰ is preferably a linear or branched alkylene group or a divalent linking group containing an oxygen atom. As the linear or branched alkylene group and the divalent linking group containing an oxygen atom in R ^20, the linear or branched alkylene group and the divalent linking group containing an oxygen atom respectively mentioned above are used. Examples are the same as the linking group.
As the structural unit represented by the formula (a0-0-12), a structural unit represented by the following general formula (a0-0-12a) or (a0-0-12b) is particularly preferable.

［式中、ＲおよびＡ’はそれぞれ前記と同じであり、ｃ及びｄはそれぞれ前記と同じであり、ｆは１〜５の整数（好ましくは１〜３の整数）である。］

[Wherein, R and A ′ are the same as defined above, c and d are the same as defined above, and f is an integer of 1 to 5 (preferably an integer of 1 to 3). ]

As the structural unit (a0) contained in the component (A1), 1 type of structural unit may be used, or 2 or more types may be used.
The proportion of the structural unit (a0) in the component (A1) is such that the resist pattern shape formed using the resist composition containing the component (A1) becomes good, and lithography such as EL margin, LWR, mask reproducibility, etc. From the viewpoint of excellent properties, it is preferably 1 to 60 mol%, more preferably 5 to 55 mol%, still more preferably 10 to 50 mol%, based on the total of all structural units constituting the component (A1). 15 to 45 mol% is most preferable.

[Structural unit (a2)]
The structural unit (a2) is a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent, and includes a lactone-containing cyclic group. .
Here, the lactone-containing cyclic group refers to a cyclic group containing one ring (lactone ring) containing a —O—C (═O) — structure. The lactone ring is counted as the first ring. When only the lactone ring is present, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure.
When the lactone cyclic group of the structural unit (a2) is used to form a resist film, the component (A1) is used to enhance the adhesion of the resist film to the substrate or to contain a developer containing water (especially an alkali development process). In the case of ()).

As the structural unit (a2), any unit can be used without any particular limitation.
Specifically, as the lactone-containing monocyclic group, a group in which one hydrogen atom is removed from a 4- to 6-membered ring lactone, for example, a group in which one hydrogen atom is removed from β-propionolactone, or γ-butyrolactone. Examples thereof include a group in which one hydrogen atom has been removed, and a group in which one hydrogen atom has been removed from δ-valerolactone. Examples of the lactone-containing polycyclic group include groups in which one hydrogen atom has been removed from a bicycloalkane, tricycloalkane, or tetracycloalkane having a lactone ring.

  More specifically, examples of the structural unit (a2) include structural units represented by general formulas (a2-1) to (a2-5) shown below.

［式中、Ｒは水素原子、低級アルキル基またはハロゲン化低級アルキル基であり；Ｒ’はそれぞれ独立に水素原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基または−ＣＯＯＲ”であり、Ｒ”は水素原子またはアルキル基であり；Ｒ^２９は単結合または２価の連結基であり、ｓ”は０または１〜２の整数であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり；ｍは０または１の整数である。］

[Wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; R ′ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or —COOR; R "is a hydrogen atom or an alkyl group; R ²⁹ is a single bond or a divalent linking group; s" is 0 or an integer of 1 to 2; A "is an oxygen atom or a sulfur atom. An alkylene group having 1 to 5 carbon atoms, an oxygen atom or a sulfur atom, and m is an integer of 0 or 1. ]

R in the general formulas (a2-1) to (a2-5) is the same as R in the structural unit (a1).
Examples of the alkyl group having 1 to 5 carbon atoms of R ′ include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group.
Examples of the alkoxy group having 1 to 5 carbon atoms of R ′ include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group.
R ′ is preferably a hydrogen atom in view of industrial availability.
R ″ is preferably a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms.
When R ″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
When R ″ is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, a fluorine atom Or a monocycloalkane which may or may not be substituted with a fluorinated alkyl group; a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane Specifically, a group in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Etc.
A ″ is preferably an alkylene group having 1 to 5 carbon atoms or —O—, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.
R ²⁹ is a single bond or a divalent linking group. The divalent linking group is the same as the divalent linking group described for Y ² in the general formula (a1-0-2), and among them, an alkylene group and an ester bond (—C (═O ) -O-) or a combination thereof. The alkylene group as the divalent linking group for R ²⁹ is more preferably a linear or branched alkylene group. Specifically, the same linear alkylene groups and branched alkylene groups as those described above for the aliphatic hydrocarbon group for Y ² can be used.
s ″ is preferably an integer of 1 to 2.
Specific examples of the structural units represented by the general formulas (a2-1) to (a2-5) are illustrated below.
In the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

As the structural unit (a2) contained in the component (A1), 1 type of structural unit may be used, or 2 or more types may be used.
As the structural unit (a2), at least one selected from the group consisting of structural units represented by the general formulas (a2-1) to (a2-5) is preferable, and the general formulas (a2-1) to ( At least one selected from the group consisting of structural units represented by a2-3) is more preferred. Among them, chemical formulas (a2-1-1), (a2-1-2), (a2-2-1), (a2-2-7), (a2-3-1) and (a2-3-5) It is preferable to use at least one selected from the group consisting of structural units represented by

The proportion of the structural unit (a2) in the component (A1) is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, based on the total of all the structural units constituting the component (A1). More preferably, it is 45 mol%.
By setting the proportion of the structural unit (a2) to the lower limit value or more, the effect of including the structural unit (a2) is sufficiently obtained, and by setting the proportion of the structural unit (a2) to the upper limit value or less, balance with other structural units is achieved. It becomes easy.

[Structural unit (a3)]
The structural unit (a3) is a structural unit derived from an acrylate 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 Units (however, the structural units (a1), (a0), (a2) described above, excluding those corresponding to the structural unit (g ′) and the structural unit (h ′)).
When the component (A1) has the structural unit (a3), the hydrophilicity of the component (A) increases, which contributes to the improvement of resolution.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, and a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom. 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. For example, a resin for a resist composition for an ArF excimer laser can be appropriately selected from those proposed. The cyclic group is preferably a polycyclic group, and more preferably 7 to 30 carbon atoms.
Among them, a structural unit derived from an acrylate ester containing an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of hydrogen atoms of a hydroxyl group, a cyano group, a carboxy group, or an alkyl group is substituted with a fluorine atom Is more preferable. Examples of the polycyclic group include groups in which two or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane and the like. Specific examples include groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, there are groups in which two or more hydrogen atoms have been removed from adamantane, groups in which two or more hydrogen atoms have been removed from norbornane, and groups in which two or more hydrogen atoms have been removed from tetracyclododecane. Industrially preferable.

  The structural unit (a3) is derived from a hydroxyethyl ester of acrylic acid 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. When the hydrocarbon group is a polycyclic group, the structural unit represented by the following formula (a3-1), the structural unit represented by the formula (a3-2), the formula ( The structural unit represented by a3-3) is preferred.

（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の整数であり、ｔ’は１〜３の整数であり、ｌは１〜５の整数であり、ｓは１〜３の整数である。）

(Wherein R is the same as above, j is an integer of 1 to 3, k is an integer of 1 to 3, t 'is an integer of 1 to 3, and l is an integer of 1 to 5) And s is an integer of 1 to 3.)

In 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 3rd and 5th positions 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.
j is preferably 1, and it is particularly preferred that the hydroxyl group is bonded to the 3-position of the adamantyl group.

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

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

As the structural unit (a3) contained in the component (A1), 1 type of structural unit may be used, or 2 or more types may be used.
In the component (A1), the proportion of the structural unit (a3) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on the total of all the structural units constituting the component (A1). 5 to 25 mol% is more preferable.
By setting the proportion of the structural unit (a3) to the lower limit value or more, the effect of including the structural unit (a3) can be sufficiently obtained, and by setting the proportion of the structural unit (a3) to the upper limit value or less, balance with other structural units can be obtained. It becomes easy.

[Structural unit (g ′)]
The structural unit (g ′) contained in the component (A1) may be one type or two or more types.
In the component (A1), the proportion of the structural unit (g ′) is preferably 0.1 to 30 mol%, and 0.5 to 15 mol% with respect to the total of all the structural units constituting the component (A1). More preferably, 1-10 mol% is further more preferable.
By setting the proportion of the structural unit (g ′) to be equal to or higher than the lower limit value, the effect of acid diffusion control is further improved, and the lithography characteristics or the resist pattern shape is improved. On the other hand, by setting it to the upper limit value or less, it becomes easy to balance with other structural units.

[Structural unit (h ')]
The structural unit (h ′) contained in the component (A1) may be one type or two or more types.
In the component (A1), the proportion of the structural unit (h ′) is preferably 0.1 to 30 mol%, and 0.5 to 15 mol% with respect to the total of all the structural units constituting the component (A1). More preferably, 1-10 mol% is further more preferable.
By setting the proportion of the structural unit (h ′) to be equal to or higher than the lower limit value, dimensional fluctuations of the resist pattern due to the influence of time are further suppressed. On the other hand, by setting it to the upper limit value or less, it becomes easy to balance with other structural units.

[Other structural units]
The component (A1) is within the range not impairing the effects of the present invention, and the structural unit (a1), structural unit (a0), structural unit (a2), structural unit (a3), structural unit (g ′), and structural unit. You may have other structural units other than a unit (h ').
Such other structural unit is not particularly limited as long as it is a structural unit that is not classified as the above-mentioned structural unit, and it is used for resist resins such as for ArF excimer laser and for KrF excimer laser (preferably for ArF excimer laser). Many things conventionally known as what is used can be used.
Such other structural unit is a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and is a non-acid dissociable aliphatic polycyclic And a structural unit (a4) containing a group and a structural unit (a5) capable of generating an acid upon exposure.

(Structural unit (a4))
The structural unit (a4) is a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and is a non-acid-dissociable aliphatic polycyclic group Is a structural unit including
In the structural unit (a4), examples of the polycyclic group include the same polycyclic groups as exemplified in the case of the structural unit (a1). For ArF excimer laser, KrF excimer Many things conventionally known as what is used for the resin component of resist compositions, such as for lasers (preferably for ArF excimer lasers), can be used.
In particular, at least one selected from a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group is preferable in terms of industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
Specific examples of the structural unit (a4) include those represented by the following general formulas (a4-1) to (a4-5).

（式中、Ｒは前記と同じである。）

(In the formula, R is as defined above.)

  When the structural unit (a4) is contained in the component (A1), the structural unit (a4) is preferably contained in an amount of 1 to 30 mol% based on the total of all the structural units constituting the component (A1). 10 to 20 mol% is more preferable.

(Structural unit (a5))
The structural unit (a5) is a structural unit capable of generating an acid upon exposure.
The structural unit (a5) is not particularly limited as long as it generates an acid upon exposure. For example, the structural unit can be copolymerized with the structural units (a1) to (a4) and (a0) described above. Any of those that have been proposed as acid generators for chemically amplified resists can be used.
The structural unit copolymerizable with the structural units (a1) to (a4), (a0) and the like is derived from an acrylate ester in which the hydrogen atom bonded to the α-position carbon atom may be substituted with a substituent. And a structural unit derived from hydroxystyrene in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.
As a conventionally proposed acid generator for a chemically amplified resist, the component (B) described later is preferable.
In the structural unit (a5), the structural site that generates an acid upon exposure is preferably an ionic structural site, and the sulfonium salt or iodonium salt exemplified in the description of the component (B) described later. The ionic structural site in is preferred. The acid anion generated by exposure is preferably a sulfonic acid anion, a carboxylic acid anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, or a tris (alkylsulfonyl) methide anion. These acid anions are more preferably generated from the side chain of the resin by exposure.

  Among them, the structural unit (a5) of the present invention is a group represented by the following general formula (a5-1-1) or (a5-2-1) in terms of acid strength, sensitivity, resolution, and roughness. It is preferable to have.

［式中、Ａは単結合又は２価の連結基であり、Ｒ^４４は置換基を有していてもよいアリーレン基であり、Ｒ^４５、Ｒ^４６はそれぞれ独立に有機基であり、Ｒ^４５、Ｒ^４６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いてもよく、Ｘ⁻は対アニオンであり、Ｒ^ｆ１、Ｒ^ｆ２はそれぞれ独立に水素原子、アルキル基、フッ素原子、又はフッ素化アルキル基であり、Ｒ^ｆ１、Ｒ^ｆ２のうち少なくとも１つはフッ素原子又はフッ素化アルキル基であり、ｎ”は１〜８の整数であり、Ｍ^ｒ＋は対カチオンであり、ｒは１〜３の整数である。］

[Wherein, A is a single bond or a divalent linking group, R ⁴⁴ is an arylene group which may have a substituent, R ⁴⁵ and R ⁴⁶ are each independently an organic group, and R ⁴⁵ , R ⁴⁶ may be bonded to each other to form a ring together with the sulfur atom in the formula, X ⁻ is a counter anion, and R ^f1 and R ^f2 are each independently a hydrogen atom, an alkyl group, a fluorine atom, Or at least one of R ^f1 and R ^f2 is a fluorine atom or a fluorinated alkyl group, n ″ is an integer of 1 to 8, M ^{r +} is a counter cation, and r is It is an integer from 1 to 3.]

In formulas (a5-1-1) and (a5-2-1), A represents a single bond or a divalent linking group.
Preferred examples of the divalent linking group for A include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.
The term “having a substituent” for the hydrocarbon group means that part or all of the hydrogen atoms in the hydrocarbon group are substituted with groups or atoms other than hydrogen atoms.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.
The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

More specifically, 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.
The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, still more preferably 1 to 5, and most preferably 1 to 2.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. 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 preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
The chain-like aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (═O).

Examples of the aliphatic hydrocarbon group including a ring in the structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and the cyclic aliphatic hydrocarbon group includes the chain described above. And a group that is bonded to the terminal of the chain-like aliphatic hydrocarbon group or intervenes in the middle of the chain-like aliphatic hydrocarbon group.
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 group, a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and examples of the monocycloalkane include cyclopentane and cyclohexane.
As the polycyclic group, a group in which two hydrogen atoms are removed from a polycycloalkane having 7 to 12 carbon atoms is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, tetra And cyclododecane.
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

Examples of the aromatic hydrocarbon group include aromatics of monovalent aromatic hydrocarbon groups such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. A divalent aromatic hydrocarbon group obtained by further removing one hydrogen atom from the nucleus of the aromatic hydrocarbon; a part of the carbon atoms constituting the ring of the divalent aromatic hydrocarbon group are oxygen atom, sulfur atom, nitrogen Aromatic hydrocarbon groups substituted with heteroatoms such as atoms; arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc. And an aromatic hydrocarbon group obtained by further removing one hydrogen atom from the nucleus of the aromatic hydrocarbon.
The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

The hetero atom in the “divalent linking group containing a hetero atom” is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.
Specific examples of the divalent linking group containing a hetero atom include —O—, —C (═O) —, —C (═O) —O—, and a carbonate bond (—O—C (═O) —. O-), -NH-, ^-NR05 ( ^R05 is an alkyl group)-, -NH-C (= O)-, = N- and the like. Moreover, the combination etc. of these "divalent coupling groups containing a hetero atom" and a bivalent hydrocarbon group are mentioned. Examples of the divalent hydrocarbon group include the same hydrocarbon groups that may have a substituent as described above, and a linear or branched aliphatic hydrocarbon group is preferable.

  A may or may not have an acid dissociable site in its structure. The “acid-dissociable site” refers to a site in the organic group that is dissociated by the action of an acid generated by exposure. When A has an acid dissociable site, it preferably has an acid dissociable site having a tertiary carbon atom.

The divalent linking group for A is preferably an alkylene group, a divalent aliphatic cyclic group or a divalent linking group containing a hetero atom.
When A is an alkylene group, the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, It is most preferable that it is 1-3. Specific examples include the same linear alkylene groups and branched alkylene groups as mentioned above.
When A is a divalent aliphatic cyclic group, the aliphatic cyclic group is the same as the cyclic aliphatic hydrocarbon group mentioned in the above “aliphatic hydrocarbon group containing a ring in the structure”. Things.
The aliphatic cyclic group is particularly preferably a group in which two or more hydrogen atoms have been removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane or tetracyclododecane.

When A is a divalent linking group containing a hetero atom, preferred examples of the linking group include —O—, —C (═O) —O—, —C (═O) —, —O—C ( ═O) —O—, —C (═O) —NH—, and —NH— (H may be substituted with a substituent such as an alkyl group or an acyl group.
_{), - S -, - S} (= O) 2 -, - S (= O) 2 -O-, a group represented by the formula -A'-O-B'-, wherein - [A'-C ( ═O) —O] _{m ′} —B′— and the like. Here, A ′ and B ′ are each independently a divalent hydrocarbon group which may have a substituent, and m ′ is an integer of 0 to 3.
When A is —NH—, H may be substituted with a substituent such as an alkyl group or an acyl group. 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.
In —A′—O—B′— or — [A′—C (═O) —O] _{m ′} —B′—, A ′ and B ′ each independently have a substituent. It is also a good divalent hydrocarbon group.
Examples of the divalent hydrocarbon group which may have a substituent in A ′ and B ′ include those mentioned above as “the divalent hydrocarbon group which may have a substituent” in A. The same thing is mentioned.
As A ′, 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 more preferable, and a methylene group or an ethylene group is particularly preferable. preferable.
B ′ is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, 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 — [A′—C (═O) —O] _{m ′} —B′—, m ′ is an integer of 0 to 3, and preferably an integer of 0 to 2. 0 or 1 is more preferable, and 1 is most preferable.
In the present invention, A is preferably a single bond, an ester bond [—C (═O) —O—], an ether bond (—O—), an alkylene group or a combination thereof, and among these, an alkylene group Is particularly preferred.

In formula (a5-1-1), R ⁴⁴ represents an arylene group which may have a substituent. There may be one or more substituents,
The arylene group R ^44, not particularly limited, for example, an arylene group having 6 to 20 carbon atoms, said arylene groups, part or all of the hydrogen atoms may be substituted. For example, it may or may not be substituted with an alkyl group, alkoxy group, halogen atom, hydroxyl group or the like.
Such an arylene group is preferably an arylene group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenylene group and a naphthylene group, and a phenylene group is particularly preferable.
The alkyl group which may be substituted with a hydrogen atom of the arylene group is preferably an alkyl group having 1 to 5 carbon atoms, and is a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Are more preferable, and a methyl group is particularly preferable.
As the alkoxy group that may be substituted for the hydrogen atom of the arylene group, 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, A tert-butoxy group is more preferable.
The halogen atom that may be substituted for the hydrogen atom of the arylene group is preferably a fluorine atom.

In formula (a5-1-1), R ⁴⁵ and R ⁴⁶ are each independently an organic group.
The organic groups of R ⁴⁵ and R ⁴⁶ are groups containing carbon atoms, and atoms other than carbon atoms (for example, hydrogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms (fluorine atoms, chlorine atoms, etc.), etc.) You may have.
As the organic group for R ⁴⁵ and R ⁴⁶ , an aryl group or an alkyl group is preferable.

The aryl group for R ⁴⁵ and R ⁴⁶ is not particularly limited, and may be, for example, an aryl group having 6 to 20 carbon atoms, and the aryl group may have part or all of its hydrogen atoms substituted. Good. For example, it may or may not be substituted with an alkyl group, alkoxy group, halogen atom, hydroxyl group or the like.
Such an aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group, and a phenyl group is particularly preferable.
The aryl group or an alkyl group which may be substituted is a hydrogen atom, an alkoxy group, the halogen atom, the alkyl group an arylene group substituted in R ^44, alkoxy groups, those similar to the halogen atom Can be mentioned.

The alkyl group of R ^45, R ^46, not particularly limited, for example, linear C1-10, branched or cyclic alkyl group, and the like. It is preferable that it is C1-C5 from the point which is excellent in resolution. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, and a decanyl group. . Among these, a methyl group is preferable because it is more excellent in resolution and can be synthesized at a low cost.

In formula (a5-1-1), R ⁴⁵ and R ⁴⁶ may be bonded to each other to form a ring together with the sulfur atom in the formula.
In such a case, it is preferable to form a 3- to 10-membered ring including a sulfur atom, and it is particularly preferable to form a 5- to 7-membered ring.
The ring structure formed with the sulfur atom may contain a hetero atom such as a sulfur atom or an oxygen atom (—O—, ═O).
Specific examples of the ring formed include, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, Thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring , Isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, phenazine ring and the like.

In formula (a5-1-1), X ⁻ represents a counter anion.
The X ⁻ counter anion is not particularly limited, and an anion of an onium salt acid generator represented by the general formula (b-1) or (b-2) in the component (B) described later. Part (R ⁴ ″ SO ₃ ⁻ ); an anion represented by the general formula (b-3) or (b-4) in the component (B) to be described later is exemplified, and particularly R ⁴ ″ SO ₃ ⁻ Preferably, it is at least one selected from fluorinated alkyl sulfonate ions having 1 to 8 carbon atoms (preferably having 1 to 4 carbon atoms) or general formulas (b1) to (b8) described later. .

In formula (a5-2-1), R ^f1 and R ^f2 each independently represent a hydrogen atom, an alkyl group, a fluorine atom, or a fluorinated alkyl group, and at least one of R ^f1 and R ^f2 is a fluorine atom or A fluorinated alkyl group;
As the alkyl group for R ^f1 and R ^f2 , an alkyl group having 1 to 5 carbon atoms is preferable. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group Group, pentyl group, isopentyl group, neopentyl group and the like.
Examples of the fluorinated alkyl group of ^{R f1,} R ^f2, group in which part or all of the hydrogen atoms of the alkyl group of the ^{R f1, R f2} is substituted with a fluorine atom is preferred.
In the present invention, R ^f1 and R ^f2 are preferably fluorine atoms.

  In formula (a5-2-1), n ″ is an integer of 1 to 8, preferably an integer of 1 to 4, and more preferably 1 or 2.

In formula (a5-2-1), M ^{r +} is a counter cation, and r is an integer of 1 to 3.
^Examples of the counter cation of ^{Mr +} include a metal cation or an onium cation.
^Examples of the metal ion of ^{Mr +} include alkali metal ions such as sodium, potassium and lithium, alkaline earth metal ions such as magnesium and calcium, iron ions and aluminum ions. Among these, sodium ion, potassium ion, and lithium ion are preferable because ion exchange to sulfonate is easy.
Examples of the onium cation of Mr ⁺ include a sulfonium cation, an iodonium cation, a phosphonium cation, a diazonium cation, an ammonium cation, and a pyridinium cation. Especially, it is preferable that it is the same as the cation part of the onium salt type | system | group acid generator represented by general formula (b-1) or (b-2) in (B) component mentioned later.

  Specific examples of the group represented by the formula (a5-1-1) or (a5-2-1) are shown below.

  The structural unit (a5) of the present invention is a structural unit represented by the following general formula (a5-1), particularly from the viewpoints of acid strength, sensitivity, resolution, roughness, ease of synthesis, and the like. A structural unit represented by general formula (a5-2) is preferable.

［式中、Ｒは水素原子、炭素数１〜５のアルキル基、又は炭素数１〜５のハロゲン化アルキル基である。Ａは単結合又は２価の連結基である。Ｒ^４４は置換基を有していてもよいアリーレン基である。Ｒ^４５、Ｒ^４６はそれぞれ独立に有機基であり、Ｒ^４５、Ｒ^４６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いてもよい。Ｘ⁻は対アニオンである。Ｒ^ｆ１、Ｒ^ｆ２はそれぞれ独立に水素原子、アルキル基、フッ素原子、又はフッ素化アルキル基であり、Ｒ^ｆ１、Ｒ^ｆ２のうち少なくとも１つはフッ素原子又はフッ素化アルキル基である。ｎ”は１〜８の整数である。Ｍ^ｒ＋は対カチオンであり、ｒは１〜３の整数である。］

[Wherein, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. A is a single bond or a divalent linking group. R ⁴⁴ is an arylene group which may have a substituent. R ⁴⁵ and R ⁴⁶ are each independently an organic group, and R ⁴⁵ and R ⁴⁶ may be bonded to each other to form a ring together with the sulfur atom in the formula. X ⁻ is a counter anion. R ^f1 and R ^f2 are each independently a hydrogen atom, an alkyl group, a fluorine atom, or a fluorinated alkyl group, and at least one of R ^f1 and R ^f2 is a fluorine atom or a fluorinated alkyl group. n ″ is an integer of 1 to 8. M ^{r +} is a counter cation and r is an integer of 1 to 3.]

In formulas (a5-1) and (a5-2), R is the same as described above, and is preferably a hydrogen atom or a methyl group.
In the formulas (a5-1) and (a5-2), A, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , X ⁻ , R ^f1 , R ^f2 , n ″, M ^{r +} , r are each represented by the above formula (a5- 1-1), the same as A, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , X ⁻ , R ^f1 , R ^f2 , n ″, M ^{r +} , r in (a5-2-1).

  When the structural unit (a5) is contained in the component (A1), the structural unit (a5) is preferably contained in an amount of 1 to 40 mol% based on the total of all the structural units constituting the component (A1). 1 to 35 mol% is more preferable, and 3 to 30 mol% is more preferable. By setting it to the lower limit value or more, lithography properties are improved, for example, roughness is further reduced. By setting it to the upper limit value or less, it is possible to balance with other structural units.

In the resist composition of the present invention, the component (A) preferably contains the polymer (A1) having the structural unit (a1).
Specifically, as the component (A1), a copolymer (A1-11-1) comprising the structural unit (a1), the structural unit (a2) and the structural unit (a3); the structural unit (a1), the structural unit (a0) ) And a structural unit (a3) copolymer (A1-11-2); a structural unit (a1), a structural unit (a0), a structural unit (a3) and a structural unit (g ′). A1-12-1); a copolymer (A1-13-1) comprising the structural unit (a1), the structural unit (a0), the structural unit (a3) and the structural unit (h ′); the structural unit (a1), Copolymer (A1-11-3) consisting of structural unit (a0), structural unit (a2) and structural unit (a3); structural unit (a1), structural unit (a0), structural unit (a2), structural unit A copolymer (A1-12-2) comprising (a3) and the structural unit (g ′); 1) the structural units (a0), the structural unit (a2), a copolymer consisting of the structural unit (a3) and the structural unit (h ') (A1-13-2) and the like.
In the component (A), as the component (A1), one type may be used alone, or two or more types may be used in combination.
As the component (A1), for example, among the above examples, only copolymers having no structural unit (g ′) or structural unit (h ′) (copolymers (A1-11-1) to (A1-11) -3)), only the copolymer having the structural unit (g ′) (at least one of the copolymers (A1-12-1) and (A1-12-2)), the structural unit (h ′). Only copolymers having at least one of copolymers (A1-13-1) and (A1-13-2), or combinations thereof can be used.
The proportion of the component (A1) in the component (A) is preferably 25% by mass or more, more preferably 50% by mass, further preferably 75% by mass, 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, MEF, exposure margin (EL margin), lithography characteristics such as roughness reduction, and resist pattern shape are further improved.

The mass average molecular weight (Mw) of the component (A1) (polystyrene conversion standard by gel permeation chromatography (GPC)) is not particularly limited, preferably 1000 to 50000, more preferably 1500 to 30000, 2000 to 2000 20000 is most preferred. If it is below the upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist, and if it is above the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are good.
The dispersity (Mw / Mn) is not particularly limited, but is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5. In addition, Mn shows a number average molecular weight.

The component (A1) can be obtained by polymerizing a monomer for deriving each structural unit by a known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN).
Further, for the component (A1), in the polymerization, a chain transfer agent such as HS—CH ₂ —CH ₂ —CH ₂ —C (CF ₃ ) ₂ —OH is used in combination, so that the terminal A —C (CF ₃ ) ₂ —OH group may be introduced into the. As described above, a copolymer introduced with a hydroxyalkyl group in which a part of hydrogen atoms of the alkyl group is substituted with a fluorine atom reduces development defects and LER (line edge roughness: uneven unevenness of line side walls). It is effective in reducing
A commercially available monomer may be used as the monomer for deriving each structural unit, or the monomer may be synthesized using a known method.

The component (A) may contain a base material component (hereinafter referred to as “component (A2)”) whose polarity is increased by the action of an acid other than the component (A1) as long as the effects of the present invention are not impaired. Good.
When the resist composition of the present invention is a resist composition that forms a positive resist pattern in an alkali development process and a negative resist pattern in a solvent development process, the molecular weight is 500 or more and less than 2500 as the component (A2). Then, a low molecular compound having an acid dissociable group and a hydrophilic group as exemplified in the description of the component (A1) may be used. Specific examples include those in which some or all of the hydrogen atoms of the hydroxyl group of the compound having a plurality of phenol skeletons are substituted with the acid dissociable group.
Examples of the low molecular weight compound include a sensitizer in a non-chemically amplified g-line or i-line resist, and a part of the hydrogen atom of the hydroxyl group of a low molecular weight phenol compound known as a heat resistance improver. Those substituted with a dissociable group are preferred, and any of them can be used arbitrarily.
Examples of the low molecular weight phenol compound include bis (4-hydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4′-hydroxyphenyl). ) Propane, 2- (2,3,4-trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-trihydroxyphenyl) propane, tris (4-hydroxyphenyl) methane, bis (4-hydroxy-) 3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3, 4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxypheny Rumethane, bis (4-hydroxy-3-methylphenyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl- 4-hydroxy-6-methylphenyl) -3,4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, Examples include 2 to 6 nuclei of formalin condensates of phenols such as phenol, m-cresol, p-cresol and xylenol. Of course, it is not limited to these. In particular, a phenol compound having 2 to 6 triphenylmethane skeletons is preferable because of excellent resolution and line edge roughness (LWR). The acid dissociable group is not particularly limited, and examples thereof include those described above.

  In the resist composition of the present invention, the content of the component (A) may be adjusted according to the resist film thickness to be formed.

<(B) component>
In the resist composition of the present invention, as the component (B), those that have been proposed as acid generators for chemically amplified resists can be used.
Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and poly (bissulfonyl) diazomethanes. There are various known diazomethane acid generators, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the like.
As the onium salt acid generator, for example, a compound represented by the following general formula (b-1) or (b-2) can be used.

［式中、Ｒ^１”〜Ｒ^３”，Ｒ^５”〜Ｒ^６”はそれぞれ独立に置換基を有していてもよいアリール基、アルキル基又はアルケニル基を表す。式（ｂ−１）におけるＲ^１”〜Ｒ^３”のうち、いずれか二つが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^４”は、置換基を有していてもよいアルキル基、ハロゲン化アルキル基、アリール基、またはアルケニル基を表す。］

[Wherein, R ¹ ″ to R ³ ″ and R ⁵ ″ to R ⁶ ″ each independently represents an aryl group, an alkyl group or an alkenyl group which may have a substituent. Any two of R ¹ ″ to R ³ ″ in formula (b-1) may be bonded to each other to form a ring together with the sulfur atom in the formula. R ⁴ ″ represents an alkyl group, a halogenated alkyl group, an aryl group, or an alkenyl group which may have a substituent.

In the formula ^{(b-1), R 1} "~R 3" , the formula (g-c1) in ^R 1 ^{"~R 3"} to be similar, respectively.

In the formula (b-1), R ⁴ ″ represents an alkyl group, a halogenated alkyl group, an aryl group, or an alkenyl group which may have a substituent.
The alkyl group for R ⁴ ″ may be linear, branched or cyclic.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The cyclic alkyl group preferably has 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.
Examples of the halogenated alkyl group for R ⁴ ″ include groups in which part or all of the hydrogen atoms of the linear, branched, or cyclic alkyl group have been substituted with halogen atoms. A fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.
In the halogenated alkyl group, the ratio of the number of halogen atoms to the total number of halogen atoms and hydrogen atoms contained in the halogenated alkyl group (halogenation rate (%)) is preferably 10 to 100%. 50 to 100% is preferable, and 100% is most preferable. The higher the halogenation rate, the better the acid strength.
The aryl group for R ⁴ ″ is preferably an aryl group having 6 to 20 carbon atoms.
The alkenyl group in R ⁴ ″ is preferably an alkenyl group having 2 to 10 carbon atoms.
In the above R ⁴ ″, “may have a substituent” means that a part or all of the hydrogen atoms in the alkyl group, halogenated alkyl group, aryl group, or alkenyl group are a substituent (hydrogen atom). It may be substituted with other atoms or groups).
The number of substituents in R ⁴ ″ may be one, or two or more.

Examples of the substituent include a halogen atom, a hetero atom, an alkyl group, a formula: R ^X -Q ^1- [where Q ¹ is a divalent linking group containing an oxygen atom, and R ^X represents a substituent. It is a C3-C30 hydrocarbon group which may have. ] Etc. which are represented by these.
Examples of the halogen atom and alkyl group include the same groups as those described as the halogen atom and alkyl group in the halogenated alkyl group in R ⁴ ″.
Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.

In the group represented by R ^X —Q ¹ —, Q ¹ is a divalent linking group containing an oxygen atom.
Q ¹ may contain an atom other than an oxygen atom. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.
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 amide bond (—C (═O) —NH. -), A carbonyl group (-C (= O)-), a non-hydrocarbon oxygen atom-containing linking group such as a carbonate bond (-O-C (= O) -O-); the non-hydrocarbon oxygen atom Examples include a combination of a containing linking group and an alkylene group.
Examples of the combination include —R ⁹¹ —O—, —R ⁹² —O—C (═O) —, —C (═O) —O—R ⁹³ —O—C (═O) — , R ^{91 to} R ⁹³ are each independently an alkylene group.) And the like.
The alkylene group for R ^{91 to} R ⁹³ is preferably a linear or branched alkylene group, and the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. preferable.
Specific examples of the alkylene group include a methylene group [—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 - ; alkylethylene groups such as ethylene group _[-CH 2 CH _2— ]; —CH (CH ₃ ) CH ₂ —, —CH (CH ₃ ) CH (CH ₃ ) —, —C (CH ₃ ) ₂ CH ₂ —, —CH (CH ₂ CH ₃ ) CH ₂ — and the like. Alkylethylene groups; trimethylene groups (n-propylene groups) [—CH ₂ CH ₂ CH ₂ —]; alkyls such as —CH (CH ₃ ) CH ₂ CH ₂ — and —CH ₂ CH (CH ₃ ) CH ₂ — trimethylene; tetramethylene group _[-CH 2 _CH 2 C _{2 CH 2 -]; - CH} (CH 3) CH 2 CH 2 CH 2 -, - CH 2 CH (CH 3) CH 2 CH 2 - alkyl tetramethylene group and the like; pentamethylene group _[-CH 2 _CH 2 CH ₂ CH ₂ CH ₂ —] and the like.
Q ¹ is preferably a divalent linking group containing an ester bond or an ether bond, and in particular, —R ⁹¹ —O—, —R ⁹² —O—C (═O) — or —C (═O) — O—R ⁹³ —O—C (═O) — is preferred.

In the group represented by R ^X -Q ^1- , the hydrocarbon group of R ^X may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

The aromatic hydrocarbon group 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, still more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic hydrocarbon group include a hydrogen atom from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Aryl groups such as aryl group, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc., from which one is removed. The number of carbon atoms in the alkyl chain in the arylalkyl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

The aromatic hydrocarbon group may have a substituent. For example, a part of carbon atoms constituting the aromatic ring of the aromatic hydrocarbon group may be substituted with a hetero atom, and the hydrogen atom bonded to the aromatic ring of the aromatic hydrocarbon group is substituted with the substituent. May be.
Examples of the former include heteroaryl groups in which some of the carbon atoms constituting the ring of the aryl group are substituted with heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and aromatic hydrocarbons in the arylalkyl groups. Examples include heteroarylalkyl groups in which some of the carbon atoms constituting the ring are substituted with the above heteroatoms.
Examples of the substituent of the aromatic hydrocarbon group in the latter example include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxygen atom (═O).
The alkyl group as a substituent of the aromatic hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. preferable.
The alkoxy group as a substituent of the aromatic hydrocarbon group is preferably an alkoxy group having 1 to 5 carbon atoms, and is a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert- A butoxy group is preferable, and a methoxy group and an ethoxy group are most preferable.
Examples of the halogen atom as a substituent for the aromatic hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent of the aromatic hydrocarbon group include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms.

The aliphatic hydrocarbon group for R ^X may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched or cyclic.
In R ^X , the aliphatic hydrocarbon group may be a group in which a part of carbon atoms constituting the aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom, and the hydrogen constituting the aliphatic hydrocarbon group A part or all of the atoms may be substituted with a substituent containing a hetero atom.
The “heteroatom” in R ^X is not particularly limited as long as it is an atom other than a carbon atom and a hydrogen atom, and examples thereof include a halogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom.
The substituent containing a hetero atom may be composed of only the hetero atom, or may be a group containing a group or atom other than the hetero atom.
Specific examples of the substituent for substituting a part of the carbon atom include —O—, —C (═O) —O—, —C (═O) —, —O—C (═O) —O. —, —C (═O) —NH—, —NH— (H may be substituted with a substituent such as an alkyl group, an acyl group, etc.), —S—, —S (═O) ₂ —, — S (= O) ₂ —O— and the like can be mentioned. When the aliphatic hydrocarbon group is cyclic, these substituents may be included in the ring structure.
Specific examples of the substituent for substituting part or all of the hydrogen atoms include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (═O), and a cyano group.
The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group, and a methoxy group or an ethoxy group. Is most preferred.
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.
As the halogenated alkyl group, a part or all of hydrogen atoms of an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, etc. And a group substituted with a halogen atom.

Examples of the aliphatic hydrocarbon group include a linear or branched saturated hydrocarbon group, a linear or branched monovalent unsaturated hydrocarbon group, or a cyclic aliphatic hydrocarbon group (aliphatic ring). Formula group) is preferred.
The linear saturated hydrocarbon group (alkyl group) preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group Group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group and the like.
The branched saturated hydrocarbon group (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 include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.

As an unsaturated hydrocarbon group, it is preferable that carbon number is 2-10, 2-5 are preferable, 2-4 are preferable, and 3 is especially preferable. Examples of the linear monovalent unsaturated hydrocarbon group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched monovalent unsaturated hydrocarbon group include a 1-methylpropenyl group and a 2-methylpropenyl group.
Among the above, the unsaturated hydrocarbon group is particularly preferably a propenyl group.

The aliphatic cyclic group may be a monocyclic group or a polycyclic group. The number of carbon atoms is preferably 3 to 30, more preferably 5 to 30, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12.
Specifically, for example, a group in which one or more hydrogen atoms have been removed from a monocycloalkane; a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as bicycloalkane, tricycloalkane, tetracycloalkane, etc. Can be mentioned. More specifically, a group in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; one or more polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. Examples include a group excluding a hydrogen atom.
When the aliphatic cyclic group does not contain a substituent containing a hetero atom in the ring structure, the aliphatic cyclic group is preferably a polycyclic group, and has one or more hydrogen atoms from the polycycloalkane. Excluded groups are preferred, and most preferred are groups in which one or more hydrogen atoms have been removed from adamantane.
When the aliphatic cyclic group includes a substituent containing a hetero atom in the ring structure, examples of the substituent containing a hetero atom include —O—, —C (═O) —O—, —S—. , —S (═O) ₂ — and —S (═O) ₂ —O— are preferable. Specific examples of the aliphatic cyclic group include groups represented by the following formulas (L1) to (L6) and (S1) to (S4).

［式中、Ｑ”は炭素数１〜５のアルキレン基、−Ｏ−、−Ｓ−、−Ｏ−Ｒ^９４−または−Ｓ−Ｒ^９５−であり、Ｒ^９４およびＲ^９５はそれぞれ独立に炭素数１〜５のアルキレン基であり、ｍは０または１の整数である。］

[Wherein, Q ″ is an alkylene group having 1 to 5 carbon atoms, —O—, —S—, —O—R ⁹⁴ — or —S—R ⁹⁵ —, and R ⁹⁴ and R ⁹⁵ are each independently carbon. An alkylene group of 1 to 5 and m is an integer of 0 or 1.]

In the formula, examples of the alkylene group for Q ″, R ⁹⁴ and R ⁹⁵ include the same alkylene groups as those described above for R ^{91 to} R ⁹³ .
In these aliphatic cyclic groups, a part of hydrogen atoms bonded to carbon atoms constituting the ring structure may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxygen atom (═O).
As said alkyl group, a C1-C5 alkyl group is preferable, and it is especially preferable that they are a methyl group, an ethyl group, a propyl group, n-butyl group, and a tert- butyl group.
Examples of the alkoxy group and the halogen atom are the same as those exemplified as the substituent for substituting part or all of the hydrogen atoms.

Among the above, R ^X is preferably a cyclic group which may have a substituent. The cyclic group may be an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a substituent. It is preferably an aliphatic cyclic group that may be used.
The aromatic hydrocarbon group is preferably a naphthyl group which may have a substituent or a phenyl group which may have a substituent.
As the aliphatic cyclic group which may have a substituent, a polycyclic aliphatic cyclic group which may have a substituent is preferable. Examples of the polycyclic aliphatic cyclic group include groups obtained by removing one or more hydrogen atoms from the polycycloalkane, groups represented by the above (L2) to (L5) and (S3) to (S4). Etc. are preferred.

Also, R ^X, since the lithography properties, resist pattern shape is further improved, which has a polar moiety is particularly preferred.
As having a polar moiety, for example, substituted groups in which some of the carbon atoms constituting the aliphatic cyclic group of the above-mentioned R ^X includes a heteroatom, i.e., -O -, - C (= O) -O -, -C (= O)-, -O-C (= O) -O-, -C (= O) -NH-, -NH- (H is substituted with a substituent such as an alkyl group or an acyl group. may _{be), - S -, - S} (= O) 2 -, - S (= O) 2 -O- , etc., in include those substituted.

Among the above, R ⁴ ″ preferably has R ^X —Q ¹ — as a substituent. In this case, R ⁴ ″ includes R ^X -Q ¹ -Y ^1- [wherein Q ¹ and R ^X is the same as above, and Y ¹ is an optionally substituted alkylene group having 1 to 4 carbon atoms or an optionally substituted fluorinated alkylene group having 1 to 4 carbon atoms. is there. ] Is preferable.
In the group represented by R ^X —Q ¹ —Y ¹ —, the alkylene group for Y ¹ includes the same alkylene groups as those described above for Q ¹ having 1 to 4 carbon atoms.
Examples of the fluorinated alkylene group for Y ¹ include groups in which some or all of the hydrogen atoms of the alkylene group have been substituted with fluorine atoms.
As Y ^1, _{specifically, -CF 2 -, - CF 2} CF 2 -, - CF 2 CF 2 CF 2 -, - CF (CF 3) CF 2 -, - CF (CF 2 CF 3) -, _{-C (CF 3) 2 -,} - CF 2 CF 2 CF 2 CF 2 -, - CF (CF 3) CF 2 CF 2 -, - CF 2 CF (CF 3) CF 2 -, - CF (CF 3) CF (CF ₃ ) —, —C (CF ₃ ) ₂ CF ₂ —, —CF (CF ₂ CF ₃ ) CF ₂ —, —CF (CF ₂ CF ₂ CF ₃ ) —, —C (CF ₃ ) (CF _{2 CF 3) -; - CHF} -, - CH 2 CF 2 -, - CH 2 CH 2 CF 2 -, - CH 2 CF 2 CF 2 -, - CH (CF 3) CH 2 -, - CH (CF 2 _{CF 3) -, - C (} CH 3) (CF 3) -, - CH 2 CH 2 CH 2 CF 2 -, - C H ₂ CH ₂ CF ₂ CF ₂ —, —CH (CF ₃ ) CH ₂ CH ₂ —, —CH ₂ CH (CF ₃ ) CH ₂ —, —CH (CF ₃ ) CH (CF ₃ ) —, —C ( _{CF 3) 2 CH 2 -;} - CH 2 -, - CH 2 CH 2 -, - CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 -, - CH (CH 2 CH 3) -, - _{C (CH 3) 2 -,} - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 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) CH 2 -, - CH (CH 2 CH 2 CH 3) -, - C (CH 3) (CH 2 CH ₃ ) — and the like.

Y ¹ is preferably a fluorinated alkylene group, and particularly preferably a fluorinated alkylene group in which the carbon atom bonded to the adjacent sulfur atom is fluorinated. Examples of such fluorinated alkylene _{group, -CF 2 -, - CF 2} CF 2 -, - CF 2 CF 2 CF 2 -, - CF (CF 3) CF 2 -, - CF 2 CF 2 CF 2 CF 2 _{-, - CF (CF 3)} CF 2 CF 2 -, - CF 2 CF (CF 3) CF 2 -, - CF (CF 3) CF (CF 3) -, - C (CF 3) 2 CF 2 -, _{-CF (CF 2 CF 3) CF} 2 -; - CH 2 CF 2 -, - CH 2 CH 2 CF 2 -, - CH 2 CF 2 CF 2 -; - CH 2 CH 2 CH 2 CF 2 -, - CH ₂ CH ₂ CF ₂ CF ₂ —, —CH ₂ CF ₂ CF ₂ CF ₂ — and the like can be mentioned.
Of _{these, -CF 2 -, - CF 2} CF 2 -, - CF 2 CF 2 CF 2 -, or _CH 2 _CF 2 CF ₂ - is _{preferable, -CF 2 -, - CF 2} CF 2 - or -CF ₂ CF ₂ CF ₂ - is more preferable, -CF ₂ - is particularly preferred.

The alkylene group or fluorinated alkylene group may have a substituent. An alkylene group or a fluorinated alkylene group has a “substituent” means that part or all of the hydrogen atom or fluorine atom in the alkylene group or fluorinated alkylene group is substituted with an atom or group other than a hydrogen atom and a fluorine atom. Means that
Examples of the substituent that the alkylene group or fluorinated alkylene group may have include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group.

In the formula ^{(b-2), R 5} "~R 6" are respectively similar to the ^R 5 ^{"~R 6"} in formula (g-c2).
"The, ^{R 4} in the above formula (b-1)" ^{R 4} in the formula (b-2) include the same as.

  Specific examples of the onium salt acid generators represented by formulas (b-1) and (b-2) include diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, bis (4-tert-butylphenyl) iodonium. Trifluoromethane sulfonate or nonafluorobutane sulfonate, triphenylsulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tri (4-methylphenyl) sulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its Nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfonium trifluoromethanesulfonate, its heptaful Lopropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of monophenyldimethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate; trifluoromethanesulfonate of diphenylmonomethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate (4-methylphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate , Trifluoromethanesulfonate of tri (4-tert-butyl) phenylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of diphenyl (1- (4-methoxy) naphthyl) sulfonium, its heptafluoropropane Sulfonate or its nonafluorobutane sulfonate, di (1-naphthyl) phenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1-phenyltetrahydrothiophenium trifluoromethanesulfonate, its heptafluoropropane sulfonate Or nonafluorobutanesulfonate thereof; 1- (4-methylphenyl) ) Tetrahydrothiophenium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, its heptafluoropropane sulfonate 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate; 1- (4-ethoxynaphthalene-1- Yl) tetrahydrothiophenium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonaflu 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate; 1-phenyltetrahydrothiopyranium trifluoromethanesulfonate , Its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1- (4-hydroxyphenyl) tetrahydrothiopyranium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate; 1- (3,5-dimethyl -4-Hydroxyphenyl) tetrahydrothiopyranium trifluoromethanesulfonate, its heptafluoropropanes Honeto or nonafluorobutanesulfonate; 1- (4-methylphenyl) trifluoromethanesulfonate tetrahydrothiophenium Pila chloride, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, and the like.

  In addition, the anion portion of these onium salts may be substituted with methanesulfonate, n-propanesulfonate, n-butanesulfonate, n-octanesulfonate, 1-adamantansulfonate, 2-norbornanesulfonate, or the like; d-camphor-10-sulfonate Further, onium salts substituted with sulfonates such as benzenesulfonate, perfluorobenzenesulfonate, and p-toluenesulfonate can also be used.

  Moreover, the onium salt which replaced the anion part of these onium salts by the anion represented by either of following formula (b1)-(b8) can also be used.

［式中、ｙは１〜３の整数であり、ｑ１〜ｑ２はそれぞれ独立に１〜５の整数であり、ｑ３は１〜１２の整数であり、ｔ３は１〜３の整数であり、ｒ１〜ｒ２はそれぞれ独立に０〜３の整数であり、ｉは１〜２０の整数であり、Ｒ^５０は置換基であり、ｍ１〜ｍ５はそれぞれ独立に０または１であり、ｖ０〜ｖ５はそれぞれ独立に０〜３の整数であり、ｗ１〜ｗ５はそれぞれ独立に０〜３の整数であり、Ｑ”は前記と同じである。］

[Wherein y is an integer of 1 to 3, q1 and q2 are each independently an integer of 1 to 5, q3 is an integer of 1 to 12, t3 is an integer of 1 to 3, and r1 ~ R2 is each independently an integer of 0 to 3, i is an integer of 1 to 20, R ⁵⁰ is a substituent, m1 to m5 are each independently 0 or 1, and v0 to v5 are each Each independently represents an integer of 0 to 3, w1 to w5 are each independently an integer of 0 to 3, and Q ″ is the same as defined above.]

As the substituent of R ^50, the same as those described as the substituent that the aliphatic hydrocarbon group may have and the substituent that the aromatic hydrocarbon group may have in the above R ^X Is mentioned.
Code (r1 and r2, w1 to w5) attached to R ⁵⁰ when it is 2 or more integer, a plurality of ^{R 50} in the compound may be the same, respectively, it may be different.

As the onium salt-based acid generator, in the general formula (b-1) or (b-2), the anion moiety ^(R 4 "SO ₃ ^-) of the following general formula (b-3) or (b- An onium salt acid generator substituted with the anion represented by 4) can also be used (the cation moiety is the same as the cation moiety in the formula (b-1) or (b-2)).

［式中、Ｘ”は、少なくとも１つの水素原子がフッ素原子で置換された炭素数２〜６のアルキレン基を表し；Ｙ”、Ｚ”は、それぞれ独立に、少なくとも１つの水素原子がフッ素原子で置換された炭素数１〜１０のアルキル基を表す。］

[Wherein X ″ represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; Y ″ and Z ″ each independently represent at least one hydrogen atom as a fluorine atom; Represents an alkyl group having 1 to 10 carbon atoms and substituted with

X ″ is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, Most preferably, it has 3 carbon atoms.
Y ″ and Z ″ are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably Has 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms.
The carbon number of the alkylene group of X ″ or the carbon number of the alkyl group of Y ″ and Z ″ is preferably as small as possible because the solubility in the resist solvent is good within the above carbon number range.
In addition, in the alkylene group of X ″ or the alkyl group of Y ″ and Z ″, as the number of hydrogen atoms substituted with fluorine atoms increases, the strength of the acid increases, and high-energy light or electron beam of 200 nm or less This is preferable because the transparency to the surface is improved.
The proportion of fluorine atoms in the alkylene group or 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. A perfluoroalkylene group or a perfluoroalkyl group.

As the onium salt-based acid generator, in the general formula (b-1) or (b-2), anion ^{- a, R h -COO (R 4 "} SO 3) - [ wherein, ^{R h} Is an alkyl group or a fluorinated alkyl group.] An onium salt-based acid generator substituted with a cation moiety can also be used (the cation moiety is the same as the cation moiety in the formula (b-1) or (b-2)).
In the above formula, examples of R ^h include the same as R ⁴ ″.
Specific examples of the “R ^h —COO ⁻ ” include trifluoroacetate ions, acetate ions, 1-adamantanecarboxylate ions and the like.

Further, as the onium salt acid generator, a sulfonium salt having a cation represented by the above general formula (g-c3) or (g-c4) in the cation part can also be used.
Furthermore, the sulfonium salt which has the cation represented by the said general formula (g-c5) or general formula (g-c6) in a cation part can also be used.

The anion part of the sulfonium salt having cations represented by the above formulas (g-c3) to (g-c6) in the cation part is not particularly limited, and the anion of the onium salt acid generators proposed so far It may be the same as the part. Examples of the anion moiety include fluorinated alkyl sulfonate ions such as the anion moiety (R ⁴ ″ SO ₃ ⁻ ) of the onium salt acid generator represented by the general formula (b-1) or (b-2). An anion represented by the general formula (b-3) or (b-4), an anion represented by any one of the formulas (b1) to (b8), and the like.

  In this specification, the oxime sulfonate acid generator is a compound having at least one group represented by the following general formula (B-1), and has a property of generating an acid upon irradiation (exposure) of radiation. It is what you have. Such oxime sulfonate-based acid generators are frequently used for chemically amplified resist compositions, and can be arbitrarily selected and used.

（式（Ｂ−１）中、Ｒ^３１、Ｒ^３２はそれぞれ独立に有機基を表す。）

(In formula (B-1), R ³¹ and R ³² each independently represents an organic group.)

The organic groups of R ³¹ and R ³² are groups containing carbon atoms, and atoms other than carbon atoms (for example, hydrogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms (fluorine atoms, chlorine atoms, etc.), etc.) You may have.
As the organic group for R ^31, a linear, branched, or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent. There is no restriction | limiting in particular as this substituent, For example, a fluorine atom, a C1-C6 linear, branched or cyclic alkyl group etc. are mentioned. Here, “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
As an alkyl group, C1-C20 is preferable, C1-C10 is more preferable, C1-C8 is more preferable, C1-C6 is especially preferable, and C1-C4 is the most preferable. As the alkyl group, a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable. The partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated alkyl group means that all of the hydrogen atoms are halogen atoms. Means an alkyl group substituted with Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.
The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. As the aryl group, a partially or completely halogenated aryl group is particularly preferable. The partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated aryl group means that all of the hydrogen atoms are halogen atoms. Means an aryl group substituted with.
R ³¹ is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.
As the organic group for R ^32, a linear, branched, or cyclic alkyl group, aryl group, or cyano group is preferable. As the alkyl group and aryl group for R ^32, the same alkyl groups and aryl groups as those described above for R ³¹ can be used.
R ³² is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.

  More preferable examples of the oxime sulfonate-based acid generator include compounds represented by the following general formula (B-2) or (B-3).

［式（Ｂ−２）中、Ｒ^３３は、シアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３４はアリール基である。Ｒ^３５は置換基を有さないアルキル基またはハロゲン化アルキル基である。］

[In Formula (B-2), R ³³ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁴ is an aryl group. R ³⁵ represents an alkyl group having no substituent or a halogenated alkyl group. ]

［式（Ｂ−３）中、Ｒ^３６はシアノ基、置換基を有さないアルキル基またはハロゲン化アルキル基である。Ｒ^３７は２または３価の芳香族炭化水素基である。Ｒ^３８は置換基を有さないアルキル基またはハロゲン化アルキル基である。ｐ”は２または３である。］

[In Formula (B-3), R ³⁶ represents a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁷ is a divalent or trivalent aromatic hydrocarbon group. ^R38 is an alkyl group having no substituent or a halogenated alkyl group. p ″ is 2 or 3.]

In the general formula (B-2), the alkyl group or halogenated alkyl group having no substituent of R ³³ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and carbon atoms. Numbers 1 to 6 are most preferable.
R ³³ is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group.
The fluorinated alkyl group for R ³³ is preferably such that the hydrogen atom of the alkyl group is 50% or more fluorinated, more preferably 70% or more fluorinated, and 90% or more fluorinated. Particularly preferred.
As the aryl group of R ³⁴ , one hydrogen atom is removed from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, or a phenanthryl group. And a heteroaryl group in which a part of carbon atoms constituting the ring of these groups is substituted with a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Among these, a fluorenyl group is preferable.
The aryl group of R ³⁴ may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group. The alkyl group or halogenated alkyl group in the substituent preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. The halogenated alkyl group is preferably a fluorinated alkyl group.
The alkyl group or halogenated alkyl group having no substituent of R ³⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.
R ³⁵ is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group.
The fluorinated alkyl group for R ³⁵ is preferably such that the hydrogen atom of the alkyl group is 50% or more fluorinated, more preferably 70% or more fluorinated, and 90% or more fluorinated. Particularly preferred is the strength of the acid generated. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.

In the general formula (B-3), the alkyl group or halogenated alkyl group having no substituent for R ³⁶ is the same as the alkyl group or halogenated alkyl group having no substituent for R ^33. Is mentioned.
Examples of the divalent or trivalent aromatic hydrocarbon group for R ³⁷ include groups obtained by further removing one or two hydrogen atoms from the aryl group for R ³⁴ .
Examples of the alkyl group or halogenated alkyl group having no substituent of R ³⁸ include the same alkyl groups or halogenated alkyl groups as those having no substituent of R ³⁵ .
p ″ is preferably 2.

Specific examples of the oxime sulfonate acid generator include α- (p-toluenesulfonyloxyimino) -benzyl cyanide, α- (p-chlorobenzenesulfonyloxyimino) -benzyl cyanide, α- (4-nitrobenzenesulfonyloxy). Imino) -benzylcyanide, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -benzylcyanide, α- (benzenesulfonyloxyimino) -4-chlorobenzylcyanide, α- (benzenesulfonyl) Oxyimino) -2,4-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -2,6-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -4-methoxybenzyl cyanide, α- ( 2-Chlorobenzenesulfonyloxyimino) 4-methoxybenzylcyanide, α- (benzenesulfonyloxyimino) -thien-2-ylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -benzylcyanide, α-[(p-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- (tosyloxyimino) -4-thienyl cyanide, α- (methylsulfonyloxyimino) -1-cyclo Pentenyl acetonitrile, α- (methylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -1-cycloheptenylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclooctene Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -cyclohexylacetonitrile, α- (ethylsulfonyloxyimino) -ethylacetonitrile, α- (propyl Sulfonyloxyimino) -propylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclohexylacetonitrile, α- (cyclohexylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- ( Ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclope N-tenyl acetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile , Α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (trifluoro Methylsulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -p- Butoxy phenylacetonitrile, alpha-(propylsulfonyl oxyimino)-p-methylphenyl acetonitrile, alpha-like (methylsulfonyloxyimino)-p-bromophenyl acetonitrile.
Further, an oxime sulfonate-based acid generator disclosed in JP-A-9-208554 (paragraphs [0012] to [0014] [chemical formula 18] to [chemical formula 19]), pamphlet of International Publication No. 04/074242, An oxime sulfonate-based acid generator disclosed in Examples 1 to 40) on pages 65 to 85 can also be suitably used.
Moreover, the following can be illustrated as a suitable thing.

Among diazomethane acid generators, specific examples of bisalkyl or bisarylsulfonyldiazomethanes include bis (isopropylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, Examples include bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, and the like.
Further, diazomethane acid generators disclosed in JP-A-11-035551, JP-A-11-035552, and JP-A-11-035573 can also be suitably used.
Examples of poly (bissulfonyl) diazomethanes include 1,3-bis (phenylsulfonyldiazomethylsulfonyl) propane and 1,4-bis (phenylsulfonyldiazo) disclosed in JP-A-11-322707. Methylsulfonyl) butane, 1,6-bis (phenylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (phenylsulfonyldiazomethylsulfonyl) decane, 1,2-bis (cyclohexylsulfonyldiazomethylsulfonyl) ethane, 1,3 -Bis (cyclohexylsulfonyldiazomethylsulfonyl) propane, 1,6-bis (cyclohexylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfonyldiazomethylsulfonyl) decane, etc. Door can be.

As the component (B), one type of acid generator described above may be used alone, or two or more types may be used in combination.
0.5-60 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of (B) component in the resist composition of this invention, 1-50 mass parts is more preferable, 1-40 mass parts Is more preferable. By setting it within the above range, pattern formation is sufficiently performed. Moreover, when each component of a resist composition is melt | dissolved in the organic solvent, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

<Other ingredients>
The resist composition of the present invention may further contain an amine component (D) (hereinafter referred to as “component (D)”) that does not fall under the above-described components as long as the effects of the present invention are not impaired. .
The component (D) is not particularly limited as long as it acts as an acid diffusion control agent, that is, a quencher that traps acid generated from the component (B) by exposure, for example. Since it has been proposed, any known one may be used. Specific examples include amines such as aliphatic amines and aromatic amines, among which aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines are preferred.
An aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 20 carbon atoms.
Examples of the aliphatic amine include an amine (alkylamine or alkyl alcohol amine) or a cyclic amine in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or hydroxyalkyl group having 20 or less carbon atoms. .
The alkyl group and the alkyl group in the hydroxyalkyl group may be linear, branched or cyclic.
When the alkyl group is linear or branched, the carbon number thereof is more preferably 2-20, and further preferably 2-8.
When the alkyl group is cyclic (when it is a cycloalkyl group), the carbon number is preferably 3 to 30, more preferably 3 to 20, still more preferably 3 to 15, and 4 to 12 carbon atoms. It is particularly preferred that the number of carbon atoms is 5-10. The alkyl group may be monocyclic or polycyclic. Specific examples include groups in which one or more hydrogen atoms have been removed from monocycloalkane, groups in which one or more hydrogen atoms have been removed from polycycloalkanes such as bicycloalkane, tricycloalkane, and tetracycloalkane. . Specific examples of the monocycloalkane include cyclopentane and cyclohexane. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
Specific examples of the alkylamine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di-n- Dialkylamines such as heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri- and trialkylamines such as n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, and tri-n-dodecylamine.
Specific examples of the alkyl alcohol amine include diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, stearyl diethanolamine, lauryldiethanolamine and the like.
Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).
Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
As the aliphatic polycyclic amine, those having 6 to 10 carbon atoms are preferable. Specifically, 1,5-diazabicyclo [4.3.0] -5-nonene, 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, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2- {2- (2-hydroxyethoxy) ) Ethoxy} ethyl] amine and the like.
Examples of the aromatic amine include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, and tribenzylamine.
These may be used alone or in combination of two or more.
(D) component is normally used in 0.01-5.0 mass parts with respect to 100 mass parts of (A) component. By setting the content in the above range, the resist pattern shape, the stability over time, and the like are improved.

The resist composition of the present invention is at least selected from the group consisting of phosphorus oxoacids and derivatives thereof as an optional component for the purpose of preventing sensitivity deterioration and improving the resist pattern shape, retention time stability, etc. One type of compound (E) (hereinafter referred to as “component (E)”) may be contained.
Examples of phosphorus oxo acids include phosphoric acid, phosphonic acid, and phosphinic acid. Among these, phosphonic acid is particularly preferable.
Examples of the oxo acid derivative of phosphorus include esters in which the hydrogen atom of the oxo acid is substituted with a hydrocarbon group, and the hydrocarbon group includes an alkyl group having 1 to 5 carbon atoms and 6 to 6 carbon atoms. 15 aryl groups and the like.
Examples of phosphoric acid derivatives include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.
Examples of phosphonic acid derivatives 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 phosphinic acid derivatives include phosphinic acid esters such as phenylphosphinic acid.
(E) A component may be used individually by 1 type and may use 2 or more types together.
(E) A component is normally used in 0.01-5.0 mass parts with respect to 100 mass parts of (A) component.

The resist composition of the present invention may contain a fluorine additive (hereinafter referred to as “component (F)”) in order to impart water repellency to the resist film.
By further containing the component (F), the hydrophobicity of the resist film surface is increased and the occurrence of defects after development is further suppressed.
As the component (F), for example, a fluorine-containing polymer compound described in JP 2010-002870 A can be used.
Specific examples of the component (F) include a copolymer having a structural unit represented by the following general formula (f1). More specifically, a polymer (homopolymer) consisting only of a structural unit represented by the following formula (f1), a copolymer of the structural unit represented by the following formula (f1) and the structural unit (a1) A copolymer of a structural unit represented by the following formula (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1) is preferable. Among the structural units (a1), the structural unit represented by the formula (a1-1-32) is particularly preferable.

［式中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基であり、Ｒ^７”はフッ素原子を含む有機基であり、Ｒ^８”は置換基を有していてもよい炭素数１〜５のアルキレン基である。］

Wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, R ⁷ ″ is an organic group containing a fluorine atom, and R ⁸ ″ is a substituent. It is a C1-C5 alkylene group which may have. ]

In the formula (f1), R ⁷ ″ is an organic group containing a fluorine atom, preferably a hydrocarbon group containing a fluorine atom. The hydrocarbon group containing a fluorine atom is more preferably a fluorinated alkyl group. Further, a fluorinated alkyl group having 1 to 5 carbon atoms is more preferable. Among them, as R ⁷ ″, a group represented by “— (CH ₂ ) o—CF ₃ ” is preferable (wherein, o is CH _2). Is an integer of 1 to 3).
In formula (f1), the carbon number of the alkylene group of R ⁸ ″ is 1 to 5, preferably 1 to 3, and more preferably 1 or 2. The hydrogen atom of the alkylene group of R ⁸ ″. May be substituted with a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms.
In the formula (f1), R is the same as described above. R is preferably a hydrogen atom or a methyl group.
(F) A component may be used individually by 1 type and may use 2 or more types together.
The content of the component (F) in the resist composition is preferably 1 to 10 parts by mass per 100 parts by mass of the component (A). By making content of (F) component into the said range, the hydrophobicity of the resist film surface increases, and the defect generation after image development is suppressed more.

  The resist composition of the present invention may further contain, if desired, miscible additives such as an additional resin for improving the performance of the resist film, a surfactant for improving coatability, a dissolution inhibitor, Plasticizers, stabilizers, colorants, antihalation agents, dyes, and the like can be added and contained as appropriate.

The resist composition of the present invention can be produced by dissolving the material in an organic solvent (hereinafter sometimes referred to as “(S) component”).
As the component (S), any component can be used as long as it can dissolve each component to be used to form a uniform solution. Conventionally, any one of known solvents for chemically amplified resists can be used. Two or more types can be appropriately selected and used.
For example, lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; Monohydric alcohols; compounds having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, monomethyl ether, monoethyl of the polyhydric alcohols or compound having the ester bond Ether alkyl such as ether, monopropyl ether, monobutyl ether or monophenyl ether Derivatives of polyhydric alcohols such as compounds having a propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monomethyl ether (PGME) among these]; cyclic ethers such as dioxane, methyl lactate, Esters such as ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, Aromatic organics such as dibenzyl ether, phenetol, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene A solvent etc. can be mentioned.
These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.
Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and EL are preferable.
Moreover, the mixed solvent which mixed PGMEA and the polar solvent is also preferable. The blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. It is preferable to be within the range. For example, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Moreover, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, More preferably, it is 3: 7-7: 3. Further, when PGME and cyclohexanone are blended as polar solvents, the mass ratio of PGMEA: (PGME + cyclohexanone) is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, and even more preferably 3. : 7 to 7: 3.
In addition, as the component (S), PGMEA, EL or a mixed solvent of PGMEA and a polar solvent and a mixed solvent of γ-butyrolactone are also preferable. In this case, the mixing ratio of the former and the latter is preferably 70:30 to 95: 5.
The amount of component (S) used is not particularly limited, but is a concentration that can be applied to a substrate or the like, and is appropriately set according to the coating film thickness. In general, the solid content concentration of the resist composition is 1 -20% by mass, preferably 2-15% by mass.

When forming a resist pattern using the resist composition of the present invention described above, as described above, the component (G) present in the unexposed portion of the resist film includes, for example, acids and ions generated from the component (B). Performs an exchange reaction and has an effect of suppressing the phenomenon of acid diffusion. On the other hand, the component (G) present in the exposed portion of the resist film is decomposed by exposure and loses basicity with respect to the acid generated from the component (B), for example. By these actions, according to the resist composition of the present invention, the lithography properties, the resist pattern shape and the like can be improved.
In addition, the resist composition of the present invention has an effect that it is possible to suppress dimensional fluctuations of the resist pattern due to the influence of time. The reason is not clear, but is presumed as follows.
In general, in addition to the base component (A) and the acid generator component (B), the resist composition includes an amine component for controlling the diffusion of acid generated from the component (B) by exposure. Etc. are suitably blended.
In such a resist composition, there is a problem that the dimension of the resist pattern formed before and after the storage fluctuates by preparing the resist composition and storing it for a certain period.
This problem is presumed to be due to the decomposition (deterioration with time) of the other compounding components due to the interaction between the amine component and the other compounding components in the resist composition.
In the resist composition of the present invention, the combination of the specific (G) component and the (H) component further reduces the nucleophilicity of the (G) component to other compounding components during the storage period. Then, since the decomposition (deterioration with time) of the other compounding components is suppressed, it is estimated that the dimensional change of the resist pattern formed before and after storage is small.

≪Resist pattern formation method≫
The resist pattern forming method of the present invention includes a step of forming a resist film on a support using the resist composition of the present invention, a step of exposing the resist film, and developing the resist film to form a resist pattern. Forming.
The resist pattern forming method of the present invention can be performed, for example, as follows.
That is, first, the resist composition of the present invention is applied onto a support with a spinner or the like, and a baking (post-apply bake (PAB)) treatment is performed, for example, at a temperature of 80 to 150 ° C. for 40 to 120 seconds, preferably A resist film is formed by applying for 60 to 90 seconds.
Next, the resist film is exposed through a mask (mask pattern) on which a predetermined pattern is formed using an exposure apparatus such as an ArF exposure apparatus, an electron beam drawing apparatus, or an EUV exposure apparatus, or a mask pattern. After performing selective exposure by drawing or the like by direct irradiation with an electron beam without passing through, baking (post-exposure baking (PEB)) treatment is performed, for example, at a temperature of 80 to 150 ° C. for 40 to 120 seconds, preferably 60 Apply for ~ 90 seconds.
Next, the resist film is developed.
The development treatment is performed using an alkaline developer in the case of an alkali development process, and using a developer (organic developer) containing an organic solvent in the case of a solvent development process.
A rinsing treatment is preferably performed after the development treatment. The rinse treatment is preferably a water rinse using pure water in the case of an alkali development process, and is preferably a rinse solution containing an organic solvent in the case of a solvent development process.
In the case of a solvent development process, after the development process or the rinse process, a process of removing the developer or rinse liquid adhering to the pattern with a supercritical fluid may be performed.
Drying is performed after development or rinsing. In some cases, a baking process (post-bake) may be performed after the development process. In this way, a resist pattern can be obtained.

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

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

The exposure method of the resist film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or may be immersion exposure (Liquid Immersion Lithography).
In immersion exposure, the space between the resist film and the lowermost lens of the exposure apparatus is filled with a solvent (immersion medium) having a refractive index larger than that of air in advance, and exposure (immersion exposure) is performed in that state. It is an 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 such a 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 fluorine-based inert liquid include a fluorine-based compound such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , and C ₅ H ₃ F ₇ as a main component. Examples thereof include liquids, and those having a boiling point of 70 to 180 ° C are preferable, and those having a boiling point of 80 to 160 ° C are more preferable. It is preferable that the fluorine-based inert liquid has a boiling point in the above range since the medium used for immersion can be removed by a simple method after the exposure is completed.
As the fluorine-based inert liquid, a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms is particularly preferable. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.
More specifically, examples of the perfluoroalkyl ether compound include perfluoro (2-butyl-tetrahydrofuran) (boiling point: 102 ° C.). Examples of the perfluoroalkylamine compound include perfluorotributylamine ( Boiling point of 174 ° C.).
As the immersion medium, water is preferably used from the viewpoints of cost, safety, environmental problems, versatility, and the like.

Examples of the alkali developer used for the development treatment in the alkali development 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 development process in the solvent development process is not particularly limited as long as it can dissolve the component (A) (component (A) before exposure). It can be selected as appropriate. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.
A known additive can be blended in the organic developer as required. Examples of the additive include a surfactant. The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.
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. 0% with respect to the total amount of the organic developer. 5 mass% is more preferable.
The development process can be carried out by a known development method, for example, a method in which a support is immersed in a developer for a certain period of time (dip method), a developer is raised on the surface of the support by surface tension, and is left for a certain period of time. (Paddle method), spraying developer on the surface of the support (spray method), coating the developer while scanning the developer coating nozzle at a constant speed on the support rotating at a constant speed The method to continue (dynamic dispensing method) etc. are mentioned.

As the organic solvent contained in the rinsing liquid used for the rinsing treatment after the development process in the solvent development process, for example, among the organic solvents mentioned as the organic solvent contained in the organic developer, those which are difficult to dissolve the resist pattern are appropriately used. You can select and use. Usually, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. Among these, at least one selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents and amide solvents is preferable, and at least one selected from alcohol solvents and ester solvents is preferable. More preferred are alcohol solvents.
The rinse treatment (washing treatment) using the rinse liquid can be performed by a known rinse method. Examples of the method include a method of continuously applying a rinsing liquid on a support rotating at a constant speed (rotary coating method), a method of immersing the support in a rinsing liquid for a predetermined time (dip method), and the surface of the support. And a method of spraying a rinse liquid (spray method).

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.
In this example, the compound represented by the chemical formula (1) is described as “compound (1)”, and the compounds represented by other chemical formulas are also described in the same manner.

[Polymer synthesis example 1 (synthesis of copolymer (2))]
In a separable flask equipped with a thermometer, a reflux tube and a nitrogen introduction tube, 12.00 g (70.52 mmol) of compound (1), 12.60 g (39.83 mmol) of compound (2), and 20. 77 g (79.15 mmol) of compound (3), 5.85 g (34.75 mmol) of compound (4), 6.95 g (29.43 mmol) of compound (5), 1.61 g (3.08 mmol) ) Compound (6) was dissolved in 76.81 g of methyl ethyl ketone (MEK). To this solution, 4.14 g (17.97 mmol) of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator.
This was dripped at 41.66 g of MEK over 4 hours at 80 ° C. in a nitrogen atmosphere. After completion of dropping, the reaction solution was stirred for 1 hour while being heated to 80 ° C., and then the reaction solution was cooled to room temperature.
The obtained reaction polymerization liquid was dropped into a large amount of n-heptane, and an operation for precipitating the polymer was performed. The precipitated white powder was filtered and dried, and the target copolymer (2) 27 0.08 g was obtained.
The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement for this copolymer (2) was 7600, and the molecular weight dispersity (Mw / Mn) was 1.68. The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz — ¹³ C-NMR) is 1 / m / n / o / p / It was q = 34.7 / 23.5 / 16.3 / 14.5 / 9.8 / 1.2.

[Polymer synthesis examples 2 to 9 (synthesis of copolymers (1) and (3) to (9))]
Copolymers (1) and (3) to (9) are the same as those described above except that the following compounds (1) to (10) for deriving structural units constituting each copolymer were used in a predetermined molar ratio. Synthesis was performed in the same manner as in Synthesis Example 1.
For each copolymer, a compound that derives each structural unit, a copolymer composition ratio determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz — ¹³ C-NMR), a mass average molecular weight in terms of standard polystyrene determined by GPC measurement, and a molecular weight The degree of dispersion (Mw / Mn) is shown in Table 1.

<Preparation of resist composition>
[Examples 1 to 52, Comparative Examples 1 to 20]
Resist compositions were prepared by mixing and dissolving the components shown in Tables 2-6.

In Tables 2-6, the numerical value in [] is a compounding quantity (mass part), and each abbreviation shows the following, respectively.
(A) -1 to (A) -9: Copolymer (1) to Copolymer (9).
(B) -1: a compound represented by the following chemical formula (B) -1.

  (G) -1 to (G) -11: Compounds represented by the following chemical formulas (G) -1 to (G) -11.

  (H) -1 to (H) -11: Compounds represented by the following chemical formulas (H) -1 to (H) -11.

(S) -1: γ-butyrolactone.
(S) -2: mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 6/4 (mass ratio).

<Formation of resist pattern>
An organic antireflection film composition “ARC-29A” (trade name, manufactured by Brewer Science Co., Ltd.) was applied on an 8-inch silicon wafer using a spinner, and baked on a hot plate at 205 ° C. for 60 seconds. By drying, an organic antireflection film having a film thickness of 82 nm was formed.
Next, each of the above resist compositions is applied onto the antireflection film using a spinner, and prebaked (PAB) for 60 seconds at a temperature shown in the following table on a hot plate, followed by drying. Thus, a resist film having a thickness of 150 nm was formed.
Next, an ArF exposure apparatus NSR-S302 (manufactured by Nikon; NA (numerical aperture) = 0.60, 2/3 annular illumination) is applied to the resist film through a mask (6% halftone). ArF excimer laser (193 nm) was selectively irradiated.
Then, a post-exposure heating (PEB) treatment was performed for 60 seconds at the temperature shown in the following table, and a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution “NMD-3” (trade name, (Tokyo Ohka Kogyo Co., Ltd.) was subjected to an alkali development treatment for 30 seconds, rinsed with pure water for 30 seconds, and then shaken off and dried.
As a result, in each example, a space-and-line resist pattern (hereinafter referred to as “SL pattern”) in which spaces having a space width of 120 nm are arranged at equal intervals (pitch 240 nm) was formed on the resist film.
The optimum exposure amount Eop (mJ / cm ² ) at which such an SL pattern is formed, that is, the sensitivity was obtained. The results are shown in the table.

[Evaluation of line width roughness (LWR)]
In accordance with the same procedure as the formation of the resist pattern, a length measurement SEM (scanning electron microscope, accelerating voltage 800 V, trade name: S-9380, Hitachi High) was used in the SL pattern formed by Eop with a space width of 120 nm and a pitch of 240 nm. Measured at 400 locations in the longitudinal direction of the space by Technologies, Inc.), and obtained the value of 3 times the standard deviation (s) (3 s) from the result, and averaged the values for 3 s in 5 locations. Was calculated as a measure of LWR. The results are shown in the table as “LWR (nm)”.
The smaller the value of 3s, the smaller the roughness of the line width, which means that a more uniform SL pattern was obtained.

[Evaluation of mask error factor (MEF)]
According to the same procedure as the formation of the resist pattern, in the Eop, using a mask pattern targeting a SL pattern having a space width of 120 nm and a pitch of 260 nm and a mask pattern targeting a SL pattern having a space width of 130 nm and a pitch of 260 nm. Each SL pattern was formed, and the MEF value was determined from the following equation. The results are shown in the table as “MEF”.
MEF = | CD ₁₃₀ −CD ₁₂₀ | / | MD ₁₃₀ −MD ₁₂₀ |
In the above formula, CD ₁₃₀ and CD ₁₂₀ are the actual space widths (nm) of the SL patterns formed using the mask patterns targeting the space widths 130 nm and 120 nm, respectively. MD ₁₃₀ and MD ₁₂₀ are space widths (nm) targeted by the mask pattern, respectively, and MD ₁₃₀ = 130 and MD ₁₂₀ = 120.
The closer this MEF value is to 1, the more the resist pattern faithful to the mask pattern is formed.

[Evaluation of exposure margin (EL margin)]
In Eop, the exposure amount when the space of the SL pattern is formed within a range of ± 5% (114 nm to 126 nm) of the target dimension (space width 120 nm) is obtained, and the EL margin (unit:%) is calculated by the following equation. Asked. The results are shown in the table as “EL (%)”.
EL margin (%) = (| E1-E2 | / Eop) × 100
E1: Exposure amount when an SL pattern having a space width of 114 nm was formed (mJ / cm ² )
E2: exposure amount (mJ / cm ² ) when an SL pattern having a space width of 126 nm was formed
Note that the larger the value of the EL margin, the smaller the change amount of the pattern size accompanying the change in the exposure amount.

[Evaluation of resist pattern shape]
The SL pattern having a space width of 120 nm and a pitch of 240 nm formed by Eop was observed using a scanning electron microscope SEM (product name SU8000, manufactured by Hitachi High-Technologies Corporation), and the cross-sectional shape of the SL pattern was evaluated. The results are shown in the table.

[Proportion (molar ratio) of the content of the component (G) and component (H) contained in the resist composition]
In the resist composition of each example, the ratio (molar ratio) of the amount of substance contained in the resist composition of the component (G) and the component (H) was calculated. The results are shown in the table as the molar ratio (G) :( H) molar ratio of component (H) to component (G).
About Examples 1-38, 45, 52, and Comparative Examples 1 and 2, the molar ratio in case both (G) component and (H) component are low molecular weight compounds (additive) is shown.
About Examples 39-43 and 46-50, the molar ratio in case (G) component is resin (base-material component) and (H) component is a low molecular weight compound (additive) is shown.
About Example 44 and 51, the molar ratio in case (G) component is a low molecular compound (additive) and (H) component is resin (base material component) is shown.

As an example, “(G) :( H) molar ratio” in Example 39 will be described.
In Example 39, the component (G) is a resin (base material component), and the component (H) is a low molecular compound (additive).
-Content amount of (G) component The copolymer (2) is used as the (G) component (base component (A)). From the following procedures (1) to (3), the content of the component (G) is determined (see Table 7).
Procedure (1): In the copolymer (2), the proportion of structural units derived from the compound (6) corresponding to the component (G) is 1.2 mol%.
Procedure (2): From the proportion (molar ratio) of the structural units determined in Procedure (1), when the total resin (the copolymer (2)) is 100 (parts by mass), it is derived from the compound (6). The ratio (mass ratio) of the structural units to be obtained is 2.73 [= (523.59 × 1.2 / 100) /2299.99×100].
Procedure (3): The proportion (mass ratio) of the structural units determined in Procedure (2) is regarded as the mass of the compound (6), and the content of the compound (6) is determined to be 5.21 (mmol) (= 2.73 / 523.59 × 10 ³ ).

-Content amount of component (H) (H) -2 (molecular weight 355.11) is used as the component (H) (additive).
In the resist composition, the content of (H) -2 is 3.39 parts by mass with respect to 100 parts by mass of component (A). From this, the content amount of (H) -2 is calculated to be 9.55 (mmol) (= 3.39 / 355.11 × 10 ³ ).
-(G): (H) molar ratio The ratio (molar ratio) of the amount of substances contained in the resist composition of the (G) component and the (H) component is as follows. (G) :( H) molar ratio = 1: (9.55 / 5.21) ≈1: 1.8.

[Evaluation of resist pattern dimensional variation due to aging]
The resist composition of each example is the same as the above Eop by the same method as the formation of the resist pattern, using a resist composition that has been frozen for one month (frozen) and a one that has been stored at room temperature for one month (room temperature). SL patterns having a space width of 120 nm and a pitch of 240 nm were respectively formed with the exposure amount of.
And the line width (dimension) of the predetermined position of each SL pattern formed by the frozen preservation goods and the room temperature preservation goods was measured, and both dimensional difference was calculated | required.
When the dimensional difference between the two is 2% or less, ◎◎ When it is over 2% and 5% or less ◎ When it is over 5% and 10% or less ○ When it is over 10% and 50% or less △, and the case where the SL pattern could not be formed in one or both of the frozen storage product and the room temperature storage product was evaluated as x, and the dimensional variation of the resist pattern due to the influence of time was evaluated. The results are shown in the table as “CD change after 1M”.

  From the results shown in the table, it can be seen that the resist compositions of Examples 1 to 52 to which the present invention is applied have excellent lithographic properties and resist pattern shapes while suppressing dimensional variations due to the influence of time.

From Examples 1 to 3, it was confirmed that the dimensional variation due to the influence of time could be more effectively suppressed when the content of the compound (H) was equal to or greater than the content of the compound (G).
In addition, the combination of the (G) component and the (H) component is preferably in consideration of the pKa value and the like from the viewpoint of suppressing dimensional variation due to the influence of time.
In addition, when a compound having the same structure as the component (G) is used as the component (H) (Examples 1 to 12, Example 45, Example 52), dimensional variation due to the influence of time can be suppressed, and It was confirmed that LWR or MEF was further improved (Examples 13 to 16 for Example 4, Examples 17 to 20 for Example 6, Examples 21 to 24 for Example 7, Example 25 for Example 8) ~ 28).

Claims (11)

A compound (G) having a monovalent group represented by the following general formula (g1) or a monovalent group represented by the general formula (g2);
A resist composition comprising: a monovalent group represented by the following general formula (h1) or a compound (H) having a monovalent group represented by the general formula (h2).

[In the formula (g1), R ² represents a single bond or a —C (═O) —O— group. However, if R ² is a single bond, N in the formula ^- is -C (= O) - those that bind to groups and are not included in the component (G). R ³ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. M ⁺ is each independently an organic cation. ]

[In the formula (h1), R ⁶ represents a single bond or a —C (═O) —O— group. R ⁷ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. ]   The resist composition according to claim 1, wherein the content of the compound (H) is greater than or equal to the content of the compound (G). The compound (G) is selected from the group consisting of a compound (Gm-1) represented by the following general formula (g1-1) and a compound (Gm-2) represented by the following general formula (g2-1). The resist composition according to claim 1, comprising a resin component having a structural unit (g ′) derived from at least one compound.

[In formula (g1-1), R ^P1 is a monovalent group represented by any of the following general formula (I) or general formula (II). R ² is a single bond or a —C (═O) —O— group. However, if R ² is a single bond, N in the formula ^- is -C (= O) - those that bind to groups and are not included in the component (G). R ³ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. In formula (g2-1), R ^P2 is a monovalent group represented by any of the following general formulas (I) to (III). X each independently represents a single bond or a divalent linking group. M ⁺ is each independently an organic cation. ]

[In formulas (I) to (III), R ^a is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and R ⁿ is a hydrogen atom or 1 to 5 carbon atoms. 5 alkyl groups. ] The compound (H) is selected from the group consisting of a compound (Hm-1) represented by the following general formula (h1-1) and a compound (Hm-2) represented by the following general formula (h2-1). The resist composition as described in any one of Claims 1-3 containing the resin component which has a structural unit (h ') induced | guided | derived from the at least 1 type of compound.

[In formula (h1-1), R ^P1 is a monovalent group represented by either the general formula (I) or the general formula (II). R ⁶ is a single bond or a —C (═O) —O— group. R ⁷ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. In the formula (h2-1), R ^P2 is a monovalent group represented by any one of the general formulas (I) to (III). X each independently represents a single bond or a divalent linking group. ]   The resin component is a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, and the acid-decomposability that increases polarity by the action of an acid The resist composition of Claim 3 or 4 which has a structural unit containing group. The compound (G) is the compound (Gm-1) in claim 3, the compound (Gm-2) in claim 3, or the compound (Gm-3) represented by the following general formula (g1-2) And at least one compound selected from the group consisting of the compound (Gm-4) represented by formula (g2-2) and the resist composition according to any one of claims 1 to 5.

[In Formula (g1-2), R ¹ is a fluorine atom, a hydroxy group, —O—R ¹⁰ group, —NH—C (═O) —R ¹⁰ group, —O—C (═O) —R ¹⁰ group. Or -C (= O) -O-R ¹⁰ group (where R ¹⁰ is a linear or branched monovalent alkyl group having 1 to ¹⁰ carbon atoms, or cyclic monovalent group having 3 to 20 carbon atoms) Or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, which may be substituted with a linear or branched chain group having 1 to 20 carbon atoms. A monovalent hydrocarbon group, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom. R ² is a single bond or a —C (═O) —O— group. However, if R ² is a single bond, N in the formula ^- is -C (= O) - those that bind to groups and are not included in the component (G). R ³ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. In formula (g2-2), R ⁴ represents a fluorine atom, a hydroxy group, —O—R ¹⁰ group, —O—C (═O) —R ¹⁰ group, or —C (═O) —O—R ¹⁰ group. (However, R ¹⁰ is a linear or branched monovalent alkyl group having 1 to ¹⁰ carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. A monovalent hydrocarbon group having a partial structure.) Which may be substituted with a linear or branched monovalent alkyl group having 1 to 20 carbon atoms or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. M ⁺ is each independently an organic cation. ] The compound (H) is the compound (Hm-1) in claim 4, the compound (Hm-2) in claim 4, or the compound (Hm-3) represented by the following general formula (h1-2) And at least one compound selected from the group consisting of the compound (Hm-4) represented by formula (h2-2) and the resist composition according to any one of claims 1 to 6.

[In the formula (h1-2), R ⁵ represents a fluorine atom, a hydroxy group, —O—R ¹⁰ group, —NH—C (═O) —R ¹⁰ group, —O—C (═O) —R ¹⁰ group. Or -C (= O) -O-R ¹⁰ group (where R ¹⁰ is a linear or branched monovalent alkyl group having 1 to ¹⁰ carbon atoms, or cyclic monovalent group having 3 to 20 carbon atoms) Or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, which may be substituted with a linear or branched chain group having 1 to 20 carbon atoms. A monovalent hydrocarbon group, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom. R ⁶ is a single bond or a —C (═O) —O— group. R ⁷ may be substituted with a fluorine atom, a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or It is a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. In the formula (h2-2), R ⁸ is a fluorine atom, a hydroxy group, —O—R ¹⁰ group, —O—C (═O) —R ¹⁰ group, or —C (═O) —O—R ¹⁰ group. (However, R ¹⁰ is a linear or branched monovalent alkyl group having 1 to ¹⁰ carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. A monovalent hydrocarbon group having a partial structure.) Which may be substituted with a linear or branched monovalent alkyl group having 1 to 20 carbon atoms or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms. ]   The resist composition as described in any one of Claims 1-7 containing the acid generator component (B) which generate | occur | produces an acid by exposure. The resist composition according to claim 1, wherein M ⁺ is an organic cation represented by the following general formula (g-c1).

[In formula (g-c1), R ¹ ″ to R ³ ″ each independently represents an aryl group, an alkyl group, or an alkenyl group which may have a substituent. Any two of R ¹ ″ to R ³ ″ may be bonded to each other to form a ring together with the sulfur atom in the formula. ]   A structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent, and having a structural unit containing an acid-decomposable group whose polarity is increased by the action of an acid The resist composition as described in any one of Claims 1-9 containing a polymer.   A step of forming a resist film using the resist composition according to claim 1 on a support, a step of exposing the resist film, and developing the resist film to form a resist pattern A resist pattern forming method including a forming step.