JP6782540B2 - Resist composition, resist pattern forming method and compound - Google Patents

Description

The present invention relates to resist compositions, resist pattern forming methods and compounds.

In lithography technology, for example, a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed to radiation such as light and electron beams through a mask on which a predetermined pattern is formed. And the development process is performed to form a resist pattern having a predetermined shape on the resist film.
A resist material whose exposed portion changes to a characteristic that dissolves in a developing solution is called a positive type, and a resist material whose exposed portion changes to a characteristic that does not dissolve in a developing solution is called a negative type.
In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization is rapidly progressing due to advances in lithography technology.
As a miniaturization method, generally, the wavelength of the exposure light source is shortened (energy is increased). Specifically, in the past, ultraviolet rays typified by g-rays and i-rays were used, but nowadays, mass production of semiconductor devices using KrF excimer lasers and ArF excimer lasers has started. Further, studies are being conducted on electron beams having a shorter wavelength (higher energy) than these excimer lasers, EUV (extreme ultraviolet), X-rays, and the like.

The resist material is required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern of fine dimensions.
Conventionally, as a resist material satisfying such a requirement, a chemically amplified resist composition containing a base material component whose solubility in a developing solution is changed by the action of an acid and an acid generator component that generates an acid by exposure has been used. It is used. For example, when the developer is an alkaline developer (alkali developing process), the positive chemically amplified resist composition includes a resin component (base resin) whose solubility in the alkaline developer is increased by the action of an acid, and an acid. Those containing a generator component are generally used. When a resist film formed using such a resist composition is selectively exposed at the time of forming a resist pattern, an acid is generated from an acid generator component in the exposed portion, and the polarity of the base resin is increased by the action of the acid. Then, the exposed part becomes soluble in the alkaline developer. Therefore, by alkaline development, a positive pattern in which the unexposed portion remains as a pattern is formed. On the other hand, when a solvent developing process using a developing solution containing an organic solvent (organic developing solution) is applied, as the polarity of the base resin increases, the solubility in the organic developing solution decreases relatively, so that the resist film The unexposed portion is dissolved and removed by an organic developer to form a negative resist pattern in which the exposed portion remains as a pattern. The solvent developing process for forming a negative resist pattern in this way is sometimes called a negative developing process (for example, Patent Document 1).

Generally, in the resist composition, in addition to the base material component and the acid generator component, a citric acid component such as an amine component is preferable in order to control the diffusion of the acid generated from the acid generator by exposure. (For example, Patent Document 2). In such a resist composition, the resist pattern formed before and after storage due to the interaction between the amine component and other compounding components by preparing the resist composition and storing it for a certain period of time. There was a problem that the dimensions fluctuated.
On the other hand, in Patent Document 2, for example, by combining two specific types of components as quencher components, decomposition (deterioration over time) of other compounded components during the storage period is suppressed.

JP-A-2009-025723 Japanese Unexamined Patent Publication No. 2013-35112

As resist patterns become finer and finer, resist materials are further required to have good lithography properties. There was still room for improvement in the resist material in order to suppress dimensional fluctuations due to the influence of time on the resist material and to achieve better lithography characteristics.
However, compounds with high quenching efficiency have a high risk over time, and on the contrary, compounds with low risk over time have low quenching efficiency. Was difficult to achieve at the same time.
The present invention has been made in view of the above circumstances, and provides a resist composition that suppresses dimensional fluctuation due to the influence of time and has good lithography characteristics, and a resist pattern forming method using the resist composition. Make it an issue.

The first aspect of the present invention is a resist composition which generates an acid by exposure and whose solubility in a developing solution is changed by the action of the acid, and comprises an acid generator component (B) which generates an acid by exposure. The resist composition is characterized by containing a photobase inactivating agent component (D0) containing a compound represented by the following general formula (d0).
A second aspect of the present invention is a step of forming a resist film using the resist composition of the first aspect, a step of exposing the resist film, and a step of developing the resist film after the exposure to form a resist pattern. This is a resist pattern forming method including a step of forming.
A third aspect of the present invention is a compound represented by the following general formula (d0).

［式中、Ｒ^１は置換基を有していてもよい炭素数１〜２０の鎖状、分岐鎖状又は環状の炭化水素基である。但し、式中のカルボニル基に隣接するＲ^１の炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。Ｒ^２は置換基を有していてもよい炭素数１〜２０の鎖状、分岐鎖状又は環状の炭化水素基である。但し、式中のスルホニル基に隣接するＲ^２の炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。Ｍ^ｍ＋はｍ価の有機カチオンである。ｍは１以上の整数である。］

[In the formula, R ¹ is a chain, branched chain or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. However, when a substituent is bonded to the carbon atom of R ¹ adjacent to the carbonyl group in the formula, the substituent is a group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more selected from. R ² is a chain, branched chain or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. However, if the substituent at a carbon atom of R ² adjacent to the sulfonyl group in the formula are bonded, the substituent group having a halogen atom, an aromatic group, and the group consisting of proton acceptor functional group It is assumed that there is no one or more selected from the above. M ^{m +} is an m-valent organic cation. m is an integer of 1 or more. ]

According to the present invention, it is possible to provide a resist composition that suppresses dimensional fluctuation due to the influence of time and has good lithography characteristics, and a resist pattern forming method using the resist composition.

As used herein and in the claims, "aliphatic" is defined as a relative concept to aromatics, meaning groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the "alkyl group" shall include linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, the "alkylene group" shall include linear, branched and cyclic divalent saturated hydrocarbon groups.
The "alkyl halide group" is a group in which a part or all of the hydrogen atom of the alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which a part or all of hydrogen atoms of the alkyl group or the alkylene group is substituted with a fluorine atom.
The "constituent unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When it is described that "it may have a substituent", when the hydrogen atom (-H) is replaced with a monovalent group and when the methylene group (-CH _2- ) is replaced with a divalent group. Includes both.
"Exposure" is a concept that includes general irradiation of radiation.

The “constituent unit derived from the acrylic acid ester” means a structural unit formed by cleaving the ethylenic double bond of the acrylic acid ester.
The "acrylic acid ester" is a compound in which the hydrogen atom at the terminal of the carboxy group of acrylic acid (CH ₂ = CH-COOH) is replaced with an organic group.
In the acrylic acid ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R ^α0 ) that replaces the hydrogen atom bonded to the carbon atom at the α-position is an atom or group other than the hydrogen atom, for example, an alkyl group having 1 to 5 carbon atoms and a halogenation having 1 to 5 carbon atoms. Alkyl groups and the like can be mentioned. In addition, itaconic acid diester in which the substituent (R ^α0 ) is substituted with a substituent containing an ester bond, and α-hydroxyacrylic ester in which the substituent (R ^α0 ) is substituted with a hydroxyalkyl group or a group modified with a hydroxyl group thereof are also available. It shall include. Unless otherwise specified, the carbon atom at the α-position of the acrylic acid ester is a carbon atom to which the carbonyl group of acrylic acid is bonded.
Hereinafter, an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent may be referred to as an α-substituted acrylic acid ester. Further, the acrylic acid ester and the α-substituted acrylic acid ester may be collectively referred to as “(α-substituted) acrylic acid ester”.

The "constituent unit derived from acrylamide" means a structural unit formed by cleavage of the ethylenic double bond of acrylamide.
In acrylamide, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, or one or both of the hydrogen atoms of the amino group of acrylamide may be substituted with a substituent. Unless otherwise specified, the carbon atom at the α-position of acrylamide is a carbon atom to which the carbonyl group of acrylamide is bonded.
As the substituent that replaces the hydrogen atom bonded to the carbon atom at the α-position of acrylamide, the same one as the substituent at the α-position (substituent (R ^α0 )) in the α-substituted acrylic acid ester is used. Can be mentioned.

"Constituent unit derived from hydroxystyrene or hydroxystyrene derivative" means a structural unit formed by cleaving the ethylenic double bond of hydroxystyrene or hydroxystyrene derivative.
The "hydroxystyrene derivative" is a concept including a hydrogen atom at the α-position of hydroxystyrene substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. Derivatives thereof include those in which the hydrogen atom at the α-position may be substituted with a substituent, and the hydrogen atom of the hydroxyl group of hydroxystyrene is substituted with an organic group; even if the hydrogen atom at the α-position is substituted with a substituent. Examples thereof include those in which a substituent other than the hydroxyl group is bonded to the benzene ring of a good hydroxystyrene. The α-position (carbon atom at the α-position) refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.
Examples of the substituent substituting the hydrogen atom at the α-position of hydroxystyrene include the same as those mentioned as the substituent at the α-position in the α-substituted acrylic acid ester.

"Constituent unit derived from vinyl benzoic acid or vinyl benzoic acid derivative" means a structural unit formed by cleavage of an ethylenic double bond of vinyl benzoic acid or a vinyl benzoic acid derivative.
The "vinyl benzoic acid derivative" is a concept including those in which the hydrogen atom at the α-position of vinyl benzoic acid is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. As those derivatives, the hydrogen atom at the α-position may be substituted with a substituent, and the hydrogen atom of the carboxy group of vinyl benzoic acid is substituted with an organic group; the hydrogen atom at the α-position is substituted with a substituent. Examples thereof include those in which a substituent other than a hydroxyl group and a carboxy group is bonded to the benzene ring of vinyl benzoic acid. The α-position (carbon atom at the α-position) refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The term "styrene derivative" is defined as including a derivative in which the hydrogen atom at the α-position of styrene is substituted with another substituent such as an alkyl group or an alkyl halide group.
“Constituent unit derived from styrene” and “constituent unit derived from styrene derivative” mean a structural unit formed by cleavage of an ethylenic double bond of styrene or a styrene derivative.

The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group). , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
Further, the alkyl halide group as the substituent at the α-position is specifically a group in which a part or all of the hydrogen atom of the above-mentioned "alkyl group as the substituent at the α-position" is substituted with a halogen atom. Be done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
Specific examples of the hydroxyalkyl group as the substituent at the α-position include a group in which a part or all of the hydrogen atom of the above-mentioned "alkyl group as the substituent at the α-position" is substituted with a hydroxyl group. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

≪Resist composition≫
The present invention is a resist composition in which an acid is generated by exposure and the solubility in a developing solution is changed by the action of the acid, and the acid generator component (B) that generates an acid by exposure and the general formula (d0). It is a resist composition which contains a photobase inactivating agent component (D0) containing a compound represented by.
In the present invention, the resist composition comprises a base material component (A) whose solubility in a developing solution changes due to the action of an acid (hereinafter, also referred to as “component (A)”) and an acid generator component that generates an acid upon exposure. (B) (hereinafter, also referred to as “component (B)”) is preferably contained.
When a resist film is formed using such a resist composition and selective exposure is performed on the resist film, an acid is generated in the exposed portion, and the action of the acid makes the component (A) soluble in a developing solution. On the other hand, since the solubility of the component (A) in the developing solution does not change in the unexposed portion, a difference in solubility in the developing solution occurs between the exposed portion and the unexposed portion. Therefore, when the resist film is developed, if the resist composition is a positive type, the exposed portion is dissolved and removed to form a positive type resist pattern, and if the resist composition is a negative type, the unexposed portion is dissolved. It is removed to form a negative resist pattern.
In the present 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 for forming a negative resist pattern in which an unexposed portion is dissolved and removed. Is called a negative resist composition.
In the present invention, the resist composition may be a positive resist composition or a negative resist composition.
Further, in the present invention, the resist composition may be used for an alkaline developing process in which an alkaline developing solution is used in the developing process at the time of forming a resist pattern, and a developing solution (organic developing solution) containing an organic solvent in the developing process. It may be for a solvent developing process using.

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

<Photobase deactivating agent component>
The resist composition of the present invention contains a photobase inactivating agent component (D0) (hereinafter, may be referred to as “(D0) component”) containing a compound represented by the following general formula (d0).
The component (D0) acts as a quencher (acid diffusion control agent) that traps acids generated from the component (B) described later, for example, by exposure, and contributes to the improvement of lithography characteristics.
Conventionally, it is known that a compound having a low pKa of a conjugate acid of the compound has a low quenching efficiency, and a compound having a high pKa of a conjugate acid has a high quenching efficiency.
On the other hand, a compound having a high pKa of a conjugate acid easily reacts with other polymers in the resist composition, and by interacting with other compounding components, decomposition (aging deterioration) of the other compounding components proceeds (in other words). If so, it is inferior in storage stability).
Therefore, as a result of diligent studies, the present inventors have adopted a photobase inactivating agent component (D0) containing a compound represented by the general formula (d0), thereby maintaining a high acid quenching effect and simultaneously storing the acid. We have developed a resist composition with excellent stability.

［式中、Ｒ^１は置換基を有していてもよい炭素数１〜２０の鎖状、分岐鎖状又は環状の炭化水素基である。但し、式中のカルボニル基に隣接するＲ^１の炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。Ｒ^２は置換基を有していてもよい炭素数１〜２０の鎖状、分岐鎖状又は環状の炭化水素基である。但し、式中のスルホニル基に隣接するＲ^２の炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。Ｍ^ｍ＋はｍ価の有機カチオンである。ｍは１以上の整数である。］

[In the formula, R ¹ is a chain, branched chain or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. However, when a substituent is bonded to the carbon atom of R ¹ adjacent to the carbonyl group in the formula, the substituent is a group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more selected from. R ² is a chain, branched chain or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. However, if the substituent at a carbon atom of R ² adjacent to the sulfonyl group in the formula are bonded, the substituent group having a halogen atom, an aromatic group, and the group consisting of proton acceptor functional group It is assumed that there is no one or more selected from the above. M ^{m +} is an m-valent organic cation. m is an integer of 1 or more. ]

In the formula (d0), R ¹ and R ² are chain, branched or cyclic hydrocarbon groups having 1 to 20 carbon atoms which may independently have a substituent.
As the chain or branched hydrocarbon group having 1 to 20 carbon atoms in R ¹ and R ² , an alkyl group having 1 to 10 carbon atoms is more preferable; as a linear or branched alkyl group, the alkyl group has a linear or branched chain structure. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylethyl group, 1,1 Preferred examples include −diethylpropyl group, 2,2-dimethylpropyl group, 2,2,-dimethylbutyl group, hexyl group, octyl group, nonyl group, decyl group and the like.
Of these, a methyl group, a t-butyl group and a decyl group are more preferable.

When the hydrocarbon groups having 1 to 20 carbon atoms in R ¹ and R ² are cyclic hydrocarbon groups, they may be aliphatic, polycyclic, or monocyclic. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 8 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, and cyclooctane. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing one hydrogen atom from polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically, adamantane. , Norbornane, cycloheptane, isobornane, tricyclodecane, tetracyclododecane and the like.
When the hydrocarbon groups having 1 to 20 carbon atoms in R ¹ and R ² are cyclic hydrocarbon groups, cyclohexane or adamantane is more preferable among the above.

The substituents that the hydrocarbon groups having 1 to 20 carbon atoms in R ¹ and R ² may have include, for example, an alkyl group, an oxygen atom (= O), -COOR ", and -OC (= O) R". , Hydrocarbon group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 6 carbon atoms is preferable. The alkyl group is preferably linear or branched. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and a hexyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
The R "in the -COOR" and -OC (= O) R "is a hydrogen atom or a linear, branched-chain 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, monocyclo Examples thereof include an alcohol, a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as bicycloalkane, tricycloalkane, and tetracycloalkane. More specifically, a monocycloalkane such as cyclopentane and cyclohexane and the like. , Adamantane, norbornan, isobornane, tricyclodecane, tetracyclododecane and other polycycloalkanes from which one or more hydrogen atoms have been removed.
The hydroxyalkyl group as the substituent preferably has 1 to 6 carbon atoms, and specifically, at least one of the hydrogen atoms of the alkyl group listed as the alkyl group as the substituent is substituted with a hydroxyl group. The group that was made is mentioned.

In the present invention, when a substituent on a carbon atom of R ¹ adjacent to the carbonyl group in the formula (d0) is attached, the substituent group having a halogen atom, an aromatic group, and proton acceptor It shall not have one or more selected from the group consisting of functional groups.
Also, if the substituent at a carbon atom of R ² adjacent to the sulfonyl group in the formula (d0) is attached, the substituent group having a halogen atom, an aromatic group, and a proton acceptor functional group It shall not have one or more species selected from the group consisting of.
Examples of the group having a halogen atom include only a halogen atom and an alkyl halide group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and it is preferable that the substituent does not have a fluorine atom.
Examples of the alkyl halide group include an alkyl halide group in which a part or all of hydrogen atoms in the alkyl group are substituted with a halogen atom (particularly a fluorine atom), and the alkyl group includes a linear alkyl group (methyl). , Ethyl, propyl, butyl, pentyl, octyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), etc. Be done.

Specific examples of the aromatic group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms. Aromatic heterocycle; etc. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
Specifically, the aromatic hydrocarbon group is a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group); a group in which one of the hydrogen atoms of the aryl group is substituted with an alkylene group (for example). , Arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group); and the like.

A proton-accepting functional group is a functional group having a group capable of electrostatically interacting with a proton or a lone electron pair, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or π. Examples thereof include functional groups having a nitrogen atom having a lone pair of electrons with a small contribution of conjugation.
Preferred partial structures of the proton acceptor functional group include, for example, crown ether, azacrown ether, tertiary amine, secondary amine, primary amine, pyridine, imidazole, pyrazine, aniline structure and the like.

In the present invention, the hydrocarbon groups having 1 to 20 carbon atoms which may have the substituents in R ¹ and R ² include those listed above and the general formulas (a2-r-1) to be described later. A group represented by any of (a2-r-7), a group represented by any of the general formulas (a5-r-1) to (a5-r-4), and a general formula (ax3-r-1). ) To (ax3-r-3) may be a group represented by any of them.
In the present invention, among the above, the group represented by the general formula (a2-r-2) is preferable.

In the general formula (d0), M ^{m +} is an m-valent organic cation, and m is an integer of 1 or more.
Examples of the m-valent organic cation of M ^{m +} include organic cations similar to the m-valent organic cations in the general formulas (b-1) to (b-3) described later.

In the present invention, the compound represented by the general formula (d0) is preferably a compound represented by the following general formula (d0-1).

［式中、Ｒ^１１及びＲ^１２のいずれか一方は置換基を有していてもよい炭素数３〜２０の環状の炭化水素基であり、他方は置換基を有していてもよい炭素数１〜２０の鎖状、分岐鎖状又は環状の炭化水素基である。但し、式中のカルボニル基に隣接するＲ^１１の炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。式中のスルホニル基に隣接するＲ^１２の炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。Ｍ^ｍ＋はｍ価の有機カチオンである。ｍは１以上の整数である。］

[In the formula, one of R ¹¹ and R ¹² is a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, and the other has a carbon number which may have a substituent. 1 to 20 chain, branched or cyclic hydrocarbon groups. However, when a substituent is bonded to the carbon atom of R ¹¹ adjacent to the carbonyl group in the formula, the substituent is a group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more selected from. When a substituent on the carbon atoms of R ¹² adjacent to the sulfonyl group in the formula are bonded, the substituent selected from the group consisting group, an aromatic group, and a proton acceptor functional group having a halogen atom It shall not have more than one kind. M ^{m +} is an m-valent organic cation. m is an integer of 1 or more. ]

In the formula (d0-1), one of R ¹¹ and R ¹² is a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, and the other has a substituent. It is also a chain, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms.
A cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent in R ¹¹ and R ^12, and a chain, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. The description of the hydrocarbon group in the above is the same as described above.
As the compound represented by the general formula (d0-1), a compound represented by any of the following general formulas (d0-1a), (d0-1b) or (d0-1c) is preferable.

［式中、Ｒ^１１ａは置換基を有していてもよい炭素数３〜２０の環状の炭化水素基であり、Ｒ^１２ａは置換基を有していてもよい炭素数１〜２０の鎖状又は分岐鎖状の炭化水素基である。但し、式中のカルボニル基に隣接するＲ^１１ａの炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。式中のスルホニル基に隣接するＲ^１２ａの炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。Ｍ^ｍ＋はｍ価の有機カチオンである。ｍは１以上の整数である。］

[In the formula, R ^11a is a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, and R ^12a is a chain having 1 to 20 carbon atoms which may have a substituent. Alternatively, it is a branched hydrocarbon group. However, when a substituent is bonded to the carbon atom of R ^11a adjacent to the carbonyl group in the formula, the substituent is a group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more selected from. When a substituent is bonded to the carbon atom of R ^12a adjacent to the sulfonyl group in the formula, the substituent is selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have more than one kind. M ^{m +} is an m-valent organic cation. m is an integer of 1 or more. ]

In the general formula (d0-1a), the cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent in R ^11a has the substituent described in R ¹ or R ² above. Examples thereof include a hydrocarbon group similar to the cyclic hydrocarbon group having 3 to 20 carbon atoms.
In the general formula (d0-1a), the chain-like or branched-chain hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R ^12a is the substitution described in R ¹ or R ² above. Examples thereof include a hydrocarbon group similar to a chain or branched hydrocarbon group having 1 to 20 carbon atoms which may have a group.

［式中、Ｒ^１１ｂは置換基を有していてもよい炭素数１〜２０の鎖状又は分岐鎖状の炭化水素基であり、Ｒ^１２ｂは置換基を有していてもよい炭素数３〜２０の環状の炭化水素基である。但し、式中のカルボニル基に隣接するＲ^１１ｂの炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。式中のスルホニル基に隣接するＲ^１２ｂの炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。Ｍ^ｍ＋はｍ価の有機カチオンである。ｍは１以上の整数である。］

[In the formula, R ^11b is a chain or branched hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ^12b has 3 carbon atoms which may have a substituent. It is a cyclic hydrocarbon group of ~ 20. However, when a substituent is bonded to the carbon atom of R ^11b adjacent to the carbonyl group in the formula, the substituent is a group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more selected from. When a substituent is attached to the carbon atom of R ^12b adjacent to the sulfonyl group in the formula, the substituent is selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have more than one kind. M ^{m +} is an m-valent organic cation. m is an integer of 1 or more. ]

In the general formula (d0-1b), the chain-like or branched-chain hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R ^11b is the substitution described in R ¹ or R ² above. Examples thereof include a hydrocarbon group similar to a chain or branched hydrocarbon group having 1 to 20 carbon atoms which may have a group.
In the general formula (d0-1b), the cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent in R ^12b has the substituent described in R ¹ or R ² above. Examples thereof include a hydrocarbon group similar to the cyclic hydrocarbon group having 3 to 20 carbon atoms.

［式中、Ｒ^１１ｃ及びＲ^１２ｃは置換基を有していてもよい炭素数１〜２０の鎖状又は分岐鎖状の炭化水素基である。Ｒ^１１ｃ及びＲ^１２ｃは同一であっても異なっていてもよい。但し、式中のカルボニル基に隣接するＲ^１１ｃの炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。式中のスルホニル基に隣接するＲ^１２ｃの炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。Ｍ^ｍ＋はｍ価の有機カチオンである。ｍは１以上の整数である。］

[In the formula, R ^11c and R ^12c are chain or branched chain hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent. R ^11c and R ^12c may be the same or different. However, when a substituent is bonded to the carbon atom of R ^11c adjacent to the carbonyl group in the formula, the substituent is a group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more selected from. When a substituent is attached to the carbon atom of R ^12c adjacent to the sulfonyl group in the formula, the substituent is selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have more than one kind. M ^{m +} is an m-valent organic cation. m is an integer of 1 or more. ]

In the general formula (d0-1c), the chain or branched hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R ^11c and R ^12c is described in R ¹ or R ² . Examples thereof include hydrocarbon groups similar to the chain or branched hydrocarbon groups having 1 to 20 carbon atoms which may have the above-described substituents. In the general formula (d0-1c), R ^11c and R ^12c may be the same or different, but are preferably different hydrocarbon groups.

Specific examples of the compound represented by the general formula (d0) will be described below. In the following formula, M ^{m +} is an m-valent organic cation, and examples thereof include organic cations similar to the m-valent organic cations in the general formulas (b-1) to (b-3) described later.

The compound represented by the general formula (d0) is bonded to the carbon atom of R ¹ adjacent to the carbonyl group in the formula (d0) or the carbon atom of R ² adjacent to the sulfonyl group in the formula (d0). Since the substituent does not have one or more selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group, the pKa of the conjugated acid can be maintained relatively high.
In the present invention, the acid dissociation constant (pKa) of the conjugate acid of the compound represented by the general formula (d0) is preferably larger than 2.5. In the present invention, the pKa of the conjugate acid of the compound represented by the general formula (d0) is more preferably 3.0 or more, and particularly preferably 4.0 or more.
In the present invention, the "acid dissociation constant (pKa)" is generally used as an index indicating the acid strength of the target substance. The pKa value of the conjugate acid of the compound represented by the general formula (d0) can be determined by measuring by a conventional method. Further, calculated values using known software such as "ACD / Labs" (trade name, manufactured by Advanced Chemistry Development) can also be used.
When the pKa of the conjugate acid is at least the above lower limit value, the quenching efficiency of the acid becomes high, and the diffusion of the acid generated from the component (B) described later can be appropriately controlled.

As the component (D0), the above-mentioned compounds may be used alone or in combination of two or more.
In the resist composition of the present invention, the content of the component (D0) is preferably 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass, and 1 to 8 parts by mass with respect to 100 parts by mass of the component (A). Parts are more preferred. When the content of the component (D0) is within the above range, the quenching effect of the acid generated from the acid generator or the like described later is sufficiently exhibited, and when each component of the resist composition is dissolved in an organic solvent, It is preferable because a uniform solution can be obtained and the storage stability is good.

Since the resist composition of the present invention contains the compound (D0) represented by the general formula (d0), the quenching effect of the acid can be maintained high, so that the diffusion length of the acid can be controlled and at the same time the storage stability. It is also excellent.
The compound represented by the general formula (d0) is bonded to the carbon atom of R ¹ adjacent to the carbonyl group in the formula (d0) or the carbon atom of R ² adjacent to the sulfonyl group in the formula (d0). Since the substituent does not have one or more selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group, the pKa of the conjugated acid can be maintained high and the diffusion length of the acid can be increased. Since it can be controlled appropriately, the quenching efficiency can be made high.
In the conventional citric acid component, when the pKa of the conjugate acid was increased, it was easy to react with other polymers in the resist composition. That is, the decomposition (deterioration with time) of the other compounding component proceeds by interacting with the ester bond of the other compounding component, in other words, the storage stability is inferior.
On the other hand, in the present invention, it is considered that the compound represented by the general formula (d0) can suppress contact with other compounding components due to steric hindrance because the anionic skeleton is bulky. This makes it possible to prevent the resist composition from deteriorating with time, and it is considered that the resist composition has excellent storage stability.
That is, the present invention is a very useful resist composition, which can achieve both improvement in quenching efficiency and reduction in risk over time.

<Acid generator component; (B) component>
The resist composition of the present invention contains an acid generator component (B) (hereinafter referred to as (B) component) that generates an acid upon exposure. The component (B) is not particularly limited, and those previously proposed as an acid generator for a chemically amplified resist can be used.
Examples of such an acid generator include onium salt-based acid generators such as iodonium salt and sulfonium salt, oxime sulfonate-based acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and diazomethanes such as poly (bissulfonyl) diazomethanes. Various kinds such as an acid generator, a nitrobenzyl sulfonate-based acid generator, an imino sulfonate-based acid generator, and a disulfon-based acid generator can be mentioned. Of these, it is preferable to use an onium salt-based acid generator.

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

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

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

{Anion part}
In the anion part formula (b-1) of the component (b-1), R ¹⁰¹ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, and the like. Alternatively, it is a chain alkenyl group which may have a substituent.

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

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

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

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

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

Among them, R ¹⁰¹ is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, a phenyl group, a naphthyl group, a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and represented by the following formulas (a2-r-1) to (a2-r-7), respectively. lactone-containing cyclic group, -SO ₂ respectively represented by the general formula below (a5-r-1) ~ (a5-r-4) - such as containing cyclic group.

In formula (b-1), Y ¹⁰¹ is a divalent linking group containing a single bond or an oxygen atom.
When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, the Y ¹⁰¹ may contain an atom other than the oxygen atom. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms and the like.
Examples of the divalent linking group containing an oxygen atom include an oxygen atom (ether bond: −O−), an ester bond (−C (= O) −O−), and an oxycarbonyl group (−OC (= O−). )-), Amid bond (-C (= O) -NH-), carbonyl group (-C (= O)-), carbonate bond (-O-C (= O) -O-) and other non-carbohydrates Oxygen atom-containing linking group of the system; Examples thereof include a combination of the oxygen atom-containing linking group of the non-hydrogen system and an alkylene group. A sulfonyl group (-SO _2- ) may be further linked to the combination. Examples of the combination include linking groups represented by the following formulas (y-al-1) to (y-al-7), respectively.

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

Wherein, V ^'101 represents a single bond or an alkylene group having 1 to 5 carbon atoms, V' ¹⁰² is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms. ]

Divalent saturated hydrocarbon group in V ^'102 is preferably an alkylene group having 1 to 30 carbon atoms.

The alkylene group for V ^'101 and V' ^102, may be linear well branched alkylene group with an alkylene group, a linear alkylene group is preferable.
As the alkylene group for V ^'101 and V' ^102, specifically, a methylene group _{[-CH 2 -]; - CH} (CH 3) -, - CH (CH 2 CH 3) -, - C (CH 3) Alkyl methylene groups such as _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2-, etc.; Group [-CH ₂ CH _2- ]; -CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH) ₃ ) Alkylethylene group such as CH _2- ; trimethylene group (n-propylene group) [-CH ₂ CH ₂ CH _2- ]; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) Alkyl methylene group such as CH _2- ; tetramethylene group [-CH ₂ CH ₂ CH ₂ CH _2- ]; -CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ Alkyltetramethylene groups such as CH _2- ; pentamethylene groups [-CH ₂ CH ₂ CH ₂ CH ₂ CH _2- ] and the like can be mentioned.
A part of the methylene groups in the alkylene group for V ^'101 or V' ¹⁰² may be substituted by a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a divalent group formed by removing one more hydrogen atom from an aliphatic hydrocarbon group of Ra ^'3 annular formula below (a1-r-1), cyclohexylene Groups, 1,5-adamantylene groups or 2,6-adamantylene groups are more preferred.

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

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

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

As a specific example of the anion portion of the component (b-1), for example,
When Y ¹⁰¹ is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anion and perfluorobutane sulfonate anion can be mentioned; when Y ¹⁰¹ is a divalent linking group containing an oxygen atom, the following formula (an) -1) An anion represented by any one of (an-3) can be mentioned.

［式中、Ｒ”^１０１は、置換基を有していてもよい脂肪族環式基、前記式（ｒ−ｈｒ−１）〜（ｒ−ｈｒ−６）でそれぞれ表される基、又は置換基を有していてもよい鎖状のアルキル基であり；Ｒ”^１０２は、置換基を有していてもよい脂肪族環式基、後述の式（ａ２−ｒ−１）〜（ａ２−ｒ−７）でそれぞれ表されるラクトン含有環式基、又は後述の一般式（ａ５−ｒ−１）〜（ａ５−ｒ−４）でそれぞれ表される−ＳＯ_２−含有環式基であり；Ｒ”^１０３は、置換基を有していてもよい芳香族環式基、置換基を有していてもよい脂肪族環式基、又は置換基を有していてもよい鎖状のアルケニル基であり；Ｖ”^１０１は、フッ素化アルキレン基であり；Ｌ”^１０１は、−Ｃ（＝Ｏ）−又は−ＳＯ_２−であり；ｖ”はそれぞれ独立に０〜３の整数であり、ｑ”はそれぞれ独立に１〜２０の整数であり、ｎ”は０または１である。］

[In the formula, R " ¹⁰¹ is an aliphatic cyclic group which may have a substituent, a group represented by the above formulas (r-hr-1) to (r-hr-6), or a substitution. It is a chain alkyl group which may have a group; R " ¹⁰² is an aliphatic cyclic group which may have a substituent, the formulas (a2-r-1) to (a2-) described later. lactone-containing cyclic group represented respectively by r-7), or below described general formula (a5-r-1) ~ (a5-r-4) with -SO ₂ respectively represented - be-containing cyclic group R " ¹⁰³ is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl which may have a substituent. Group; V " ¹⁰¹ is a fluorinated alkylene group; L" ¹⁰¹ is -C (= O)-or -SO _2- ; v "is an independently integer of 0-3. q "is an independently integer of 1 to 20, and n" is 0 or 1. ]

The aliphatic cyclic group which may have a substituent of R " ¹⁰¹ , R" ¹⁰² and R " ¹⁰³ is preferably the group exemplified as the cyclic aliphatic hydrocarbon group in R ¹⁰¹ . Examples of the substituent include the same substituents which may substitute the cyclic aliphatic hydrocarbon group in R ¹⁰¹ .

The aromatic cyclic group which may have a substituent in R " ¹⁰³ is preferably a group exemplified as an aromatic hydrocarbon group in the cyclic hydrocarbon group in R ^101. The substituent is preferably a group. , R ¹⁰¹ , the same as the substituent which may replace the aromatic hydrocarbon group.

The chain-like alkyl group which may have a substituent at R " ¹⁰¹ is preferably a group exemplified as the chain-like alkyl group at R ^{101. It} has a substituent at R " ¹⁰³ . The good chain alkenyl group is preferably the group exemplified as the chain alkenyl group in R ¹⁰¹ . V ^"101 is preferably a fluorinated alkylene group having 1 to 3 carbon atoms, particularly _{preferably, -CF 2 -, - CF 2} CF 2 -, - CHFCF 2 -, - CF (CF 3) CF 2 - , -CH (CF ₃ ) CF _2- .

-In the anion part formula (b-2) of the component (b-2), R ¹⁰⁴ and R ¹⁰⁵ may independently have a substituent, even if they have a cyclic group and a substituent. Examples thereof include a good chain alkyl group and a chain alkenyl group which may have a substituent, respectively, which are similar to R ¹⁰¹ in the formula (b-1). However, R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring.
R ¹⁰⁴ and R ¹⁰⁵ are preferably chain-like alkyl groups which may have a substituent, and are linear or branched-chain alkyl groups, or linear or branched-chain fluorinated alkyl groups. Is more preferable.
The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and further preferably 1 to 3 carbon atoms. The carbon number of the chain alkyl group of R ¹⁰⁴ and R ¹⁰⁵ is preferably as small as possible because the solubility in the resist solvent is also good within the range of the carbon number. Further, in the chain alkyl groups of R ¹⁰⁴ and R ^105, the larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and the stronger the acid strength, and the higher the strength of the acid with respect to high-energy light or electron beam of 200 nm or less. It is preferable because it improves transparency. The ratio of fluorine atoms in the chain alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all hydrogen atoms are substituted with fluorine atoms. It is a perfluoroalkyl group.
In formula (b-2), V ¹⁰² and V ¹⁰³ are independently single-bonded, alkylene groups, or fluorinated alkylene groups, respectively, which are similar to V ¹⁰¹ in formula (b-1). Can be mentioned.
In formula (b-2), L ^{101 to} L ¹⁰² are independently single bonds or oxygen atoms, respectively.

-In the anion part formula (b-3) of the component (b-3), R ^{106 to} R ¹⁰⁸ may independently have a substituent, even if they have a cyclic group or a substituent. Examples thereof include a good chain alkyl group and a chain alkenyl group which may have a substituent, respectively, which are similar to R ¹⁰¹ in the formula (b-1).
L ^{103 to} L ¹⁰⁵ are each independently single-bonded, -CO- or -SO _2- .

{Cation part}
In the formulas (b-1), (b-2) and (b-3), M'm ⁺ is an m-valent organic cation other than the cation in the compound of the formula (b1-1), and among them, a sulfonium cation. Alternatively, it is preferably an iodonium cation, and cations represented by the following general formulas (ca-1) to (ca-4) are particularly preferable.

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

[In the formula, R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² represent aryl groups, alkyl groups or alkenyl groups, which may have independent substituents, respectively, and R ^{201 to} R ²⁰³ and R ²⁰⁶ to R ²⁰⁶ . R ²⁰⁷ and R ^{211 to} R ²¹² may be bonded to each other to form a ring together with the sulfur atom in the formula. R ^{208 to} R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²¹⁰ contains an aryl group, an alkyl group, an alkenyl group, or -SO _2- which may have a substituent. It is a cyclic group, L ²⁰¹ represents −C (= O) − or −C (= O) −O−, Y ²⁰¹ independently represents an arylene group, an alkylene group or an alkenylene group, and x is 1 or 2, where W ²⁰¹ represents a (x + 1) valence linking group. ]

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

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

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

R ^'201 which may have a substituent cyclic group, substituent having optionally also good chain alkyl group or have a substituent which may chain alkenyl groups, is the ^Examples of the same as R ¹⁰¹ in the formula (b-1) can be mentioned, and a cyclic group which may have a substituent or a chain alkyl group which may have a substituent may be described later. The same as the acid dissociable group represented by (a1-r-2) can also be mentioned.

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

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

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

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

In the formula (ca-4), x is 1 or 2.
W ²⁰¹ is a (x + 1) valence, i.e., a divalent or trivalent linking group.
As the divalent linking group in W ^{201, a} divalent hydrocarbon group which may have a substituent is preferable, and a hydrocarbon group similar to Ya ²¹ in the general formula (a2-1) described later can be exemplified. .. The divalent linking group in W ²⁰¹ may be linear, branched or cyclic, and is preferably cyclic. Of these, a group in which two carbonyl groups are combined at both ends of the arylene group is preferable. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferable.
^Examples of the trivalent linking group in W ²⁰¹ include a group obtained by removing one hydrogen atom from the divalent linking group in W ²⁰¹ , and a group in which the divalent linking group is further bonded to the divalent linking group. Can be mentioned. As the trivalent linking group in W ²⁰¹ , a group in which two carbonyl groups are bonded to an arylene group is preferable.

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

［式中、ｇ１、ｇ２、ｇ３は繰返し数を示し、ｇ１は１〜５の整数であり、ｇ２は０〜２０の整数であり、ｇ３は０〜２０の整数である。］

[In the formula, g1, g2, and g3 indicate the number of repetitions, g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 0 to 20. ]

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

[In the formula, R " ²⁰¹ is a hydrogen atom or a substituent, and the substituents are the same as those listed as the substituents that R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have. is there.]

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

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

As the component (B), the above-mentioned acid generator may be used alone or in combination of two or more.
The content of the component (B) in the resist composition of the present invention is preferably 0.5 to 60 parts by mass, more preferably 1 to 50 parts by mass, and 1 to 40 parts by mass with respect to 100 parts by mass of the component (A). Is even more preferable. By setting the content of the component (B) in the above range, pattern formation is sufficiently performed. Further, when each component of the resist composition is dissolved in an organic solvent, a uniform solution is obtained and the storage stability is improved, which is preferable.

<Ingredient (A)>
In the present invention, the "base material component" is an organic compound having a film-forming ability, and an organic compound having a molecular weight of 500 or more is preferably used. When the molecular weight of the organic compound is 500 or more, the film forming ability is improved, and in addition, a nano-level photosensitive resin pattern is easily formed.
Organic compounds used as base material components 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. Hereinafter, the term "low molecular weight compound" refers to a non-polymer having a molecular weight of 500 or more and less than 4000.
As the polymer, a polymer having a molecular weight of 1000 or more is usually used. Hereinafter, the term "resin" refers to a polymer having a molecular weight of 1000 or more.
As the molecular weight of the polymer, the polystyrene-equivalent weight average molecular weight by GPC (gel permeation chromatography) shall be used.
As the component (A), a resin may be used, a low molecular weight compound may be used, or these may be used in combination.
The component (A) may be one in which the solubility in a developing solution is increased by the action of an acid, or the solubility in a developing solution may be decreased by the action of an acid.
Further, in the present invention, the component (A) may generate an acid by exposure.

In the present invention, (A) component, the structural unit containing an acid decomposable group that exhibits increased polarity by the action of an acid (sometimes referred to hereinafter, "constituent unit (a1)".) _- SO 2 - containing cyclic A structural unit derived from an acrylic acid ester containing a group (hereinafter, may be referred to as "constituent unit (a2)"), a structural unit containing a polar group-containing aliphatic hydrocarbon group (hereinafter, "constituent unit (a3)). ”), A structural unit containing an acid non-dissociable cyclic group (hereinafter, may be referred to as“ structural unit (a4) ”), a configuration containing a lactone-containing cyclic group or a carbonate-containing cyclic group. It preferably contains a polymer compound (A1) having a unit (hereinafter, may be referred to as “constituent unit (a5)”).

(Structural unit (a1))
The structural unit (a1) is a structural unit containing an acid-degradable group whose polarity is increased by the action of an acid.
An "acid-degradable group" is a group having an acid-degradable property in which at least a part of the bonds in the structure of the acid-degradable group can be cleaved by the action of an acid.
Examples of the acid-degradable group whose polarity is increased by the action of an acid include a group which is decomposed by the action of an acid to produce 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, may be referred to as “OH-containing polar group”) is preferable, a carboxy group or a hydroxyl group is preferable, and a carboxy group is particularly preferable.
More specific examples of the acid-degradable group include a group in which the polar group is protected by an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group).
Here, the "acid dissociative group" is
(I) A group having acid dissociation that allows the bond between the acid dissociating group and an atom adjacent to the acid dissociating group to be cleaved by the action of an acid, or a group having acid dissociation.
(Ii) A group capable of cleaving the bond between the acid dissociative group and an atom adjacent to the acid dissociative group by further decarboxylation after the partial bond is cleaved by the action of the acid. ,
Refers to both.
The acid dissociable group constituting the acid-degradable group needs to be a group having a lower polarity than the polar group produced by the dissociation of the acid-dissociable group, whereby the acid-dissociable group due to the action of the acid. When is dissociated, a polar group having a higher polarity than the acid dissociative group is generated and the polarity is increased. As a result, the polarity of the entire (A1) component increases. As the polarity increases, the solubility in the developer changes relatively, and when the developer is an organic developer, the solubility decreases.

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

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

Wherein, Ra ^'1, Ra' ² represents a hydrogen atom or an alkyl group, Ra ^'3 is a hydrocarbon group, Ra' ³ is, Ra ^'1, Ra' ² of bonded either to form a ring Good. ]

Wherein (a1-r-1), as the Ra ^'1, Ra' ² alkyl groups, in the description of the α-substituted acrylic acid esters, mentioned as α-position substituent which may be bonded to the carbon atoms of Similar to the alkyl group, a methyl group or an ethyl group is preferable, and a methyl group is most preferable.

The ra ^'3 hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, the alkyl group is more preferably 1 to 10 carbon atoms; preferably a linear or branched alkyl group, specifically, , Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylethyl group, 1,1-diethylpropyl group Examples thereof include a 2,2-dimethylpropyl group and a 2,2, -dimethylbutyl group.

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

In the case of an aromatic hydrocarbon group, the aromatic ring contained is specifically an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene, etc .; the carbon atom constituting the aromatic hydrocarbon ring. Aromatic heterocycles partially substituted with heteroatoms; etc. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like.
Specifically, the aromatic hydrocarbon group is a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group); a group in which one of the hydrogen atoms of the aryl group is substituted with an alkylene group (for example). , Arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl 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 number.

Ra ^'3 is, ra' ^1, if ra ^'2 of bonded either to form a ring, a cyclic group, 4- to 7-membered ring is preferred, 4 to 6-membered ring is more preferable. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

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

［式中、Ｒａ’^４〜Ｒａ’^６は炭化水素基であり、Ｒａ’^５、Ｒａ’^６は互いに結合して環を形成してもよい。］

Wherein, Ra ^'4 ~Ra' ⁶ is a hydrocarbon group, Ra ^'5, Ra' ⁶ may be bonded to each other to form a ring. ]

Examples of the hydrocarbon group Ra ^'4 ~Ra' ⁶ include the same as the Ra ^'3. Ra ^'4 is preferably an alkyl group having 1 to 5 carbon atoms. Ra If ^'5, Ra' ⁶ are bonded to each other to form a ring, a group represented by the following general formula (a1-r2-1).
On the other hand, Ra ^'4 ~Ra' ⁶ are not bonded to each other, when an independent hydrocarbon groups include groups represented by the following general formula (a1-r2-2).

［式中、Ｒａ’^１０は炭素数１〜１０のアルキル基、Ｒａ’^１１はＲａ’^１０が結合した炭素原子と共に脂肪族環式基を形成する基、Ｒａ’^１２〜Ｒａ’^１４は、それぞれ独立に炭化水素基を示す。］

Wherein, Ra ^'10 is an alkyl group having 1 to 10 carbon atoms, Ra' ¹¹ is' group to form an aliphatic cyclic group together with the carbon atom ^{to which 10} are bonded, Ra 'Ra ¹² to Ra' ¹⁴ each Independently shows a hydrocarbon group. ]

Wherein (a1-r2-1), Ra 'alkyl group of the alkyl group having 1 to 10 carbon atoms ^10, Ra in formula (a1-r-1)' a linear or branched alkyl group of ³ The groups listed as are preferred. Wherein (a1-r2-1), Ra 'aliphatic cyclic ^{group 11} is configured, Ra in formula (a1-r-1)' group listed as a cyclic alkyl group of ³ is preferred.

Wherein (a1-r2-2), it is preferable that Ra is ^'12 and Ra' ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, the alkyl group, Ra in formula (a1-r-1) The group listed as the linear or branched alkyl group of ' ³ is more preferable, the linear alkyl group having 1 to 5 carbon atoms is more preferable, and the methyl group or the ethyl group is particularly preferable. ..
Wherein (a1-r2-2) that, Ra ^'13 has the formula (a1-r-1) in the Ra' ³ of the illustrated linear hydrocarbon group, branched or cyclic alkyl group Is preferable. Among these, it is more preferably a group listed as a cyclic alkyl group of Ra ^'3.

Specific examples of the above formula (a1-r2-1) are given below. In the following formula, "*" indicates a bond.

Specific examples of the above formula (a1-r2-2) will be given below.

Among the polar groups, the acid dissociable group that protects the hydroxyl group includes, for example, an acid dissociable group represented by the following general formula (a1-r-3) (hereinafter, for convenience, “tertiary alkyloxycarbonylic acid”. (Sometimes referred to as a dissociative group)).

［式中、Ｒａ’^７〜Ｒａ’^９はアルキル基を示す。］

Wherein, Ra ^'7 ~Ra' ⁹ is an alkyl group. ]

Wherein (a1-r-3), Ra '7 ~Ra' 9 is preferably an alkyl group having 1 to 5 carbon atoms, 1 to 3 is more preferable.
The total carbon number of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

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

Among the above, the structural unit (a1) is preferably a structural unit derived from an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent.
As the structural unit (a1), a structural unit represented by the following general formula (a1-1) or (a1-2) is 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る。Ｖａ^１はエーテル結合、ウレタン結合、又はアミド結合を有していてもよい２価の炭化水素基であり、ｎ_ａ１は０〜２であり、
Ｒａ^１は上記式（ａ１−ｒ−１）〜（ａ１−ｒ−２）で表される酸解離性基である。Ｗａ^１はｎ_ａ２＋１価の炭化水素基であり、ｎ_ａ２は１〜３であり、Ｒａ^２は上記式（ａ１−ｒ−１）または（ａ１−ｒ−３）で表される酸解離性基である。］

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

In the general formula (a1-1), the alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group, an ethyl group, or the like. Examples thereof include propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. The alkyl halide group having 1 to 5 carbon atoms is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable from the viewpoint of industrial availability.
The hydrocarbon group of Va ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromaticity. The aliphatic hydrocarbon group as the divalent hydrocarbon group in Va ¹ may be saturated or unsaturated, and is usually preferably saturated.
More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.
Examples of Va ¹ include those in which the divalent hydrocarbon group is bonded via an ether bond, a urethane bond, or an amide bond.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], a trimethylene group [ − (CH ₂ ) ₃ −], tetramethylene group [− (CH ₂ ) ₄ −], pentamethylene group [− (CH ₂ ) ₅ −] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ). Alkylmethylene groups such as _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _2-, etc.;- 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) Examples thereof include an alkylalkylene group such as an alkyltetramethylene group such as CH ₂ CH ₂ CH ₂ − and −CH ₂ CH (CH ₃ ) CH ₂ CH ₂ −. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

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

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

In the formula (a1-2), n _{a2 +1} monovalent hydrocarbon group for Wa ¹ may be an aliphatic hydrocarbon group may be an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and a linear or branched aliphatic hydrocarbon group. A group in which a ring-containing aliphatic hydrocarbon group is combined in the structure can be mentioned, and specifically, the same group as Va ¹ of the above formula (a1-1) can be mentioned.
The _na2 + 1 valence is preferably 2 to 4 valence, more preferably 2 or 3 valence.

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

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

The ratio of the constituent unit (a1) in the component (A) is preferably 20 to 80 mol%, more preferably 20 to 75 mol%, and 25 to 70 mol% with respect to all the constituent units constituting the component (A). Is even more preferable. By setting the value to the lower limit or higher, the lithographic characteristics such as sensitivity, resolution, and LWR are also improved. Further, by setting the value to the upper limit or less, it is possible to balance with other structural units.

(Structural unit (a2))
The structural unit (a2), -SO ₂ - is a structural unit containing an containing cyclic group.
-SO 2 of the structural unit (a2) _- containing cyclic group, is effective in increasing the adhesion (A1) when the components used for forming a resist film, the resist film to the substrate.
In the present invention, the component (A1) preferably has a structural unit (a2).
Incidentally, the structural unit (a1) is -SO 2 within the structure _- if it is intended to include containing cyclic group, although the structural unit also corresponds with the structural unit (a2), such structural units the structural unit ( It corresponds to a1) and does not correspond to the structural unit (a2).

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

［式中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基であり、Ｙａ^２１は単結合または２価の連結基であり、Ｌａ^２１は−Ｏ−、−ＣＯＯ−、−ＣＯＮ（Ｒ’）−、−ＯＣＯ−、−ＣＯＮＨＣＯ−又は−ＣＯＮＨＣＳ−であり、Ｒ’は水素原子またはメチル基を示す。ただしＬａ^２１が−Ｏ−の場合、Ｙａ^２１は−ＣＯ−にはならない。Ｒａ^２１は−ＳＯ_２−含有環式基である。］

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, Ya ²¹ is a single bond or a divalent linking group, and La ²¹ is −O. -, -COO-, -CON (R')-, -OCO-, -CONHCO- or -CONHCS-, where R'indicates a hydrogen atom or a methyl group. However, when La ²¹ is −O−, Ya ²¹ is not −CO−. Ra ²¹ is -SO ₂ - containing cyclic group. ]

The divalent linking group of Ya ²¹ is not particularly limited, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, and the like are preferable.

(Divalent hydrocarbon group which may have a substituent)
The hydrocarbon group as the divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like, and specifically, the above formula (a1-). Examples thereof include the groups exemplified by Va ¹ in 1).

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

As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure (two hydrogen atoms are removed from the aliphatic hydrocarbon ring). Group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a linear or branched aliphatic hydrocarbon group, or a group in which the cyclic aliphatic hydrocarbon group is linear or branched. Examples include groups intervening in the middle of group hydrocarbon groups. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
Specific examples of the cyclic aliphatic hydrocarbon group include the group exemplified by Va ¹ in the above formula (a1-1).
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, a carbonyl group and the like.
As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.
As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, 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 methoxy. Groups and ethoxy groups are most preferred.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
Examples of the alkyl halide group as the substituent include a group in which a part or all of the hydrogen atom of the alkyl group is substituted with the halogen atom.
The cyclic aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom as a part of the carbon atom constituting the ring structure. The substituent containing a hetero atom, -O -, - C (= O) -O -, - S -, - S (= O) 2 -, - S (= O) 2 -O- are preferred.

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

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

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

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

In the formula (a2-1), ^{Ra 21} is -SO ₂ - containing cyclic group.

And _- "-SO 2 containing cyclic group", -SO 2 _- within the ring skeleton thereof shows a cyclic group containing a ring containing, in particular, -SO 2 _- sulfur atom (S) is in A cyclic group that forms part of the cyclic skeleton of the cyclic group. A ring containing −SO ₂ − in its ring skeleton is counted as the first ring, and if it is only the ring, it is a monocyclic group, and if it has another ring structure, it is a polycyclic group regardless of its structure. It is called. The −SO ₂ − containing cyclic group may be monocyclic or polycyclic.
R ¹ -SO as cyclic hydrocarbon group in the ₂ - containing cyclic group, in particular, -O-SO ₂ - within the ring skeleton cyclic group containing, i.e. -O-SO ₂ - -O Medium It is preferred that —S— is a cyclic group containing a sultone ring that forms part of the ring skeleton. -SO ₂ - containing cyclic group, and more specifically, include groups represented by the following general formula (a5-r-1) ~ (a5-r-4).

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

Wherein, Ra ^'51 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, hydroxyl group, -COOR - in ", OC (= O) R ", a hydroxyalkyl group or a cyano group Yes; R "is a hydrogen atom or an alkyl group; A" is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and n'is 0 to 2. Is an integer of. ]

In the general formulas (a5-r-1) to (a5-r-4), A "is the same as A" in the general formulas (a2-r-1) to (a2-r-7) described later. .. Alkyl group in ra ^'51, an alkoxy group, a halogen atom, a halogenated alkyl group, -COOR ", - OC (= O) R", The hydroxyalkyl group, the formula (a2-r-1) ~ (a2 it is the same as Ra ^'21 of -r-7) in.

Specific examples of the groups represented by the general formulas (a5-r-1) to (a5-r-4) are given below. "Ac" in the formula indicates an acetyl group.

The -SO ₂ - containing cyclic group, among the above, is preferably a group represented by the formula (a5-r-1), the formula (r-sl-1-1), (r-sl- It is more preferable to use at least one selected from the group consisting of the groups represented by any of 1-18), (r-sl-3-1) and (r-sl-4-1), and the above chemical formula. The group represented by (r-sl-1-1) is most preferable.

The structural unit (a2) contained in the component (A1) may be one type or two or more types.
When the component (A1) has a constituent unit (a2), the ratio of the constituent unit (a2) is preferably 1 to 80 mol% with respect to the total of all the constituent units constituting the component (A1). It is more preferably 5 to 70 mol%, further preferably 10 to 65 mol%, and particularly preferably 10 to 60 mol%. By setting it to the lower limit value or more, the effect of containing the constituent unit (a2) can be sufficiently obtained, and by setting it to the upper limit value or less, it is possible to balance with other constituent units, and various lithography characteristics and patterns can be obtained. The shape becomes good.

(Structural unit (a3))
The structural unit (a3) is a structural unit containing a polar group-containing aliphatic hydrocarbon group (however, excluding those corresponding to the above-mentioned structural units (a1) and (a2)).
It is considered that the component (A1) having the constituent unit (a3) enhances the hydrophilicity of the component (A) and contributes to the improvement of the resolution.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, a hydroxyalkyl group in which a part of hydrogen atoms of the alkyl group is replaced with a fluorine atom, and the like, and a hydroxyl group is particularly preferable.
Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be a monocyclic group or a polycyclic group, and for example, in the resin for the resist composition for ArF excimer laser, it can be appropriately selected and used from a large number of proposed ones. The cyclic group is preferably a polycyclic group, and more preferably has 7 to 30 carbon atoms.
Among them, a structural unit derived from an acrylic acid 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 a group obtained by removing two or more hydrogen atoms from a bicycloalkane, a tricycloalkane, a tetracycloalkane, or the like. Specific examples thereof include groups obtained by removing two or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, there are a group in which two or more hydrogen atoms are removed from adamantane, a group in which two or more hydrogen atoms are removed from norbornane, and a group in which two or more hydrogen atoms are removed from tetracyclododecane. Industrially preferable.

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

［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。］

[In the formula, R is the same as above, j is an integer of 1-3, k is an integer of 1-3, t'is an integer of 1-3, and l is an integer of 1-5. And s is an integer of 1-3. ]

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

In the formula (a3-2), k is preferably 1. The cyano group is preferably attached to the 5- or 6-position of the norbornyl group.
In formula (a3-3), t'is preferably 1. l is preferably 1. s is preferably 1. In these, it is preferable that a 2-norbornyl group or a 3-norbornyl group is bonded to the terminal of the carboxy group of acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5 or 6 position of the norbornyl group.

The structural unit (a3) contained in the component (A1) may be one kind or two or more kinds.
The ratio of the constituent unit (a3) in the component (A1) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, based on the total of all the constituent units constituting the resin component (A1). It is preferable, 5 to 25 mol% is more preferable.
By setting the ratio of the constituent unit (a3) to the lower limit value or more, the effect of containing the constituent unit (a3) can be sufficiently obtained, and by setting it to the upper limit value or less, a balance with other constituent units can be obtained. It will be easier.

(Structural unit (a4))
The structural unit (a4) is a structural unit containing an acid non-dissociative cyclic group. Since the component (A1) has the structural unit (a4), the dry etching resistance of the resist pattern to be formed is improved. In addition, the hydrophobicity of the component (A1) is increased. The improvement of hydrophobicity is considered to contribute to the improvement of resolution, resist pattern shape, etc., especially in the case of organic solvent development.
The "acid non-dissociative cyclic group" in the structural unit (a4) is contained in the structural unit as it is without dissociation even if the acid acts when an acid is generated from the component (B) described later by exposure. The remaining cyclic group.
As the structural unit (a4), for example, a structural unit derived from an acrylic acid ester containing an acid non-dissociative aliphatic cyclic group is preferable. As the cyclic group, for example, the same ones as those exemplified in the case of the above-mentioned structural unit (a1) can be exemplified, such as for ArF excimer laser, for KrF excimer laser (preferably for ArF excimer laser), and the like. Many conventionally known ones used for the resin component of the resist composition of the above 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 that it is easily available industrially. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
As the structural unit (a4), specifically, those having the structures of the following general formulas (a4-1) to (a4-7) can be exemplified.

［式中、Ｒ^αは、水素原子、メチル基またはトリフルオロメチル基を示す。］

[In the formula, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group. ]

The structural unit (a4) contained in the component (A1) may be one kind or two or more kinds.
When the constituent unit (a4) is contained in the component (A1), the ratio of the constituent unit (a4) is preferably 1 to 30 mol% with respect to the total of all the constituent units constituting the component (A1). More preferably, it is 10 to 20 mol%.

(Structural unit (a5))
The structural unit (a5) is a structural unit containing a lactone-containing cyclic group or a carbonate-containing cyclic group.
The lactone-containing cyclic group or carbonate-containing cyclic group of the structural unit (a5) is effective in enhancing the adhesion of the resist film to the substrate when the component (A1) is used for forming the resist film. is there.
When the structural unit (a1) contains a lactone-containing cyclic group or a carbonate-containing cyclic group in its structure, the structural unit also corresponds to the structural unit (a5), but such a structural unit is It corresponds to the structural unit (a1) and does not correspond to the structural unit (a5).

The structural unit (a5) is preferably a structural unit in which Ra ²¹ in the formula (a2-1) is a lactone-containing cyclic group or a carbonate-containing cyclic group.

The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing −OC (= O) − in its cyclic skeleton. The lactone ring is counted as the first ring, and when it has only a lactone ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
The lactone-containing cyclic group as cyclic hydrocarbon group of R ^1, any can be used without being particularly limited. Specific examples thereof include groups represented by the following general formulas (a2-r-1) to (a2-r-7). Hereinafter, "*" represents a bond.

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

Wherein, Ra ^'21 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, hydroxyl group, -COOR - in ", OC (= O) R ", a hydroxyalkyl group or a cyano group Yes; R "is a hydrogen atom or an alkyl group; A" is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and n'is 0 to 2. And m'is 0 or 1. ]

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

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

The "carbonate-containing cyclic group" refers to a cyclic group containing a ring (carbonate ring) containing -OC (= O) -O- in its cyclic skeleton. The carbonate ring is counted as the first ring, and when it has only a carbonate ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group.
The carbonate ring-containing cyclic group as cyclic hydrocarbon group of R ^1, any can be used without being particularly limited. Specific examples thereof include groups represented by the following general formulas (ax3-r-1) to (ax3-r-3).

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

[In the formula, ^Ra'x31 is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, -COOR ", -OC (= O) R", a hydroxyalkyl group or a cyano group. Yes; R "is a hydrogen atom or an alkyl group; A" is an alkylene group having 1 to 5 carbon atoms, which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and q'is 0 or 1. is there. ]

A "in the general formulas (ax3-r-1) to (ax3-r-3) is the same as A" in the general formula (a2-r-1).
Alkyl group in ra ^'31, an alkoxy group, a halogen atom, a halogenated alkyl group, -COOR ", - OC (= O) R", The hydroxyalkyl group, each of the general formulas (a2-r-1) ~ ( a2-r-7) as in the same as those exemplified in the description of the Ra ^'21 of the like.

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

Among the above, as the lactone-containing cyclic group, the group represented by the general formula (a2-r-1) or (a2-r-2) is preferable, and the group represented by the chemical formula (r-lc-1-1) is preferable. Groups are more preferred.

The structural unit (a5) contained in the component (A1) may be one type or two or more types.
When the component (A1) has a constituent unit (a5), the ratio of the constituent unit (a5) is preferably 1 to 80 mol% with respect to the total of all the constituent units constituting the component (A1). It is more preferably 5 to 70 mol%, further preferably 10 to 65 mol%, and particularly preferably 10 to 60 mol%. By setting it to the lower limit value or more, the effect of containing the constituent unit (a5) can be sufficiently obtained, and by setting it to the upper limit value or less, it is possible to balance with other constituent units, and various types such as DOF and CDU can be obtained. The lithography characteristics and pattern shape of the above are improved.

The component (A1) is obtained by polymerizing a monomer that induces each structural unit by a known radical polymerization using a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate. be able to.
Further, the component (A1), during the polymerization, by using a combination of chain transfer agent such as _{HS-CH 2 -CH 2 -CH 2} -C (CF 3) 2 -OH, end -C (CF ₃ ) _2- OH group may be introduced into the. In this way, the copolymer in which the hydroxyalkyl group in which a part of the hydrogen atom of the alkyl group is replaced with the fluorine atom is introduced can reduce development defects and LER (line edge roughness: non-uniform unevenness of the line side wall). It is effective in reducing the amount of water.

In the present invention, the weight average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of the component (A1) is not particularly limited, and is preferably 1000 to 50000, more preferably 1500 to 30000, and 2000. ~ 20000 is the most preferable. When it is not more than the upper limit of this range, it has sufficient solubility in a resist solvent to be used as a resist, and when it is more than the lower limit of this range, the dry etching resistance and the cross-sectional shape of the resist pattern are good.

As the component (A1), one type may be used alone, or two or more types may be used in combination.
The ratio of the component (A1) to the base material component (A) is preferably 25% by mass or more, more preferably 50% by mass, further preferably 75% by mass, and 100% based on the total mass of the base material component (A). It may be% by mass. When the ratio is 25% by mass or more, the lithography characteristics are further improved.

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

<Basic compound component; (D) component>
In addition to the component (D0), the resist composition of the present invention may further contain an acid diffusion control agent component (hereinafter, also referred to as “component (D)”).
The component (D) acts as a quencher (acid diffusion control agent) that traps the acid generated by exposure from the component (B) and the like.
The component (D) in the present invention may be a photodisintegrating base (D1) (hereinafter referred to as “component (D1)”) that is decomposed by exposure and loses acid diffusion controllability, and the component (D1) may be used. It may be a nitrogen-containing organic compound (D2) (hereinafter, referred to as “(D2) component”) which does not correspond to the above.

[(D1) component]
By using a resist composition containing the component (D1), it is possible to improve the contrast between the exposed portion and the non-exposed portion when forming the resist pattern.
The component (D1) is not particularly limited as long as it is decomposed by exposure and loses acid diffusion controllability, and is a compound represented by the following general formula (d1-1) (hereinafter, “component (d1-1)”). The compound represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component") and the compound represented by the following general formula (d1-3) (hereinafter referred to as "(d1-d1-) component"). 3) One or more compounds selected from the group consisting of "components") are preferable.
The components (d1-1) to (d1-3) do not act as a quencher because they decompose in the exposed portion and lose the acid diffusion controllability (basicity), but act as a quencher in the unexposed portion.

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

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

{(D1-1) component}
-In the anion part formula (d1-1), Rd ¹ has a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is also a good chain alkenyl group, and examples thereof include those similar to R ¹⁰¹ .
Among these, Rd ¹ may have an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a substituent. Chained hydrocarbon groups are preferred. As the substituent that these groups may have, a hydroxyl group, a fluorine atom or a fluorinated alkyl group is preferable.
As the aromatic hydrocarbon group, a phenyl group or a naphthyl group is more preferable.
The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
As the chain hydrocarbon group, a chain alkyl group is preferable. The chain alkyl group preferably has 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Linear alkyl groups such as groups and decyl groups; 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 other branched alkyl groups;

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

A preferable specific example of the anion portion of the component (d1-1) is shown below.

-In the cation part formula (d1-1), M ^{m +} is an m-valent organic cation.
The organic cation of M ^{m +} is not particularly limited, and examples thereof include the same cations represented by the general formulas (ca-1) to (ca-4), respectively, and the above formula (ca-1-). The cations represented by 1) to (ca-1-63) are preferable.
As the component (d1-1), one type may be used alone, or two or more types may be used in combination.

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

A preferable specific example of the anion portion of the component (d1-2) is shown below.

-In the cation part formula (d1-2), M ^{m +} is an m-valent organic cation, which is the same as M ^{m +} in the above formula (d1-1).
As the component (d1-2), one type may be used alone, or two or more types may be used in combination.

{(D1-3) component}
-In the anion part formula (d1-3), Rd ³ has a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It is also a good chain alkenyl group, which is similar to R ^101, and is preferably a cyclic group containing a fluorine atom, a chain alkyl group, or a chain alkenyl group. Of these, an alkyl fluorinated group is preferable, and the same group as the alkyl fluorinated group of Rd ¹ is more preferable.

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

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

Examples of the cyclic group in Rd ⁴ are the same as those in R ¹⁰¹ above, and one or more hydrogen atoms are excluded from cycloalkanes such as cyclopentane, cyclohexane, adamantan, norbornane, isobornane, tricyclodecane, and tetracyclododecane. An alicyclic group or an aromatic group such as a phenyl group or a naphthyl group is preferable. When Rd ⁴ is an alicyclic group, the resist composition is well dissolved in an organic solvent, so that the lithography characteristics are improved. Further, when Rd ⁴ is an aromatic group, the resist composition has excellent light absorption efficiency and good sensitivity and lithography characteristics in lithography using EUV or the like as an exposure light source.

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

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

-In the cation part formula (d1-3), M ^{m +} is an m-valent organic cation, which is the same as M ^{m +} in the above formula (d1-1).
As the component (d1-3), one type may be used alone, or two or more types may be used in combination.

As the component (D1), only one of the above components (d1-1) to (d1-3) may be used, or two or more of them may be used in combination.
The content of the component (D1) is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and 1 to 8 parts by mass with respect to 100 parts by mass of the component (A). It is more preferably parts by mass.
When the content of the component (D1) is at least a preferable lower limit value, particularly good lithography characteristics and a resist pattern shape can be obtained. On the other hand, when it is not more than the upper limit value, the sensitivity can be maintained well and the throughput is also excellent.

The method for producing the above-mentioned components (d1-1) and (d1-2) is not particularly limited, and can be produced by a known method.

The content of the component (D1) is preferably 0.5 to 10.0 parts by mass, and more preferably 0.5 to 8.0 parts by mass with respect to 100 parts by mass of the component (A). , 1.0 to 8.0 parts by mass is more preferable. When it is at least the lower limit of the above range, particularly good lithography characteristics and resist pattern shape can be obtained. When it is not more than the upper limit value of the above range, the sensitivity can be maintained well and the throughput is also excellent.

((D2) component)
The component (D) may contain a nitrogen-containing organic compound component (hereinafter, referred to as the component (D2)) that does not correspond to the above component (D1).
The component (D2) is not particularly limited as long as it acts as an acid diffusion control agent and does not correspond to the component (D1), and any known component may be used. Of these, aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines, are preferable.
The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms.
Examples of the aliphatic amine include amines (alkylamines or alkylalcoholamines) in which at least one hydrogen atom of ammonia NH ₃ is replaced with an alkyl group or a hydroxyalkyl group having 12 or less carbon atoms, or a cyclic amine.
Specific examples of alkylamines and alkylalcohol amines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di. Dialkylamines such as -n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine , Tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine and other trialkylamines; diethanolamine, triethanolamine, diisopropanolamine, tri Alkyl alcohol amines such as isopropanolamine, di-n-octanolamine and tri-n-octanolamine can be mentioned. Among these, trialkylamines having 5 to 10 carbon atoms are more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

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

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

Further, as the component (D2), an aromatic amine may be used.
Aromatic amines include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indol, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxy. Examples thereof include carbonylpyrrolidine.

The component (D2) may be used alone or in combination of two or more.
The component (D2) is usually used in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the component (A). Within the above range, the shape of the resist pattern, stability over time, and the like are improved.

As the component (D), one type may be used alone, or two or more types may be used in combination.
When the resist composition of the present invention contains the component (D), the component (D) is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the component (A), and is 0.3 to 15 parts by mass. It is more preferably 12 parts by mass, and even more preferably 0.5 to 12 parts by mass. When it is at least the lower limit of the above range, the lithography characteristics such as LWR are further improved when the resist composition is prepared. Moreover, a better resist pattern shape can be obtained. When it is not more than the upper limit value of the above range, the sensitivity can be maintained well and the throughput is also excellent.

<Arbitrary ingredient>
[(E) component]
In the present invention, for the purpose of preventing deterioration of sensitivity, improving the shape of the resist pattern, stability over time, etc., the resist composition is composed of organic carboxylic acid, phosphorus oxo acid and its derivative as arbitrary components. It is possible to contain at least one compound (E) (hereinafter, referred to as the component (E)) selected from the above group.
As the organic carboxylic acid, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
Examples of the oxo acid of phosphorus include phosphoric acid, phosphonic acid, phosphinic acid and the like, and among these, phosphonic acid is particularly preferable.
Examples of the derivative of the oxo acid of phosphorus include an ester in which the hydrogen atom of the oxo acid is replaced with a hydrocarbon group, and the hydrocarbon group includes an alkyl group having 1 to 5 carbon atoms and 6 to 6 carbon atoms. Examples include 15 aryl groups.
Examples of the phosphoric acid derivative include phosphoric acid esters such as phosphoric acid di-n-butyl ester and phosphoric acid diphenyl ester.
Examples of the phosphonic acid derivative include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester.
Examples of the derivative of phosphinic acid include phosphinic acid ester and phenylphosphinic acid.
As the component (E), one type may be used alone, or two or more types may be used in combination.
The component (E) is usually used in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the component (A).

[(F) component]
In the present invention, the resist composition may contain a fluorine additive (hereinafter referred to as "component (F)") in order to impart water repellency to the resist film.
Examples of the component (F) include JP-A-2010-002870, JP-A-2010-032994, JP-A-2010-277043, JP-A-2011-13569, and JP-A-2011-128226. The described fluorine-containing polymer compound can be used.
More specifically, as the component (F), a polymer having a structural unit (f1) represented by the following formula (f1-1) can be mentioned. The polymer is a polymer (copolymer) consisting of only the structural unit (f1) represented by the following formula (f1-1); the structural unit (f1) represented by the following formula (f1-1), and Copolymer with the structural unit (a1); the structural unit (f1) represented by the following formula (f1-1), the structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1). Is preferably a copolymer of. Here, the structural unit (a1) copolymerized with the structural unit (f1) represented by the following formula (f1-1) is 1-ethyl-1-cyclooctyl (meth) acrylate or the above formula (a1). The structural unit represented by -2-11) is preferable.

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

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

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

In the formula (f1-1), Rf ¹⁰¹ is preferably an organic group containing a fluorine atom and preferably a hydrocarbon group containing a fluorine atom.
The hydrocarbon group containing a fluorine atom may be linear, branched or cyclic, and preferably has 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms. , 1 to 10 carbon atoms are particularly preferable.
Further, as for the hydrocarbon group containing a fluorine atom, it is preferable that 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more is fluorinated, and 60% or more is fluorinated. It is particularly preferable that it is fluorinated because the hydrophobicity of the resist film during immersion exposure is increased.
Among ^these, as ^{Rf 101,} particularly preferably a fluorinated hydrocarbon group having 1 to 5 carbon atoms, a methyl _{group, -CH 2 -CF 3, -CH 2} -CF 2 -CF 3, -CH (CF 3) 2 , -CH _2- CH _2- CF ₃ , -CH _2- CH _2- CF _2- CF _2- CF _2- CF ₃ are most preferable.

The weight average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of the component (F) is preferably 1000 to 50000, more preferably 5000 to 40,000, and most preferably 1000 to 30000. When it is not more than the upper limit value of this range, it has sufficient solubility in a resist solvent to be used as a resist, and when it is more than the lower limit value of this range, the dry etching resistance and the cross-sectional shape of the resist pattern are good.
The dispersity (Mw / Mn) of the component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5.

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

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

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

The resist composition of the present invention includes additives that are more miscible as desired, such as additional resins for improving the performance of resist films, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, etc. Dyes and the like can be appropriately added and contained.

≪Resist pattern formation method≫
The resist pattern forming method according to the second aspect 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 a step after the exposure. It includes a step of developing a resist film to form a resist pattern.
The resist pattern forming method of the present invention can be carried out, for example, as follows.
First, the resist composition of the present invention is applied onto a support with a spinner or the like, and a bake (post-apply bake (PAB)) treatment is performed, for example, under a temperature condition of 80 to 150 ° C. for 40 to 120 seconds, preferably 60. Apply for ~ 90 seconds to form a resist film.
Next, the resist film is exposed or masked through a mask (mask pattern) on which a predetermined pattern is formed by using an exposure device such as an ArF exposure device, an electron beam drawing device, or an EUV exposure device. After selective exposure such as drawing by direct irradiation of electron beams without intervention, baking (post-exposure baking (PEB)) treatment is performed, for example, under a temperature condition of 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to 60 to. Apply for 90 seconds.
Next, the resist film after the exposure is developed.
In the case of an alkaline developing process, an alkaline developing solution is used, and in the case of a solvent developing process, a developing solution containing an organic solvent (organic developing solution) is used for the developing process.
After the development treatment, a rinsing treatment is preferably performed. In the case of the alkaline development process, the rinsing treatment is preferably a water rinse using pure water, and in the case of the solvent development process, it is preferable to use a rinse solution containing an organic solvent.
In the case of the solvent development process, after the development treatment or the rinsing treatment, a treatment for removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be performed.
Drying is performed after the development treatment or the rinsing treatment. In some cases, a baking process (post-baking) may be performed after the development process. In this way, a resist pattern can be obtained.

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

Wavelength used for the exposure is not particularly limited, ArF excimer laser, KrF excimer laser, _{F 2} excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays It 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 a normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or an immersion exposure (Liquid Imaging Lithography).
In immersion exposure, the space between the resist film and the lens at the lowest position of the exposure apparatus is previously filled with a solvent (immersion medium) having a refractive index larger than the refractive index of air, and exposure (immersion exposure) is performed in that state. This is an exposure method.
As the immersion medium, a solvent having a refractive index larger than that of air and smaller than that 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 fluorine-based compounds 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 main components. Examples thereof include liquids, which have a boiling point of 70 to 180 ° C., and more preferably 80 to 160 ° C. It is preferable that the fluorine-based inert liquid has a boiling point in the above range because the medium used for immersion can be removed by a simple method after the end of exposure.
As the fluorine-based inert liquid, a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms is particularly preferable. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.
Further, specifically, the perfluoroalkyl ether compound may include perfluoro (2-butyl-tetrahydrofuran) (boiling point 102 ° C.), and the perfluoroalkylamine compound may include perfluorotributylamine (perfluorotributylamine). Boiling point 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 alkaline developer used in the developing process in the alkaline developing process include an aqueous solution of 0.1 to 10 mass% tetramethylammonium hydroxide (TMAH).
The organic solvent contained in the organic developer used in the developing process in the solvent developing process may be any known organic solvent as long as it can dissolve the component (A) (component (A) before exposure). It can be selected as appropriate. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents and the like, and hydrocarbon solvents can be used.
A known additive can be added to the organic developer, if necessary. Examples of the additive include a surfactant. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used.
When a surfactant is blended, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0.% With respect to the total amount of the organic developer. 5% by mass is more preferable.

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

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

A third aspect of the present invention is a compound represented by the following general formula (d0).

［式中、Ｒ^１は置換基を有していてもよい炭素数１〜２０の鎖状、分岐鎖状又は環状の炭化水素基である。但し、式中のカルボニル基に隣接するＲ^１の炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。Ｒ^２は置換基を有していてもよい炭素数１〜２０の鎖状、分岐鎖状又は環状の炭化水素基である。但し、式中のスルホニル基に隣接するＲ^２の炭素原子に置換基が結合している場合、該置換基は、ハロゲン原子を有する基、芳香族基、及びプロトンアクセプター性官能基からなる群より選ばれる１種以上を有さないものとする。Ｍ^ｍ＋はｍ価の有機カチオンである。ｍは１以上の整数である。］

[In the formula, R ¹ is a chain, branched chain or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. However, when a substituent is bonded to the carbon atom of R ¹ adjacent to the carbonyl group in the formula, the substituent is a group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more selected from. R ² is a chain, branched chain or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. However, if the substituent at a carbon atom of R ² adjacent to the sulfonyl group in the formula are bonded, the substituent group having a halogen atom, an aromatic group, and the group consisting of proton acceptor functional group It is assumed that there is no one or more selected from the above. M ^{m +} is an m-valent organic cation. m is an integer of 1 or more. ]

In the above formula, the description of R ^1, R ² , and M ^{m +} is the same as described above.
Further, the compound of the third aspect of the present invention is preferably a compound represented by the general formula (d0-1), and the general formula (d0-1a), (d0-1b) or (d0). It is more preferable that the compound is represented by any one of -1c).

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

[Example of compound synthesis]
5.23 g (55.0 mmol) of methanesulfonamide was dissolved in 52.3 g of tetrahydrofuran (THF) and ice-cooled with stirring. After adding 6.07 g (60.0 mmol) of triethylamine to this, a solution prepared by dissolving 6.03 g (50.0 mmol) of pivaloyl chloride in 30.2 g of THF was added dropwise over 1 hour, and further 3 hours. Stirring was performed.
A 5% aqueous hydrochloric acid solution and t-butyl methyl ether were added dropwise to the reaction solution, the temperature was raised to room temperature, and then a liquid separation operation was performed to extract the organic phase. After repeating the step of washing the obtained organic phase with 52.3 g of pure water, the organic phase was concentrated to obtain 7.17 g of Intermediate D0-1-1.
To 7.17 g of Intermediate D0-1-1, 71.7 g of pure water and 1.76 g of sodium hydroxide were added and dissolved. To this, 15.10 g of triphenylsulfonium bromide and 71.7 g of dichloromethane were added and then stirred, and a liquid separation operation was performed to extract the organic phase. After repeating the step of washing the obtained organic phase with 71.7 g of pure water, the organic phase was concentrated to obtain 14.66 g of a photobase deactivator (D0) -1.
The obtained compound was subjected to NMR measurement, and the structure was identified from the following results.
^{1 1} H NMR (DMSO-d6, 400 MHz): δ7.71-8.00 (15H, Ph), (ppm) = 2.68 (3H, CH3), 1.12 (9H, C (CH ₃ ) 3)

The following (D0) -2 to (D0) -19 were synthesized by the same method as described above. The pKa value of the conjugate acid of the compound is also described below. The following pKa values were calculated using ACD / Labs Software V11.02.

<Preparation of resist composition>
(Examples 1 to 23, Comparative Examples 1 to 16)
Each component shown in Tables 1 to 3 was mixed and dissolved to prepare a resist composition. However, Examples 1, 3, 6, 10, 12, 15, 19, 20, and 21 are reference examples.

Each abbreviation in the above table has the following meanings. The value in [] is the blending amount (part by mass).
(A) -1 to (A) -3: The following polymer compounds (A) -1 to (A) -3.
(B) -1: The following compound (B) -1.
(D0) -1 to (D0) -19: The above compound (D0) -1 to (D0) -19.
(F) -1: The following polymer compound (F) -1.
(S) -1: A mixed solvent of PGMEA / PGME / cyclohexanone (mass ratio 45/30/25).
(S) -2: γ-Butyrolactone.

<Formation of resist pattern 1: Alkaline development positive type>
(Examples 1 to 9, Comparative Examples 1 to 7)
The organic antireflection film composition "ARC29" (trade name, manufactured by Brewer Science Co., Ltd.) is applied onto an 8-inch silicon wafer using a spinner, and baked on a hot plate at 205 ° C. for 60 seconds to dry. As a result, an organic antireflection film having a film thickness of 82 nm was formed.
Next, the resist composition is applied onto the film using a spinner, prebaked (PAB) on a hot plate at a temperature of 110 ° C. for 60 seconds, and dried to obtain a film thickness of 90 nm. A resist film was formed.
Next, an ArF excimer laser (193 nm) was applied to the resist film by an exposure apparatus NSR-S609B (NA = 1.07 Dipole 0.97 / 0.78 with polaro manufactured by Nikon Corporation) via a mask pattern (6% halftone). And selectively irradiated.
Then, at 23 ° C., alkali development was carried out for 10 seconds using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.).
As a result, a line-and-space pattern (hereinafter, may be referred to as "LS pattern") was formed in each of the examples.
In each example, a line-and-space pattern with a line width of 50 nm / pitch of 100 nm was formed.

<Formation of resist pattern 2: Solvent development negative type>
(Examples 10 to 23, Comparative Examples 8 to 16)
The organic antireflection film composition "ARC29" (trade name, manufactured by Brewer Science Co., Ltd.) is applied onto an 8-inch silicon wafer using a spinner, and baked on a hot plate at 205 ° C. for 60 seconds to dry. As a result, an organic antireflection film having a film thickness of 82 nm was formed.
Next, the resist composition is applied onto the film using a spinner, prebaked (PAB) on a hot plate at a temperature of 90 ° C. for 60 seconds, and dried to obtain a film thickness of 100 nm. A resist film was formed.
Next, an ArF excimer laser (193 nm) was applied to the resist film by an exposure apparatus NSR-S609B (NA = 1.07 Dipole 0.97 / 0.78 with polaro manufactured by Nikon Corporation) via a mask pattern (6% halftone). And selectively irradiated.
Then, at 23 ° C., solvent development was carried out with butyl acetate for 16 seconds, and shake-off drying was performed. As a result, a line-and-space pattern was formed in each of the examples.
In each example, a line-and-space pattern with a line width of 50 nm / pitch of 100 nm was formed.

[Evaluation of Optimal Exposure (Eop)]
The optimum exposure amount Eop (mJ / cm ² ) at which the target size LS pattern is formed was determined by the resist pattern forming method. The results are also shown in Tables 4 to 6 below as "sensitivity (mJ / cm ² )".

[Evaluation of exposure margin (EL margin)]
In the exposure amount at which the LS pattern is formed, the exposure amount when the line of the LS pattern is formed within the range of ± 5% of the target dimension was obtained, and the EL margin (unit:%) was obtained by the following equation. The results are listed in Tables 4 to 6 below as "5% EL (%)".
EL margin (%) = (| E1-E2 | / Eop) x 100
E1: Exposure amount (mJ / cm ² ) when an LS pattern with a hole width of 47.5 nm is formed.
E2: Exposure amount (mJ / cm ² ) when an LS pattern having a hole width of 52.5 nm is formed.
The larger the value of the EL margin, the smaller the amount of change in the pattern size due to the change in the exposure amount.
In the above EL margin calculation formula, "Eop" means the optimum exposure amount (mJ / cm ² ). The Eop was determined by a conventional method.

[Evaluation of mask error factor (MEEF)]
According to the same procedure as the resist pattern formation, mask patterns having a target size (line width) of 45 to 55 nm (1 nm increments, 11 points in total) are used, and each line and space pattern having a pitch of 100 nm is subjected to the same exposure amount. Formed.
At that time, the slope of a straight line (MEEF) was calculated when the line width (nm) of the pattern formed on the resist film using each mask pattern was plotted on the vertical axis with the target size (nm) as the horizontal axis. The results are also shown in Tables 4 to 6 below as "MEEF".
The closer the value of MEEF (slope of a line) is to 1, the better the mask reproducibility.

[Evaluation of LWR (Linewise Roughness)]
In the LS pattern formed by the above <formation of resist pattern>, the hole width is adjusted by a length measuring SEM (scanning electron microscope, acceleration voltage 300 V, trade name: S-9380, manufactured by Hitachi High-Technologies Corporation). Measurements were made at 400 points in the longitudinal direction, a triple value (3s) of the standard deviation (s) was obtained from the results, and the averaged value for 3s at 400 points was calculated as a scale indicating LWR. The results are also shown in Tables 4 to 6 below as "LWR (nm)".
The smaller the value of 3s, the smaller the roughness of the line width, which means that an LS pattern having a more uniform width was obtained.

[Evaluation of shape]
The LS pattern was observed by a length measuring SEM (scanning electron microscope, accelerating voltage 800V, trade name: S-9220, manufactured by Hitachi, Ltd.). The results are also shown in Tables 4 to 6 below as "rectangularity".

[Storage stability]
1) For each of the resist compositions before and after being stored at room temperature for January, a contact hole pattern was formed by the resist pattern forming method at the optimum exposure amount Eop, and the hole diameter (CD) was measured.
2) For the resist compositions of each example, the difference (CD fluctuation value) before and after storage was calculated after storing at room temperature for January. The results are also shown in Tables 4 to 6 below as "storage stability".
When ΔCD was less than 1 nm, it was regarded as excellent in storage stability of the resist composition, and was evaluated as “◯”, and other cases were evaluated as “x”.

As shown in the above results, the resist composition of the present invention was excellent in storage stability and lithographic characteristics.
Among the above, Example 4 using compound (D0) -4 and Example 5 using compound (D0) -5 in which at least one of the terminal groups is a cyclic hydrocarbon group as the component (D0). Was particularly excellent in MEEF, EL margin, and LWR.

Claims (6)

A resist composition that generates an acid upon exposure and changes its solubility in a developing solution by the action of the acid.
Acid generator component (B) that generates acid by exposure and
A photobase inactivating agent component (D0) containing a compound represented by the following general formula (d0-1a ) and
(However, those containing a compound represented by the following formula (1) are excluded).

Wherein the fat R ^11a may include a monocyclic or polycyclic alicyclic hydrocarbon group having a carbon number of 3 to 20 (this alicyclic hydrocarbon groups may have a substituent) It is a group hydrocarbon group. However, when a substituent is bonded to a carbon atom that is directly covalently bonded to the carbonyl group in R ^11a in the formula, the substituent is a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more species selected from the group consisting of. R ^12a is a chain-like or branched-chain hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. However, when a substituent is bonded to a carbon atom that is directly covalently bonded to the sulfonyl group in R ^12a in the formula, the substituent is a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more species selected from the group consisting of. M ^{m +} is an m-valent organic cation. m is an integer of 1 or more. ]

[In formula (1), R ⁰¹ is a single-bonded, substituted or unsubstituted methanediyl group, a substituted or unsubstituted ethanediyl group, or a substituted or unsubstituted 1,2-benzenediyl group. R ⁰² is −SO ₂ R ⁰⁴ . R ⁰⁴ is a monovalent organic group having 1 to 20 carbon atoms. R ⁰³ is a monovalent organic group having 1 to 30 carbon atoms. n is an integer of 1 or more and 3 or less. When n is 2 or more, a plurality of R ^01s may be the same or different. M " ⁺ is a monovalent radiolytic onium cation. However, two or more of R ⁰¹ , R ⁰² and R ⁰³ form a ring structure having 5 to 30 ring members by these bonds. May be good.] A resist composition that generates an acid upon exposure and changes its solubility in a developing solution by the action of the acid.
Acid generator component (B) that generates acid by exposure and
A photobase inactivating agent component (D0) containing a compound represented by the following general formula (d0-1b) and
(However, those containing a compound represented by the following formula (1) are excluded).

Wherein, R ^11b is a linear or branched hydrocarbon radical having 1 to 20 carbon atoms that may have a substituent. However, when a substituent is bonded to a carbon atom that is directly covalently bonded to the carbonyl group in R ^11b in the formula, the substituent is a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more species selected from the group consisting of. R ^12b is an aliphatic hydrocarbon group containing a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 20 carbon atoms (the alicyclic hydrocarbon group may have a substituent). Is. However, when a substituent is bonded to a carbon atom that is directly covalently bonded to the sulfonyl group in R ^12b in the formula, the substituent is a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more species selected from the group consisting of. M ^{m +} is an m-valent organic cation. m is an integer of 1 or more. ]

[In formula (1), R ⁰¹ is a single-bonded, substituted or unsubstituted methanediyl group, a substituted or unsubstituted ethanediyl group, or a substituted or unsubstituted 1,2-benzenediyl group. R ⁰² is −SO ₂ R ⁰⁴ . R ⁰⁴ is a monovalent organic group having 1 to 20 carbon atoms. R ⁰³ is a monovalent organic group having 1 to 30 carbon atoms. n is an integer of 1 or more and 3 or less. When n is 2 or more, a plurality of R ^01s may be the same or different. M " ⁺ is a monovalent radiolytic onium cation. However, two or more of R ⁰¹ , R ⁰² and R ⁰³ form a ring structure having 5 to 30 ring members by these bonds. May be good.] The resist composition according to claim 1 or 2, wherein the pKa of the conjugate acid of the compound represented by the general formula (d0-1a) or the general formula (d0-1b) is greater than 2.5. A step of forming a resist film using the resist composition according to any one of claims 1 to 3 on a support, a step of exposing the resist film, and a step of developing the resist film after the exposure. A resist pattern forming method including a step of forming a resist pattern. Compounds represented by the following general formula (d0-1a) ( excluding compounds represented by the following formula (1)).

Wherein the fat R ^11a may include a monocyclic or polycyclic alicyclic hydrocarbon group having a carbon number of 3 to 20 (this alicyclic hydrocarbon groups may have a substituent) It is a group hydrocarbon group. However, when a substituent is bonded to a carbon atom that is directly covalently bonded to the carbonyl group in R ^11a in the formula, the substituent is a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more species selected from the group consisting of. R ^12a is a chain-like or branched-chain hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. However, when a substituent is bonded to a carbon atom that is directly covalently bonded to the sulfonyl group in R ^12a in the formula, the substituent is a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have one or more species selected from the group consisting of. M ^{m +} is an m-valent organic cation. m is an integer of 1 or more. ]

[In formula (1), R ⁰¹ is a single-bonded, substituted or unsubstituted methanediyl group, a substituted or unsubstituted ethanediyl group, or a substituted or unsubstituted 1,2-benzenediyl group. R ⁰² is −SO ₂ R ⁰⁴ . R ⁰⁴ is a monovalent organic group having 1 to 20 carbon atoms. R ⁰³ is a monovalent organic group having 1 to 30 carbon atoms. n is an integer of 1 or more and 3 or less. When n is 2 or more, a plurality of R ^01s may be the same or different. M " ⁺ is a monovalent radiolytic onium cation. However, two or more of R ⁰¹ , R ⁰² and R ⁰³ form a ring structure having 5 to 30 ring members by these bonds. May be good.] Compounds represented by the following general formula (d0-1b) (excluding compounds represented by the following formula (1)).

[In the formula, R ^11b Is a chain-like or branched-chain hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. However, R in the formula ^11b When a substituent is bonded to a carbon atom that is directly covalently bonded to the carbonyl group, the substituent is selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have more than a seed. R ^12b Is an aliphatic hydrocarbon group containing a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 20 carbon atoms (the alicyclic hydrocarbon group may have a substituent). .. However, R in the formula ^12b In the case where a substituent is bonded to a carbon atom that directly covalently bonds with a sulfonyl group, the substituent is selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group. It shall not have more than a seed. M ^{m +} Is an m-valent organic cation. m is an integer of 1 or more. ]

[In equation (1), R ⁰¹ Is a single-bonded, substituted or unsubstituted methanediyl group, a substituted or unsubstituted ethanediyl group, or a substituted or unsubstituted 1,2-benzenediyl group. R ⁰² Is -SO ₂ R ⁰⁴ Is. R ⁰⁴ Is a monovalent organic group having 1 to 20 carbon atoms. R ⁰³ Is a monovalent organic group having 1 to 30 carbon atoms. n is an integer of 1 or more and 3 or less. When n is 2 or more, multiple R ⁰¹ May be the same or different. M " ^＋ Is a monovalent radiolytic onium cation. However, R ⁰¹ , R ⁰² And R ⁰³ Two or more of them may form a ring structure having 5 to 30 ring members by these bonds. ]