JP6219175B2 - Compound production method and polymer compound production method - Google Patents

Description

  The present invention relates to a method for producing a compound useful for a resist composition and a method for producing a polymer compound.

A technique (pattern formation technique) in which a fine pattern is formed on a substrate and etching is performed using the fine pattern as a mask to process a lower layer of the pattern (pattern formation technique) is widely adopted in the manufacture of semiconductor elements and liquid crystal display elements. The fine pattern is usually made of an organic material and is formed by a technique such as a lithography method or a nanoimprint method. For example, in a lithography method, a resist film is formed on a support such as a substrate using a resist material containing a base material component such as a resin, and the resist film is selected by radiation such as light or an electron beam. A step of forming a resist pattern having a predetermined shape on the resist film is performed by performing a general exposure and developing. And a semiconductor element etc. are manufactured through the process of processing a board | substrate by an etching using this resist pattern as a mask.
The resist material is classified into a positive type and a negative type. A resist material whose solubility in an exposed portion of a developer increases is called a positive type, and a resist material whose solubility in an exposed portion of a developer decreases is called a negative type. .
As the developer, an alkaline aqueous solution (alkali developer) such as a tetramethylammonium hydroxide (TMAH) aqueous solution is usually used. Developers containing organic solvents such as aromatic organic solvents, aliphatic hydrocarbon organic solvents, ether organic solvents, ketone organic solvents, ester organic solvents, amide organic solvents, alcohol organic solvents, etc. (Organic developer) is also used as a developer.

In recent years, pattern miniaturization has been progressing rapidly due to advances in lithography technology.
As a technique for miniaturization, the exposure light source is generally shortened in wavelength (increased energy). Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used, but mass production of semiconductor elements using a KrF excimer laser or an ArF excimer laser has been started. Further, studies have been made on EB (electron beam), EUV (extreme ultraviolet), X-rays, and the like having shorter wavelengths (higher energy) than these excimer lasers.

Along with the shortening of the wavelength of the exposure light source, the resist material is required to be improved in lithography characteristics such as sensitivity to the exposure light source and resolution capable of reproducing a pattern with a fine dimension. A chemically amplified resist composition is known as a resist material that satisfies such requirements.
As the chemically amplified resist composition, generally, a 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 upon exposure is used. Yes. For example, when the developer is an alkali developer (alkaline development process), a substrate component that has increased solubility in an alkali developer due to the action of an acid is used.

  Conventionally, a resin (base resin) is mainly used as a base material component of a chemically amplified resist composition. At present, as a base resin of a chemically amplified resist composition used in ArF excimer laser lithography and the like, it has a structural unit derived from (meth) acrylic acid ester in its main chain because of its excellent transparency near 193 nm. Resin (acrylic resin) is the mainstream.

  Here, “(meth) acrylic acid” means one or both of acrylic acid having a hydrogen atom bonded to the α-position and methacrylic acid having a methyl group bonded to the α-position. “(Meth) acrylic acid ester” means one or both of an acrylic acid ester having a hydrogen atom bonded to the α-position and a methacrylic acid ester having a methyl group bonded to the α-position. “(Meth) acrylate” means one or both of an acrylate having a hydrogen atom bonded to the α-position and a methacrylate having a methyl group bonded to the α-position.

  The base resin of the chemically amplified resist composition generally has a plurality of types of structural units in order to improve lithography properties and the like. For example, a structural unit having an acid-decomposable group that decomposes by the action of an acid generated from an acid generator to generate an alkali-soluble group, a structural unit having a lactone structure, a structural unit having a polar group such as a hydroxyl group, etc. are used. (For example, refer to Patent Document 1). When the base resin is an acrylic resin, as the acid-decomposable group, generally, a carboxy group in (meth) acrylic acid or the like is protected with an acid-dissociable group such as a tertiary alkyl group or an acetal group. Things are used.

A positive development process that combines a positive chemically amplified resist composition, that is, a chemically amplified resist composition whose solubility in an alkali developer increases upon exposure, and an alkaline developer is a negative chemically amplified type. Compared to a negative development process in which a resist composition and an alkali developer are combined, there are advantages such as a simple photomask structure and excellent pattern characteristics. Therefore, at present, a positive development process in which a positive chemically amplified resist composition and an alkali developer are combined is mainly used for forming a fine pattern.
When the positive development process is applied, when the resist film obtained by coating the positive chemically amplified resist composition on the support is selectively exposed, the exposed portion of the resist film is a base resin. The acid-decomposable groups in the resist film are decomposed by the action of the acid generated from the acid generator, etc., and change from poorly soluble to soluble in an alkaline developer, while the unexposed part of the resist film remains hardly soluble in alkali. Therefore, by developing with an alkali developer, dissolution contrast can be provided between the exposed and unexposed areas, and a positive resist pattern can be formed.
In order to improve lithography properties and the like, conventionally, for example, a structural unit having an acid-decomposable group in which a side chain portion is long and an oxygen atom (-O-) and a carbonyl group are introduced into the side chain portion, And a chemically amplified resist composition using the polymer compound as a base resin has been proposed (see Patent Document 2).

JP 2003-241385 A JP 2009-223300 A

With the increasing performance and miniaturization of electronic devices, further improvements in resist pattern shape are required for pattern formation when manufacturing semiconductor elements and the like. However, there is still room for improvement in the shape of a resist pattern formed using a conventional resist composition, and there is a demand for further improvement in lithography characteristics and the like.
This invention is made | formed in view of the said situation, Comprising: It makes the subject the resist material which can form the resist pattern of a more favorable shape.

  The present inventors have used a polymer compound having a specific structure introduced in the side chain portion as a base resin in forming a resist pattern with a resist composition. It was found that the dissolution contrast with the part increases and the lithography properties are further improved. However, it has been conventionally difficult to obtain a monomer having a specific structure introduced in the side chain portion, which constitutes the polymer compound as the base resin. On the other hand, the present inventors have found that the objective monomer can be synthesized by adopting a specific tertiary amine as a base in such synthesis, and the present invention has been completed.

That is, the first aspect of the present invention is a compound represented by the following general formula (m0-1) and a tertiary alcohol represented by the following general formula (m0-2). And a tertiary amine having an acid dissociation constant (pKa) of the conjugate acid of 7 or less (provided that R ^ca1 , R ^ca2 and R ^{ca3 in the} general formula (ca) bind to each other). To obtain a compound represented by the following general formula (m0) having Ra ⁰¹ as an acid-dissociable group by reacting in the presence of the non-existing nitrogen atom is a part of the aromatic ring). This is a method for producing a compound.

［式中、Ｒは、水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｖａ^０１及びＶａ^０２は、それぞれ独立に、炭素数が２〜１０の炭化水素基である。Ｖａ^０１−Ｌａ^０−は、Ｖａ^０１−Ｃ（＝Ｏ）Ｏ−又はＶａ^０１−ＯＣ（＝Ｏ）−である。ｎ_ａ０は、１〜５の整数である。Ｒａ^０１は、炭素数５以上の第３級炭素原子を有する鎖状炭化水素基、又は、炭素数４以上の第３級炭素原子を有する環状炭化水素基である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Va ⁰¹ and Va ⁰² are each independently a hydrocarbon group having 2 to 10 carbon atoms. Va ⁰¹ -La ⁰ -is Va ⁰¹ -C (= O) O- or Va ⁰¹ -OC (= O)-. n _a0 is an integer of 1 to 5. Ra ⁰¹ is a chain hydrocarbon group having a tertiary carbon atom having 5 or more carbon atoms or a cyclic hydrocarbon group having a tertiary carbon atom having 4 or more carbon atoms. ]

［式中、Ｒ^ｃａ１、Ｒ^ｃａ２及びＲ^ｃａ３は、それぞれ独立に、置換基を有してもよい炭化水素基であり；Ｒ^ｃａ１、Ｒ^ｃａ２及びＲ^ｃａ３のうち２つ以上が結合して環を形成し、第３級アミンを形成してもよい。］

[Wherein, R ^ca1 , R ^ca2 and R ^ca3 each independently represent a hydrocarbon group which may have a substituent; two or more of R ^ca1 , R ^ca2 and R ^ca3 are bonded to form a ring. To form a tertiary amine. ]

The second aspect of the present invention is obtained by the step (I) of obtaining the compound represented by the general formula (m0) by the method for producing the compound of the first aspect of the present invention, and the step (I). It characterized in that it has a step (II) polymerizing the compound represented by al the above general formula (m0), and a method for producing a polymer.

According to the method for producing a compound of the present invention, a monomer that is a raw material of a polymer compound useful as a base resin for a resist composition can be produced.
According to the method for producing a polymer compound of the present invention, a polymer compound useful as a base resin for a resist composition can be produced. In addition, according to the resist composition containing the polymer compound, a resist pattern having a better shape can be formed.

In the present specification and claims, “aliphatic” is a relative concept with respect to aromatics, and is defined to mean groups, compounds, etc. that do not have aromaticity.
Unless otherwise specified, the “alkyl group” includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
The “alkylene group” includes linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified.
The “halogenated alkyl group” is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
“Fluorinated alkyl group” or “fluorinated alkylene group” refers to a group in which part or all of the hydrogen atoms of an alkyl group or alkylene group are substituted with fluorine atoms.
“Structural unit” means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When it is described as “may have a substituent”, when a hydrogen atom (—H) is substituted with a monovalent group, and when a methylene group (—CH ₂ —) is substituted with a divalent group And both.
“Exposure” is a concept including general irradiation of radiation.

“A structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.
“Acrylic acid ester” is a compound in which the hydrogen atom at the carboxy group terminal of acrylic acid (CH ₂ ═CH—COOH) is substituted with an organic group.
In the acrylate ester, the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent. The substituent (R ^α0 ) for substituting the hydrogen atom bonded to the α-position carbon atom is an atom or group other than a hydrogen atom, such as an alkyl group having 1 to 5 carbon atoms or a halogenated group having 1 to 5 carbon atoms. An alkyl group etc. are mentioned. In addition, itaconic acid diesters in which the substituent (R ^α0 ) is substituted with a substituent containing an ester bond, and α-hydroxyacrylic esters in which the substituent (R ^α0 ) is substituted with a hydroxyalkyl group or a group with a modified hydroxyl group thereof Shall be included. The α-position carbon atom of the acrylate ester is a carbon atom to which a carbonyl group of acrylic acid is bonded unless otherwise specified.
Hereinafter, an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position is substituted with a substituent may be referred to as an α-substituted acrylate ester. Further, the acrylate ester and the α-substituted acrylate ester may be collectively referred to as “(α-substituted) acrylate ester”.

“Structural 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, and one or both of the hydrogen atoms of the amino group of acrylamide may be substituted with a substituent. The α-position carbon atom of acrylamide is a carbon atom to which the carbonyl group of acrylamide is bonded unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom bonded to the α-position carbon atom of acrylamide are the same as those described as the α-position substituent (substituent (R ^α0 )) in the α-substituted acrylic ester. Can be mentioned.

“A structural unit derived from hydroxystyrene or a hydroxystyrene derivative” means a structural unit formed by cleavage of an ethylenic double bond of hydroxystyrene or a hydroxystyrene derivative.
“Hydroxystyrene derivative” is a concept including those in which the hydrogen atom at the α-position of hydroxystyrene is substituted with another substituent such as an alkyl group or an alkyl halide group, and derivatives thereof. These derivatives include those in which the hydrogen atom of the hydroxy styrene of the hydroxystyrene which may be substituted with a substituent at the α-position is substituted with an organic group; the hydrogen atom at the α-position is substituted with a substituent The thing etc. which the substituents other than a hydroxyl group couple | bonded with the benzene ring of good hydroxystyrene are mentioned. The α-position (α-position carbon atom) of hydroxystyrene refers to a carbon atom to which a benzene ring is bonded unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom at the α-position of hydroxystyrene include the same substituents (substituent (R ^α0 )) given as the substituent at the α-position in the α-substituted acrylic ester.

The “structural unit derived from vinyl benzoic acid or a vinyl benzoic acid derivative” means a structural unit configured 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 a compound 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. These derivatives include those in which the hydrogen atom at the carboxy group of vinyl benzoic acid, which may be substituted with a hydrogen atom at the α-position, 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. In addition, the α-position (carbon atom at the α-position) of vinylbenzoic acid refers to a carbon atom to which a benzene ring is bonded unless otherwise specified.

“Styrene” is a concept that includes styrene and those in which the α-position hydrogen atom of styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group.
“Structural unit derived from styrene” and “structural unit derived from styrene derivative” mean a structural unit formed by cleavage of an ethylenic double bond of styrene or a styrene derivative.

The alkyl group as a substituent at the α-position is preferably a linear or branched alkyl group, 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.
Specific examples of the halogenated alkyl group as the substituent at the α-position include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as the substituent at the α-position” are substituted with a halogen atom. It is done. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
Specific examples of the hydroxyalkyl group as a substituent at the α-position include a group in which part or all of the hydrogen atoms of the “alkyl group as the substituent at the α-position” are substituted with a hydroxyl group. 1-5 are preferable and, as for the number of the hydroxyl groups in this hydroxyalkyl group, 1 is the most preferable.

≪Method for producing compound≫
The method for producing a compound according to the first aspect of the present invention includes a compound represented by the following general formula (m0-1) (hereinafter also referred to as “compound (m0-1)”), and a general formula (m0-2). ) Is a compound represented by the following general formula (ca), wherein the acid dissociation constant (pKa) of the conjugate acid is A tertiary amine that is 7 or less (except that the nitrogen atom to which R ^ca1 , R ^ca2, and R ^{ca3 in the} general formula (ca) are bonded is part of an aromatic ring) the tertiary amine "and be reacted in the presence of also referred) of, (represented by m0), compound to acid-labile group and Ra ⁰¹ (hereinafter" compound (m0) following general formula also called ") Is the way to get.

［式中、Ｒは、水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｖａ^０１及びＶａ^０２は、それぞれ独立に、炭素数が２〜１０の炭化水素基である。Ｖａ^０１−Ｌａ^０−は、Ｖａ^０１−Ｃ（＝Ｏ）Ｏ−又はＶａ^０１−ＯＣ（＝Ｏ）−である。ｎ_ａ０は、１〜５の整数である。Ｒａ^０１は、炭素数５以上の第３級炭素原子を有する鎖状炭化水素基、又は、炭素数４以上の第３級炭素原子を有する環状炭化水素基である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Va ⁰¹ and Va ⁰² are each independently a hydrocarbon group having 2 to 10 carbon atoms. Va ⁰¹ -La ⁰ -is Va ⁰¹ -C (= O) O- or Va ⁰¹ -OC (= O)-. n _a0 is an integer of 1 to 5. Ra ⁰¹ is a chain hydrocarbon group having a tertiary carbon atom having 5 or more carbon atoms or a cyclic hydrocarbon group having a tertiary carbon atom having 4 or more carbon atoms. ]

［式中、Ｒ^ｃａ１、Ｒ^ｃａ２及びＲ^ｃａ３は、それぞれ独立に、置換基を有してもよい炭化水素基であり；Ｒ^ｃａ１、Ｒ^ｃａ２及びＲ^ｃａ３のうち２つ以上が結合して環を形成し、第３級アミンを形成してもよい。］

[Wherein, R ^ca1 , R ^ca2 and R ^ca3 each independently represent a hydrocarbon group which may have a substituent; two or more of R ^ca1 , R ^ca2 and R ^ca3 are bonded to form a ring. To form a tertiary amine. ]

-About the compound (compound (m0-1)) represented by general formula (m0-1) In said formula (m0-1), R is a hydrogen atom, a C1-C5 alkyl group, or C1-C1. 5 halogenated alkyl groups.
The alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n- Examples thereof include a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is particularly preferable from the viewpoint of industrial availability.

In the formula (m0-1), Va ⁰¹ and Va ⁰² are each independently a hydrocarbon group having 2 to 10 carbon atoms.
The hydrocarbon group in Va ⁰¹ and Va ⁰² may each independently be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group as the hydrocarbon group in Va ⁰¹ and Va ⁰² may be saturated or unsaturated, and is usually preferably saturated.
More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

The linear or branched aliphatic hydrocarbon group has 2 to 10 carbon atoms, preferably 2 to 6, more preferably 2 to 5, particularly preferably 2 or 3, and most preferably 2.
Specific examples of the linear aliphatic hydrocarbon group (linear alkylene group) include a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], and a trimethylene group [— ( CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like.
Specific examples of the branched aliphatic hydrocarbon group (branched alkylene group) include —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, and —C (CH ₃ ) ₂ —. _{, -C (CH 3) (CH} 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - and the like alkyl methylene groups; -CH ( _{CH 3) CH 2 -, -} CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH 3 ) ₂ -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) CH _{2 CH 2 CH 2 -, - CH} 2 CH (CH 3) CH 2 CH 2 - and the like alkyl of And alkyl alkylene groups such as tetramethylene group. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the linear aliphatic hydrocarbon group (linear alkylene group) or the branched aliphatic hydrocarbon group (branched chain). And the same as the alkylene group).
The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 10 carbon atoms, specifically adamantane. , Norbornane, isobornane, tricyclodecane and the like.

The aromatic hydrocarbon group as the hydrocarbon group in Va ⁰¹ and Va ⁰² is a hydrocarbon group having an aromatic ring.
The aromatic hydrocarbon group has 3 to 10 carbon atoms, preferably 5 to 10 and particularly preferably 6 to 10.
Specific examples of the aromatic ring of the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene and naphthalene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. A ring etc. are mentioned. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene group); a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group) ) In which one of the hydrogen atoms is substituted with an alkylene group (for example, a group obtained by removing one hydrogen atom from an aryl group in an arylalkyl group such as a benzyl group or a phenethyl group). The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

Each of Va ⁰¹ and Va ⁰² is preferably an aliphatic hydrocarbon group, more preferably a linear or branched aliphatic hydrocarbon group, and a linear aliphatic hydrocarbon group ( A linear alkylene group) is more preferable.
Va ⁰¹ and Va ⁰² may be the same as or different from each other.

In the formula (m0-1), Va ⁰¹ -La ⁰ -is Va ⁰¹ -C (= O) O- or Va ⁰¹ -OC (= O)-, and Va ⁰¹ -OC (= O) -Is preferred.
In the formula _{(m0-1), n a0} is an integer of 1 to 5, preferably 1, 2 or 3, more preferably 1 or 2, particularly preferably 1.

Specific examples of the compound (m0-1) are shown below. In the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

· Formula tertiary alcohol (Compound (M0-2)) represented by (M0-2) the formula (M0-2) in, ^{Ra 01} for, having a tertiary carbon atom having 5 or more carbon atoms A chain hydrocarbon group or a cyclic hydrocarbon group having a tertiary carbon atom having 4 or more carbon atoms.
As will be described later, this Ra ⁰¹ is a group exhibiting acid dissociation in the compound (m0) obtained by the method for producing a compound of this embodiment.

The chain hydrocarbon group having a tertiary carbon atom in Ra ⁰¹ is a branched chain hydrocarbon group, and the chain hydrocarbon group having a tertiary carbon atom has 5 or more carbon atoms. , Preferably 5 to 20, more preferably 5 to 10, and particularly preferably 8. The chain hydrocarbon group bonded to the tertiary carbon atom is preferably a saturated hydrocarbon group (alkyl group), more preferably an alkyl group having 1 to 5 carbon atoms, and a methyl group, an ethyl group, or an isopropyl group. Further preferred.
Specifically, as the “chain hydrocarbon group having a tertiary carbon atom” in Ra ⁰¹ , among the acid dissociable groups exemplified in the structural unit (a1) described later, a branched chain having 5 or more carbon atoms A hydrocarbon group.

The cyclic hydrocarbon group having a tertiary carbon atom in Ra ⁰¹ may be a monocyclic hydrocarbon group or a polycyclic hydrocarbon group.
The carbon number of the monocyclic hydrocarbon group in Ra ⁰¹ is 4 or more, preferably 5 to 15, and more preferably 6 to 10.
The carbon number of the polycyclic hydrocarbon group in Ra ⁰¹ is preferably 7 or more, more preferably 8 to 16, and still more preferably 11 to 14.
If Ra ⁰¹ is a monocyclic hydrocarbon group, as such ^{ra 01,} in the group represented by the general formula below (a1-r2-1), Ra ' 10 is a branched alkyl group Those are preferred. In addition, as Ra ⁰¹ , an aliphatic monocyclic group formed by Ra ′ ¹¹ together with a carbon atom to which Ra ′ ¹⁰ is bonded in a group represented by the following general formula (a1-r2-1), carbon A group in which one hydrogen atom is removed from a monocycloalkane of several 3 to 8 is preferable. Specific examples of the monocycloalkane include cyclopentane, cyclohexane, cyclooctane and the like, and cyclopentane and cyclohexane are preferable.
If Ra ⁰¹ is a polycyclic hydrocarbon group, as such ^{ra 01,} in the group represented by the general formula below (a1-r2-1), Ra ' 10 is a branched alkyl group Those are preferred. In addition, as Ra ⁰¹ , an aliphatic polycyclic group formed by Ra ′ ¹¹ together with a carbon atom to which Ra ′ ¹⁰ is bonded in a group represented by the following general formula (a1-r2-1), carbon A group obtained by removing one hydrogen atom from a polycycloalkane of several 7 to 12 is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Adamantane and norbornane are preferable.

Specific examples of Ra ⁰¹ are given below. In the formula, “*” represents a bond (the same applies hereinafter).

As Ra ⁰¹ , when the compound (m0) is used as a resist material, a resist pattern having a more excellent shape can be easily obtained. Therefore, a branched hydrocarbon group having 5 or more carbon atoms, 4 or more carbon atoms, or the like. These monocyclic hydrocarbon groups are preferable, and a branched hydrocarbon group having 5 or more carbon atoms is more preferable because a resist pattern with good lithography characteristics can be obtained more easily.

  Specific examples of the compound (m0-2) are shown below.

-About a specific tertiary amine A specific tertiary amine is a compound represented by the above general formula (ca), and a tertiary amine having an acid dissociation constant (pKa) of a conjugate acid of 7 or less ( Provided that the nitrogen atom to which R ^ca1 , R ^ca2 and R ^{ca3 in the} general formula (ca) are bonded is not part of the aromatic ring.
Such a specific tertiary amine acts as a base and neutralizes with HCl generated in the reaction between the compound (m0-1) and the compound (m0-2).

In the present invention, the “acid dissociation constant (pKa)” is generally used as an index indicating the acid strength of a target substance. The pKa value of the conjugate acid of such a specific tertiary amine can be determined by measuring by a conventional method. In addition, calculated values using known software such as “ACD / Labs” (trade name, manufactured by Advanced Chemistry Development) can also be used.
The pKa value of the conjugate acid of the specific tertiary amine is 7 or less, preferably 5 to 7, and more preferably 5 to 6.5. If this pKa value is below an upper limit, reaction with a compound (m0-1) and a compound (m0-2) will progress more favorably. In addition, when the pKa value is within the above-described preferable range, the reaction between the compound (m0-1) and the compound (m0-2) proceeds more favorably.

In the formula (ca), R ^ca1 , R ^ca2 and R ^ca3 are each independently a hydrocarbon group which may have a substituent.
The hydrocarbon groups in R ^ca1 , R ^ca2 and R ^ca3 may each independently be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group as the hydrocarbon group in R ^ca1 , R ^ca2, and R ^ca3 include a linear or branched alkyl group, or a cyclic aliphatic hydrocarbon group.
The linear alkyl group preferably has 1 to 5 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group, or an n-butyl group is preferable.
The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group and the like.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocycloalkane is preferable. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane and the like, and cyclopentane is particularly preferred. The polycyclic aliphatic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, specifically adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

The aromatic hydrocarbon group as the hydrocarbon group in R ^ca1 , R ^ca2 and R ^ca3 is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. It is preferable that carbon number of an aromatic ring is 5-30, 5-20 are more preferable, 6-15 are more preferable, and 6-12 are especially preferable. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene and phenanthrene; aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms Can be mentioned. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specific examples of the aromatic hydrocarbon group for R ^ca1 , R ^ca2, and R ^ca3 include a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group); 2 A group obtained by removing one hydrogen atom from an aromatic compound containing the above aromatic ring (for example, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocyclic ring 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, etc.). The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocyclic ring preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

The “ ^optionally substituted” in R ^ca1 , R ^ca2 and R ^ca3 means hydrogen in the linear or branched alkyl group, cyclic hydrocarbon group or aromatic hydrocarbon group. It means that some or all of the atoms or carbon atoms may be substituted with a substituent (an atom or group other than a hydrogen atom).
The number of substituents in R ^ca1 , R ^ca2 and R ^ca3 may be one or two or more.
Examples of the substituent include a halogen atom, a hetero atom, an alkyl group, an ester bond, and an oxo group (═O).
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.
Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.
As said alkyl group, a C1-C6 alkyl group is preferable. The alkyl group is preferably linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
The ester bond as a substituent (when the methylene group (—CH ₂ —) is substituted with a divalent group) in R ^ca1 , R ^ca2 and R ^ca3 is —C (═O) —O—, —O—C _{(= O) -, - O} -S (= O) 2 -, - S (= O) 2 -O- , and the like.

In addition, examples of the specific tertiary amine include those in which two or more of R ^ca1 , R ^ca2 and R ^ca3 are bonded to form a ring to form a tertiary amine.

In the method for producing a compound of this embodiment, the specific tertiary amine has a nitrogen atom to which R ^ca1 , R ^ca2 and R ^{ca3 in the} general formula (ca) are bonded as a part of an aromatic ring. Is not included.
In the general formula (ca), the nitrogen atom to which R ^ca1 , R ^ca2 and R ^ca3 are bonded is a part of an aromatic ring, such as pyridine, pyrimidine, pyrazine, triazine, quinoline, isoquinoline, acridine, lutidine Etc. Those in which such a nitrogen atom is part of an aromatic ring are likely to act on the compound (m0-1) as a nucleophile. For this reason, when the nitrogen atom is a part of an aromatic ring, the reaction between the compound (m0-1) and the compound (m0-2) does not proceed, and is represented by the target general formula (m0). It becomes difficult to obtain the compound (compound (m0)).

The following is a specific tertiary amine, that is, a compound represented by the above general formula (ca), wherein the acid dissociation constant (pKa) of the conjugate acid is 7 or less (provided that the general amine Specific examples are shown below (except for the case where the nitrogen atom to which R ^ca1 , R ^ca2 and R ^{ca3 in} formula (ca) are bonded is part of an aromatic ring).
The pKa shown together with a specific example shows a calculated value using “Software V11.02 (1994-2013 ACD / Labs)” (trade name, manufactured by Advanced Chemistry Development).

  Among these specific tertiary amines, dimethylaniline (DMA) and dibutylaniline (DBA) are preferable because the target compound (m0) can be easily obtained in a high yield.

[Reaction of Compound (m0-1) with Compound (m0-2)]
In the method for producing the compound of this embodiment, the compound (m0-1) and the compound (m0-2) are reacted in the presence of such a specific tertiary amine, whereby Ra ⁰¹ is converted into an acid-dissociable group. The compound (m0) is obtained.
The method of reacting the compound (m0-1) and the compound (m0-2) is, for example, by dissolving the compound (m0-2) in a suitable organic solvent, and adding such a specific tertiary amine thereto. Stir. Subsequently, it can implement by adding and stirring a compound (m0-1) there.

  In the reaction of the compound (m0-1) with the compound (m0-2), the organic solvent for dissolving the compound (m0-2) is tetrahydrofuran, tert-butyl methyl ether, dichloromethane, acetonitrile, chloroform, methylene chloride. Etc. are preferred. The amount of the organic solvent used is preferably 50 to 1000 parts by mass and more preferably 100 to 600 parts by mass with respect to 100 parts by mass of the compound (m0-2). An organic solvent may be used individually by 1 type, and may use 2 or more types together.

  The specific tertiary amine used for the reaction of the compound (m0-1) and the compound (m0-2) may be used alone or in combination of two or more. The amount of the specific tertiary amine used is preferably about 1 to 10 mol per 1 mol of the compound (m0-2).

The reaction time between the compound (m0-1) and the compound (m0-2) varies depending on the reactivity between the compound (m0-1) and the compound (m0-2), the reaction temperature, etc. 1 to 100 hours are preferable, and 0.5 to 50 hours are more preferable.
The reaction temperature of such a reaction is preferably 50 to 150 ° C, more preferably about 70 to 90 ° C.
The amount of the compound (m0-1) used in such a reaction is usually preferably about 0.5 to 10 mol, more preferably about 1 to 5 mol, relative to 1 mol of the compound (m0-2).

As the compound (m0-1) and the compound (m0-2), commercially available compounds may be used, or synthesized compounds may be used.
Compound (m0-1) (carboxylic acid chloride) is, for example, thionyl chloride (SOCl ₂ ), oxalyl chloride ((COCl) ₂ ), sulfuryl chloride (SO ₂ Cl ₂ ) or the like with respect to the carboxylic acid as the base. Those obtained by reacting the above electrophilic halogenating agent can be used.

After completion of the reaction between the compound (m0-1) and the compound (m0-2), the compound (m0) which is the final target product in the reaction solution may be isolated and purified.
For isolation and purification, conventionally known methods can be used. For example, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc. can be used alone or in combination of two or more thereof. it can.
The structure of the compound (m0) obtained as described above is as follows: ¹ H-nuclear magnetic resonance (NMR) spectrum method, ¹³ C-NMR spectrum method, ¹⁹ F-NMR spectrum method, infrared absorption (IR) spectrum method, mass It can be confirmed by a general organic analysis method such as analysis (MS) method, elemental analysis method or X-ray crystal diffraction method.

· The compound represented by the general formula (m0) for (compound (m0)) of the formula ^{(m0) R, Va 01,} Va 02, Va 01 -La 0 -, n a0 is the formula (m0-1) ^{R in, Va 01, Va 02, Va} 01 -La 0 -, respectively similar to the _{n a0.}
^{Ra 01} in the formula (m0) is the same as ^{Ra 01} in the formula (M0-2).
The compound (m0) is a compound having Ra ⁰¹ in the general formula (m0) as an acid dissociable group.
The “acid-dissociable group (Ra ⁰¹ )” used herein is an acid dissociation in which the bond between an acid-dissociable group and an atom (—O—) adjacent to the acid-dissociable group can be cleaved by the action of an acid. A group having a property. The acid dissociable group needs to be a group having a lower polarity than the polar group (carboxy group) generated by dissociation of the acid dissociable group, whereby the acid dissociable group is dissociated by the action of an acid. In this case, a polar group having a polarity higher than that of the acid dissociable group is generated and the polarity is increased. As a result, the polarity of the entire polymer compound obtained by polymerizing the compound (m0) increases. Due to the increase in polarity, the solubility in the developer changes relatively during the development of resist pattern formation. When the developer is an alkaline developer, the solubility increases, and the developer is an organic developer. In the case of, the solubility decreases.

Specific examples of the compound (m0) are shown below. In the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

≪Method for producing polymer compound≫
The method for producing a polymer compound according to the second aspect of the present invention is a compound represented by the above general formula (m0) (compound (M)) produced by the method for producing a compound according to the first aspect of the present invention. m0)).
As a method for producing such a polymer compound, for example, compound (m0) and an arbitrary monomer are dissolved in a polymerization solvent, and azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (for example, V- And a known radical polymerization method in which polymerization is carried out by adding a radical polymerization initiator such as 601).
In the polymerization, a chain transfer agent such as HS—CH ₂ —CH ₂ —CH ₂ —C (CF ₃ ) ₂ —OH is used in combination, so that —C (CF ₃ ) ₂ —OH is terminated at the terminal. Groups may be introduced. As described above, a copolymer introduced with a hydroxyalkyl group in which a part of hydrogen atoms of the alkyl group is substituted with a fluorine atom reduces development defects and LER (line edge roughness: uneven unevenness of line side walls). It is effective in reducing
As an optional monomer, a compound copolymerizable with the compound (m0), for example, a structural unit (a1) containing an acid-decomposable group whose polarity increases by the action of an acid described later (corresponding to the structural unit (a0) A lactone-containing cyclic group, a structural unit (a2) containing a —SO ₂ -containing cyclic group or a carbonate-containing cyclic group, a structural unit (a3) containing a polar group-containing aliphatic hydrocarbon group, Examples thereof include a monomer that derives each structural unit such as the structural unit (a4) containing a dissociable aliphatic cyclic group and the structural unit (a6) that generates an acid upon exposure.

(Resist composition)
The polymer compound produced by the polymer compound production method of this embodiment is useful as a resin for a resist composition, and is preferably useful as a base component (base resin).

Such a resist composition is a resist composition that generates an acid upon exposure and changes its solubility in a developer by the action of an acid, and is a base material component (A) whose solubility in a developer changes by the action of an acid. Those containing (hereinafter also referred to as “component (A)”) are preferred.
When a resist film is formed using such a resist composition and the resist film is selectively exposed, an acid is generated in the exposed portion of the resist film, and the developer of component (A) is produced by the action of the acid. However, since the solubility of the component (A) in the developing solution does not change in the unexposed portion of the resist film, the solubility in the developing solution between the exposed portion and the unexposed portion of the resist film is changed. A sex difference arises. Therefore, when the resist film is developed, when the resist composition is positive, the exposed portion is dissolved and removed to form a positive resist pattern, and when the resist composition is negative, the unexposed portion is dissolved. This is removed to form a negative resist pattern.
In this specification, a resist composition in which an exposed portion is dissolved and removed to form a positive resist pattern is referred to as a positive resist composition, and an unexposed portion is dissolved and removed to form a negative resist pattern. Is referred to as a negative resist composition.
Such a resist composition may be a positive resist composition or a negative resist composition.
Further, such a resist composition may be used for an alkali development process using an alkali developer for the development process at the time of forming a resist pattern, and a solvent using a developer containing an organic solvent (organic developer) for the development process. It may be for a development process.

Such a resist composition has an acid generating ability to generate an acid upon exposure, and the component (A) may generate an acid upon exposure, and an additive component blended separately from the component (A) An acid may be generated by exposure.
Specifically, such a resist composition includes:
(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;
(3) The component (A) is a component that generates an acid upon exposure, and may further contain a component (B).
That is, in the case of the above (2) and (3), the component (A) is a “base material component that generates an acid upon exposure and changes its solubility in a developer due to the action of the acid”. When the component (A) is a base material component that generates an acid upon exposure and changes its solubility in a developer due to the action of the acid, the component (A1) described later generates an acid upon exposure, and A polymer compound whose solubility in a developing solution is changed by the action of an acid is preferable. As such a polymer compound, a resin having a structural unit (a6) that generates an acid upon exposure can be used. The structural unit (a6) that generates an acid upon exposure will be described later.

<(A) component>
In the present invention, the “base component” is an organic compound having a film forming ability, and preferably an organic compound having a molecular weight of 500 or more is 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 resist pattern is easily formed.
Organic compounds used as the base material component are roughly classified into non-polymers and polymers.
As the non-polymer, those having a molecular weight of 500 or more and less than 4000 are usually used. Hereinafter, the “low molecular compound” refers to a non-polymer having a molecular weight of 500 or more and less than 4000.
As the polymer, those having a molecular weight of 1000 or more are usually used. Hereinafter, the term “resin” or “polymer compound” refers to a polymer having a molecular weight of 1000 or more.
As the molecular weight of the polymer, a polystyrene-reduced mass average molecular weight by GPC (gel permeation chromatography) is used.
As the component (A) used in such a resist composition, at least the component (A1) (described later) is used, and other high molecular compounds and / or low molecular compounds may be used in combination with the component (A1).

[(A1) component]
The component (A1) is a polymer compound produced by the polymer compound production method according to the second aspect of the present invention described above, that is, a structural unit (a0) represented by the general formula (a0-1) described later. ).
When a resist film formed using a resist composition containing such a component (A1) is exposed, the structural unit (a0) has at least a partial bond in its structure cleaved by the action of an acid, and has a polarity. Increase. Therefore, such a resist composition becomes a positive type in the alkali development process and a negative type in the solvent development process. Since the polarity of the component (A1) changes before and after exposure, by using the component (A1), a good development contrast can be obtained not only in the alkali development process but also in the solvent development process.
That is, when an alkali development process is applied, the component (A1) is hardly soluble in an alkali developer before exposure, and when an acid is generated by exposure, the polarity increases due to the action of the acid, and the alkali developer Increased solubility in Therefore, in the formation of a resist pattern, when a resist film obtained by applying the resist composition on a support is selectively exposed, the exposed portion changes from slightly soluble to soluble in an alkaline developer. Since the unexposed portion remains hardly soluble in alkali and does not change, a positive resist pattern can be formed by alkali development.
On the other hand, when the solvent development process is applied, the component (A1) is highly soluble in an organic developer before exposure, and when acid is generated by exposure, the polarity of the acid increases due to the action of the acid. Solubility in developer is reduced. Therefore, in the formation of the resist pattern, when the resist film obtained by applying the resist composition on the support is selectively exposed, the exposed portion changes from soluble to poorly soluble in an organic developer. On the other hand, since the unexposed portion remains soluble and does not change, by developing with an organic developer, a contrast can be provided between the exposed portion and the unexposed portion, and a negative resist pattern can be formed.

(Structural unit (a0))
The structural unit (a0) is a structural unit represented by the following general formula (a0-1).

［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る。Ｖａ^０１及びＶａ^０２は、それぞれ独立に、炭素数が２〜１０の炭化水素基である。Ｖａ^０１−Ｌａ^０−は、Ｖａ^０１−Ｃ（＝Ｏ）Ｏ−又はＶａ^０１−ＯＣ（＝Ｏ）−である。ｎ_ａ０は、１〜５の整数である。Ｒａ^０１は、炭素数５以上の第３級炭素原子を有する鎖状炭化水素基、又は、炭素数４以上の第３級炭素原子を有する環状炭化水素基である。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Va ⁰¹ and Va ⁰² are each independently a hydrocarbon group having 2 to 10 carbon atoms. Va ⁰¹ -La ⁰ -is Va ⁰¹ -C (= O) O- or Va ⁰¹ -OC (= O)-. n _a0 is an integer of 1 to 5. Ra ⁰¹ is a chain hydrocarbon group having a tertiary carbon atom having 5 or more carbon atoms or a cyclic hydrocarbon group having a tertiary carbon atom having 4 or more carbon atoms. ]

^R in general formula ^{(a0-1), Va 01, Va 02, Va} 01 -La 0 -, n a0 is, ^R in the above formula ^{(m0-1), Va 01, Va} 02, Va 01 -La 0 The same as-and _na0 .
^{Ra 01} in general formula (a0-1) is the same as ^{Ra 01} in the formula (m0), by the action of an acid, between atoms (-O-) adjacent to ^{Ra 01} and ^{Ra 01} It is a group having acid dissociation properties that can cleave the bond.

Specific examples of the structural unit represented by the above formula (a0-1) are shown below. In the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The structural unit (a0) contained in the component (A1) may be one type or two or more types.
The proportion of the structural unit (a0) in the component (A1) is preferably 10 to 50 mol%, more preferably 10 to 40 mol%, and more preferably 10 to 35 mol% with respect to all the structural units constituting the component (A1). Is more preferable.
By setting the proportion of the structural unit (a0) to the lower limit value or more, a resist pattern with improved lithography properties such as sensitivity, resolution, and LWR (line width roughness) can be easily obtained in resist pattern formation. On the other hand, by setting it to the upper limit value or less, it is possible to balance with other structural units.

(Other structural units)
In addition to the structural unit (a0), the component (A1) may further have another structural unit.
The other structural unit is not particularly limited as long as it is a structural unit that is not classified into the structural unit (a0) described above. For ArF excimer laser, KrF excimer laser (preferably for ArF excimer laser), etc. Many things conventionally known can be used as what is used for resin for resists, For example, the structural unit (a1)-(a4) shown below, a structural unit (a6), etc. are mentioned.

Structural unit (a1):
In addition to the structural unit (a0), the component (A1) further includes a structural unit (a1) (excluding those corresponding to the structural unit (a0)) containing an acid-decomposable group that increases in polarity by the action of an acid. May be.
The “acid-decomposable group” is an acid-decomposable group that can cleave at least part of bonds in the structure of the acid-decomposable group by the action of an acid.
Examples of the acid-decomposable group whose polarity increases by the action of an acid include a group that decomposes by the action of an acid to generate a polar group.
Examples of the polar group include a carboxy group, a hydroxyl group, an amino group, a sulfo group (—SO ₃ H), and the like. Among these, a polar group containing —OH in the structure (hereinafter sometimes referred to as “OH-containing polar group”) is preferable, a carboxy group or a hydroxyl group is more preferable, and a carboxy group is particularly preferable.
More specifically, examples of the acid-decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).
The term “acid-dissociable group” as used herein refers to (i) a group having acid-dissociable properties capable of cleaving a bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group by the action of an acid. Or (ii) after a partial bond is cleaved by the action of an acid, a further decarboxylation reaction causes a bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group to be cleaved. Both of the possible groups.
The acid-dissociable group constituting the acid-decomposable group must be a group having a lower polarity than the polar group generated by dissociation of the acid-dissociable group. Is dissociated, a polar group having a polarity higher than that of the acid dissociable group is generated to increase the polarity. As a result, the polarity of the entire component (A1) increases. As the polarity increases, the solubility in the developer changes relatively. When the developer is an alkaline developer, the solubility increases. When the developer is an organic developer, the solubility increases. Decrease.

The acid dissociable group in the structural unit (a1) is not particularly limited, and those that have been proposed as acid dissociable groups of the base resin for chemically amplified resists can be used.
Among the polar groups, examples of the acid dissociable group that protects a carboxy group or a hydroxyl group include an acid dissociable group represented by the following general formula (a1-r-1) (hereinafter referred to as “acetal acid dissociable for convenience”). Group ”).

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

[In the formula, Ra ′ ¹ and Ra ′ ² are a hydrogen atom or an alkyl group, Ra ′ ³ is a hydrocarbon group, and Ra ′ ³ is bonded to either Ra ′ ¹ or Ra ′ ² to form a ring. It may be formed. ]

In formula (a1-r-1), the alkyl group of Ra ′ ¹ and Ra ′ ² is preferably an alkyl group having 1 to 5 carbon atoms, and a linear or branched alkyl group having 1 to 5 carbon atoms. More specifically, specific examples include 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. An ethyl group is preferred, and a methyl group is most preferred.

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

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

In the case of an aromatic hydrocarbon group, specific examples of the aromatic ring contained include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene; carbon atoms constituting the aromatic hydrocarbon ring An aromatic heterocycle partially substituted with a heteroatom is exemplified. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specifically, the aromatic hydrocarbon group is a group obtained by removing 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, Benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group and other arylalkyl groups). The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

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

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

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

[Wherein, Ra ′ ^{4 to} Ra ′ ⁶ are each a hydrocarbon group, and Ra ′ ⁵ and Ra ′ ⁶ may be bonded to each other to form a ring. ]

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

［式中、Ｒａ’^１０は炭素数１〜１０のアルキル基であり、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である。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, and Ra ′ ¹¹ is a group that forms an aliphatic cyclic group together with the carbon atom to which Ra ′ ¹⁰ is bonded. Ra ′ ^{12 to} Ra ′ ¹⁴ each independently represent a hydrocarbon group. ]

Formula (a1-r2-1) in, Ra 'alkyl group having 1 to 10 carbon atoms ^10, Ra in formula (a1-r-1)' was mentioned as the linear or branched alkyl group of ³ Groups are preferred. In formula (a1-r2-1), the aliphatic cyclic group that Ra ′ ¹¹ comprises is a monocyclic alicyclic hydrocarbon group of Ra ′ ³ in formula (a1-r-1), or polycyclic The groups listed as alicyclic hydrocarbon groups of the formula are preferred.

In Formula (a1-r2-2), Ra ′ ¹² and Ra ′ ¹⁴ are preferably each independently an alkyl group having 1 to 10 carbon atoms, and the alkyl group in Formula (a1-r-1) The group mentioned as the linear or branched alkyl group of Ra ′ ³ is more preferable, a linear alkyl group having 1 to 5 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable. preferable.
In formula (a1-r2-2), Ra ′ ¹³ represents a linear or branched alkyl group exemplified as the hydrocarbon group for Ra ′ ³ in formula (a1-r-1), or monocyclic Or it is preferable that it is a polycyclic alicyclic hydrocarbon group. Among these, a group exemplified as a monocyclic or polycyclic alicyclic hydrocarbon group of Ra ′ ³ is more preferable.

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

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

  Examples of the acid dissociable group for protecting the hydroxyl group among the polar groups include, for example, an acid dissociable group represented by the following general formula (a1-r-3) (hereinafter referred to as “tertiary alkyloxycarbonyl acid for convenience”). Sometimes referred to as a “dissociable group”).

［式中、Ｒａ’^７〜Ｒａ’^９はそれぞれアルキル基を示す。］

[Wherein, Ra ′ ^{7 to} Ra ′ ⁹ each represents an alkyl group. ]

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

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

Among the above, the structural unit (a1) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent.
As the structural unit (a1), structural units represented by any of the following general formulas (a1-1) to (a1-3) are 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の整数であり、Ｒａ^１は、上記式（ａ１−ｒ−１）又は（ａ１−ｒ−２）で表される酸解離性基である。Ｗａ^１は、ｎ_ａ２＋１価の炭化水素基であり、ｎ_ａ２は１〜３の整数である。Ｒａ^２は、上記式（ａ１−ｒ−１）又は（ａ１−ｒ−３）で表される酸解離性基である。Ｗａ^２は、ｎ_ａ３＋１価の炭化水素基であり、ｎ_ａ３は１〜３の整数であり、Ｖａ^２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、Ｒａ^３は、上記式（ａ１−ｒ−１）又は（ａ１−ｒ−２）で表される酸解離性基である。］

[Wherein, R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Va ¹ is a divalent hydrocarbon group which may have an ether bond, a urethane bond or an amide bond, n _a1 is an integer of 0 to 2, and Ra ¹ is the above formula (a1-r-1 Or an acid dissociable group represented by (a1-r-2). Wa ¹ is a n _a2 +1 valent hydrocarbon group, and n _a2 is an integer of 1 to 3. Ra ² is an acid dissociable group represented by the above formula (a1-r-1) or (a1-r-3). Wa ² is a n _a3 +1 valent hydrocarbon group, n _a3 is an integer of 1 to 3, and Va ² is a divalent carbon which may have an ether bond, a urethane bond, or an amide bond. It is a hydrogen group, and Ra ³ is an acid dissociable group represented by the above formula (a1-r-1) or (a1-r-2). ]

In the general formulas (a1-1) to (a1-3), the alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
The halogenated alkyl group having 1 to 5 carbon atoms in R is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and is most preferably a hydrogen atom or a methyl group in terms of industrial availability.

In the formula (a1-1), Va ¹ is a divalent hydrocarbon group which may have an ether bond, a urethane bond or an amide bond.
The divalent hydrocarbon group in Va ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group as a 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.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

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

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

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, or those having these bonds in the hydrocarbon chain.

In the formula (a1-1), n _a1 is an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

In the formula (a1-2), the n _a2 +1 valent hydrocarbon group in Wa ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, 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 including a ring in the structure, or a linear or branched aliphatic hydrocarbon group. It includes a group formed by combining an aliphatic hydrocarbon group in the structure containing a ring, and specific examples thereof include the same groups as Va ¹ in the aforementioned formula (a1-1).
The n _a2 +1 valence is preferably 2 to 4, and more preferably 2 or 3.

In the formula (a1-3), the n _a3 +1 valent hydrocarbon group in Wa ² may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or a linear or branched aliphatic hydrocarbon group. It includes a group formed by combining an aliphatic hydrocarbon group in the structure containing a ring, and specific examples thereof include the same groups as Va ¹ in the aforementioned formula (a1-1).
The n _a3 +1 valence is preferably 2 to 4, and more preferably 2 or 3.
In the formula (a1-3), Va ² includes the same group as Va ¹ in the formula (a1-1).

  As the formula (a1-2), a structural unit represented by general formula (a1-2-01) shown below is particularly desirable.

In the formula (a1-2-01), Ra ² is an acid dissociable 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 described above.

Specific examples of the structural units represented by the above formulas (a1-1) and (a1-2) are shown below. In the following formulas, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The structural unit (a1) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a1), the proportion of the structural unit (a1) is preferably 70 mol% or less, preferably 60 mol% or less with respect to the total of all the structural units constituting the component (A1). Is more preferably 50 mol% or less, and the lower limit is preferably 10 mol% or more.
By setting the proportion of the structural unit (a1) to be equal to or less than the above preferable upper limit value, it is possible to easily balance with other structural units, and it is easy to obtain a resist pattern having a good shape. On the other hand, if it is at least the preferred lower limit, lithography properties such as sensitivity, resolution, and LWR are further improved.

Structural unit (a2):
In such a resist composition, in addition to the structural unit (a0), the component (A1) includes a structural unit (a2) containing a lactone-containing cyclic group, an —SO ₂ -containing cyclic group, or a carbonate-containing cyclic group. It is preferable to further have.
The lactone-containing cyclic group, -SO ₂ -containing cyclic group or carbonate-containing cyclic group of the structural unit (a2) can be used to adhere the resist film to the substrate when the component (A1) is used for forming the resist film. It is effective in enhancing the sex.
In addition, when the structural unit (a0) or the structural unit (a1) includes a lactone-containing cyclic group, an —SO ₂ — containing cyclic group, or a carbonate-containing cyclic group in the structure, the structural unit is a constituent. Although it corresponds to the unit (a2), such a structural unit corresponds to the structural unit (a0) or the structural unit (a1) and does not correspond to the structural unit (a2).

The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing —O—C (═O) — in the ring skeleton. The lactone ring is counted as the first ring. When only the lactone ring is present, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
Any lactone-containing cyclic group can be used without any particular limitation. Specific examples include groups represented by general formulas (a2-r-1) to (a2-r-7) shown below.

［式中、Ｒａ’^２１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基であり；Ａ”は酸素原子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 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom, alkyl group, lactone-containing cyclic group, carbonate-containing cyclic group, or —SO ₂ -containing cyclic group; A ″ is a carbon that may contain an oxygen atom or a sulfur atom An alkylene group having 1 to 5 atoms, an oxygen atom or a sulfur atom, n ′ is an integer of 0 to 2, and m ′ is 0 or 1. ]

In the general formula (a2-r-1) ~ (a2-r-7), the alkyl group in Ra ^'21, preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
The alkoxy group 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.
Examples of the halogen atom in Ra ′ ²¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
'Examples of the halogenated alkyl group for ^21, the Ra' Ra part or all of the hydrogen atoms of the alkyl group in ²¹ can be mentioned it has been substituted with the aforementioned halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

In —COOR ″ and —OC (═O) R ″ in Ra ′ ²¹ , R ″ is any hydrogen atom, alkyl group, lactone-containing cyclic group, carbonate-containing cyclic group, or —SO ₂ -containing cyclic group. It is.
The alkyl group for R ″ may be linear, branched or cyclic, and preferably has 1 to 15 carbon atoms.
When R ″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably a methyl group or an ethyl group. preferable.
When R ″ is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, a fluorine atom Or a group obtained by removing one or more hydrogen atoms from a monocycloalkane which may or may not be substituted with a fluorinated alkyl group; a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane A group in which one or more hydrogen atoms are removed from a monocycloalkane such as cyclopentane, cyclohexane, etc .; more specifically, a group in which one or more hydrogen atoms are removed; adamantane, norbornane, isobornane, tri Examples include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as cyclodecane or tetracyclododecane. That.
Examples of the lactone-containing cyclic group for R ″ include the same groups as those represented by general formulas (a2-r-1) to (a2-r-7).
The carbonate-containing cyclic group in R ″ is the same as the carbonate-containing cyclic group described later, and is specifically represented by the following general formulas (ax3-r-1) to (ax3-r-3). Group.
The —SO ₂ — containing cyclic group in R ″ is the same as the later-described —SO ₂ — containing cyclic group, and specifically, the following general formulas (a5-r-1) to (a5-r— And groups represented by 4).

As the hydroxyalkyl group in Ra ′ ²¹ , those having 1 to 6 carbon atoms are preferable, and specific examples include a group in which at least one hydrogen atom of the alkyl group in Ra ′ ²¹ is substituted with a hydroxyl group. .

In the general formulas (a2-r-2), (a2-r-3), and (a2-r-5), A ″ includes an oxygen atom (—O—) or a sulfur atom (—S—). An alkylene group having 1 to 5 carbon atoms, an oxygen atom or a sulfur atom. The alkylene group having 1 to 5 carbon atoms in A ″ is preferably a linear or branched alkylene group, a methylene group, Examples include an ethylene group, an n-propylene group, and an isopropylene group. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include a group in which —O— or —S— is interposed between the terminal or carbon atoms of the alkylene group, such as —O—CH _{2. -, - CH 2 -O-CH} 2 -, - S-CH 2 -, - CH 2 -S-CH 2 - , and the like. A ″ is preferably an alkylene group having 1 to 5 carbon atoms or —O—, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

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

The “—SO ₂ -containing cyclic group” refers to a cyclic group containing a ring containing —SO ₂ — in the ring skeleton, specifically, the sulfur atom (S) in —SO ₂ — is It is a cyclic group that forms part of the ring skeleton of the cyclic group. The ring containing —SO ₂ — in the ring skeleton is counted as the first ring, and when it is only the ring, it is a monocyclic group, and when it has another ring structure, it is a polycyclic group regardless of the structure. Called. The —SO ₂ — containing cyclic group may be monocyclic or polycyclic.
-SO ₂ - containing cyclic group, in particular, -O-SO ₂ - within the ring skeleton cyclic group containing, i.e. -O-SO ₂ - -O-S- medium is a part of the ring skeleton A cyclic group containing a sultone ring to be formed is preferable. More specifically, examples of the —SO ₂ — containing cyclic group include groups represented by general formulas (a5-r-1) to (a5-r-4) shown below.

［式中、Ｒａ’^５１はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基、水酸基、−ＣＯＯＲ”、−ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基またはシアノ基であり；Ｒ”は水素原子、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数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 independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom, alkyl group, lactone-containing cyclic group, carbonate-containing cyclic group, or —SO ₂ -containing cyclic group; A ″ is a carbon that may contain an oxygen atom or a sulfur atom It is a C 1-5 alkylene group, an oxygen atom or a sulfur atom, and n ′ is an integer of 0-2. ]

In the general formulas (a5-r-1) and (a5-r-2), A ″ represents the general formulas (a2-r-2), (a2-r-3), and (a2-r-5). Same as A ″ in the middle. As the alkyl group, alkoxy group, halogen atom, halogenated alkyl group, —COOR ″, —OC (═O) R ″, and hydroxyalkyl group in Ra ′ ⁵¹ , the above general formulas (a2-r-1) to (a2 The same as Ra ′ ²¹ in −r-7).

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

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

The “carbonate-containing cyclic group” refers to a cyclic group containing a ring (carbonate ring) containing —O—C (═O) —O— in the ring skeleton. When the carbonate ring is counted as the first ring, the carbonate ring alone is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group.
Any carbonate ring-containing cyclic group can be used without any particular limitation. Specific examples 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、アルキル基、ラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基であり；Ａ”は酸素原子もしくは硫黄原子を含んでいてもよい炭素数１〜５のアルキレン基、酸素原子または硫黄原子であり、ｐ’は０〜３の整数であり、ｑ’は０または１である。］

[ ^Wherein , Ra ′ ^x31 each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, —COOR ″, —OC (═O) R ″, a hydroxyalkyl group or a cyano group. Yes; R ″ is a hydrogen atom, alkyl group, lactone-containing cyclic group, carbonate-containing cyclic group, or —SO ₂ -containing cyclic group; A ″ is a carbon that may contain an oxygen atom or a sulfur atom It is an alkylene group of formulas 1 to 5, an oxygen atom or a sulfur atom, p ′ is an integer of 0 to 3, and q ′ is 0 or 1. ]

In the general formulas (ax3-r-1) to (ax3-r-3), A ″ is the same as A ″ in the general formula (a2-r-1).
As the alkyl group, alkoxy group, halogen atom, halogenated alkyl group, —COOR ″, —OC (═O) R ″, and hydroxyalkyl group in Ra ′ ^x31 , the above general formulas (a2-r-1) to ( a2-r-7) as in the same as those exemplified in the description of the Ra ^'21 of the like.

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

Among these, a lactone-containing cyclic group or an —SO ₂ — containing cyclic group is preferable, and among these, a lactone-containing cyclic group is more preferable. Specifically, the group represented by the general formula (a2-r-1), (a2-r-2) or (a5-r-1) is more preferable, and the chemical formula (r-lc-1-1) is more preferable. ) To (r-lc-1-7), (r-lc-2-1) to (r-lc-2-13), (r-sl-1-1), (r-sl-1-18) ) Is preferred.

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

［式中、Ｒは水素原子、炭素数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−又は−ＯＣＯ−である。ただしＬａ^２１が−Ｏ−の場合、Ｙａ^２１は−ＣＯ−にはならない。Ｒａ^２１はラクトン含有環式基、カーボネート含有環式基、又は−ＳＯ_２−含有環式基である。］

[Wherein, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, Ya ²¹ is a single bond or a divalent linking group, and La ²¹ is —O -, -COO- or -OCO-. However, when La ²¹ is —O—, Ya ²¹ is not —CO—. Ra ²¹ is a lactone-containing cyclic group, a carbonate-containing cyclic group, or an —SO ₂ -containing cyclic group. ]

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

-About the 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. .
An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
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. Specifically, the above-described formula (a1- The group illustrated by Va ¹ in 1) is mentioned.

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

The cyclic aliphatic hydrocarbon group in the aliphatic hydrocarbon group containing a ring may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group. Most preferred is an ethoxy group.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as the substituent include groups in which part or all of the hydrogen atoms of the alkyl group have been substituted with the halogen atoms.
In the cyclic aliphatic hydrocarbon group, a part of carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As the substituent containing the hetero atom, —O—, —C (═O) —O—, —S—, —S (═O) ₂ —, and —S (═O) ₂ —O— are preferable.

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

-About the bivalent coupling group containing a hetero atom The hetero atom in the bivalent coupling group containing a hetero atom is atoms other than a carbon atom and a hydrogen atom, for example, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, etc. Is mentioned.

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

Ya ²¹ is preferably a single bond, an ester bond [—C (═O) —O—], an ether bond (—O—), a linear or branched alkylene group, or a combination thereof. .

In the formula (a2-1), Ra ²¹ is the lactone-containing cyclic group, —SO ₂ — containing cyclic group, or carbonate-containing cyclic group described above, and the lactone-containing cyclic group, —SO ₂ — contained. Cyclic groups are preferred, and lactone-containing cyclic groups are particularly preferred.

The structural unit (a2) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a2), the proportion of the structural unit (a2) is preferably 1 to 70 mol% with respect to the total of all the structural units constituting the component (A1). 5-70 mol% is more preferable, 10-65 mol% is further more preferable, and 10-60 mol% is especially preferable.
By setting the proportion of the structural unit (a2) to be equal to or higher than the lower limit value, the effect of including the structural unit (a2) can be sufficiently obtained. On the other hand, by setting the ratio to the upper limit value or lower, balance with other structural units is achieved. Therefore, various lithography characteristics and pattern shapes are improved.

Structural unit (a3):
In such a resist composition, the component (A1) contains the structural unit (a3) containing the polar group-containing aliphatic hydrocarbon group in addition to the structural unit (a0) (provided that the structural unit (a0) and the structural unit described above). It is preferable to further include a unit (a1) or a constituent unit (a2) that is not included).
When the component (A1) has the structural unit (a3), the hydrophilicity of the component (A) increases, which contributes to the improvement of resolution.

Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, and a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom. A hydroxyl group is particularly preferable.
Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) and a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be a monocyclic group or a polycyclic group. For example, a resin for a resist composition for an ArF excimer laser can be appropriately selected from those proposed. The cyclic group is preferably a polycyclic group, and more preferably 7 to 30 carbon atoms.
Among them, a structural unit derived from an acrylate ester containing an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of hydrogen atoms of a hydroxyl group, a cyano group, a carboxy group, or an alkyl group is substituted with a fluorine atom Is more preferable. Examples of the polycyclic group include groups in which two or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane and the like. Specific examples include groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, there are groups in which two or more hydrogen atoms have been removed from adamantane, groups in which two or more hydrogen atoms have been removed from norbornane, and groups in which two or more hydrogen atoms have been removed from tetracyclododecane. Industrially preferable.

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

［式中、Ｒは前記と同じであり、ｊは１〜３の整数であり、ｋは１〜３の整数であり、ｔ’は１〜３の整数であり、ｌは１〜５の整数であり、ｓは１〜３の整数である。］

[Wherein, R is the same as above, j is an integer of 1 to 3, k is an integer of 1 to 3, t ′ is an integer of 1 to 3, and l is an integer of 1 to 5] And s is an integer of 1 to 3. ]

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

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

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

As the structural unit (a3) contained in the component (A1), 1 type of structural unit may be used, or 2 or more types may be used.
When the component (A1) has the structural unit (a3), the proportion of the structural unit (a3) is preferably 1 to 40 mol% with respect to the total of all the structural units constituting the component (A1). It is more preferably 2 to 30 mol%, further preferably 5 to 25 mol%, and particularly preferably 10 to 20 mol%.
By setting the proportion of the structural unit (a3) to a preferable lower limit value or more, resolution is further improved in resist pattern formation. On the other hand, by setting it to a preferable upper limit value or less, it becomes easy to balance with other structural units.

Structural unit (a4):
In addition to the structural unit (a0), the component (A1) may further include a structural unit (a4) containing an acid non-dissociable aliphatic cyclic group.
When the component (A1) has the structural unit (a4), the dry etching resistance of the formed resist pattern is improved. Moreover, the hydrophobicity of (A) component increases. The improvement in hydrophobicity contributes to improvement in resolution, resist pattern shape, etc., particularly in the case of a solvent development process.
The “acid non-dissociable cyclic group” in the structural unit (a4) is generated when an acid is generated in the resist composition by exposure (for example, an acid is generated from the structural unit (a6) or the component (B) described later). In this case, the cyclic group remains in the structural unit without being dissociated even when the acid acts.
As the structural unit (a4), for example, a structural unit derived from an acrylate ester containing a non-acid-dissociable aliphatic cyclic group is preferable. As the cyclic group, many conventionally known groups can be used as resin components of resist compositions such as for ArF excimer laser and for KrF excimer laser (preferably for ArF excimer laser). .
In particular, at least one selected from a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group is preferable in terms of industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
Specific examples of the structural unit (a4) include structural units represented by general formulas (a4-1) to (a4-7) shown below.

［式中、Ｒ^αは前記と同じである。］

[Wherein, R ^α is the same as defined above. ]

The structural unit (a4) contained in the component (A1) may be one type or two or more types.
When the component (A1) has the structural unit (a4), the proportion of the structural unit (a4) is preferably 1 to 40 mol% with respect to the total of all the structural units constituting the component (A1). More preferably, it is 5-20 mol%.
By setting the proportion of the structural unit (a4) to a preferable lower limit value or more, the effect of including the structural unit (a4) can be sufficiently obtained. On the other hand, by setting the proportion of the structural unit (a4) to a preferable lower limit value or less, It becomes easy to balance.

Structural unit (a6):
In addition to the structural unit (a0), the component (A1) may further include a structural unit (a6) that generates an acid upon exposure.
The structural unit (a6) is not particularly limited as long as it generates an acid upon exposure. For example, the structural unit (a6) can be copolymerized with the structural unit (a0), and is an acid generator for a conventional chemically amplified resist. A structural unit in which a structure proposed as:
As the structural unit copolymerizable with the structural unit (a0), a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the α-position may be substituted with a substituent, hydroxystyrene or hydroxystyrene Preferred examples include structural units derived from derivatives.
As a compound having a structure conventionally proposed as an acid generator for a chemically amplified resist, a component (B) described later is preferable.

  As the structural unit (a6), for example, a structural unit (a6a) having an anion group capable of generating an acid upon exposure in the side chain, or a structural unit (a6c) having a cationic group capable of decomposing upon exposure in the side chain can be mentioned. .

Structural Unit (a6a) The structural unit (a6a) is a structural unit having in its side chain an anionic group that generates an acid upon exposure.
The anion group that generates an acid upon exposure is not particularly limited, and a sulfonate anion, an amide anion, and a methide anion are preferable. Among these, as the anionic group, a group represented by any one of the following general formulas (a6a-r-1), (a6a-r-2), and (a6a-r-3) is more preferable.

［式中、Ｖａ’^６１はフッ素原子を有する２価の炭化水素基である。Ｌａ’^６３〜Ｌａ’^６５は−ＳＯ_２−又は単結合である。Ｒａ’^６１〜Ｒａ’^６３はそれぞれ独立に置換基を有していてもよい炭化水素基である。］

[In the formula, Va ′ ⁶¹ represents a divalent hydrocarbon group having a fluorine atom. La ′ ^{63 to} La ′ ⁶⁵ are —SO ₂ — or a single bond. Ra ′ ^{61 to} Ra ′ ⁶³ are each independently a hydrocarbon group which may have a substituent. ]

In the formula (a6a-r-1), Va ′ ⁶¹ is a divalent hydrocarbon group having a fluorine atom. The divalent hydrocarbon group in Va ′ ⁶¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and most preferably 1 to 3.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
Such a linear or branched aliphatic hydrocarbon group has a fluorine atom, and all of the hydrogen atoms of the aliphatic hydrocarbon group may be substituted with a fluorine atom. Further, in addition to the fluorine atom, it may be substituted with an oxo group (═O) or 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 (excluding two hydrogen atoms from the aliphatic hydrocarbon ring) Group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and the cyclic aliphatic hydrocarbon group is a linear or branched chain fatty acid. Group intervening in the middle of the group hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those similar to the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane. , Norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
Such a cyclic aliphatic hydrocarbon group may have a fluorine atom, and all of the hydrogen atoms of the cyclic aliphatic hydrocarbon group may be substituted with a fluorine atom. Further, in addition to the fluorine atom, it may be substituted with a substituent such as an alkyl group, an alkoxy group, a hydroxyl group or an oxo group (═O).
The alkyl group in the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group in the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group, and a methoxy group. An ethoxy group is most preferred.

In the divalent hydrocarbon group for Va ′ ⁶¹ , the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. It is preferable that carbon number of an aromatic ring is 5-30, 5-20 are more preferable, 6-15 are more preferable, and 6-12 are especially preferable. However, the carbon number does not include the carbon number in the substituent.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene and phenanthrene; aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms Can be mentioned. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, the aromatic hydrocarbon group is a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic compound containing two or more aromatic rings A group obtained by removing two hydrogen atoms from (for example, biphenyl, fluorene, etc.); 1 of the hydrogen atoms of a group (aryl group or heteroaryl group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring A group substituted with an alkylene group (for example, an aryl group in an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) A group in which one atom is further removed). The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.
Such an aromatic hydrocarbon group has a fluorine atom, and all of the hydrogen atoms of the aromatic hydrocarbon group may be substituted with a fluorine atom. Further, in addition to the fluorine atom, it may be substituted with a substituent such as an alkyl group, an alkoxy group, a hydroxyl group or an oxo group (═O). The alkyl group and alkoxy group as the substituent are the same as the alkyl group and alkoxy group as the substituent of the cyclic aliphatic hydrocarbon group.

  Among the anionic groups represented by the formula (a6a-r-1), a group represented by the following general formula (a6a-r-11) is preferable.

［式中、Ｒ^ｆ１及びＲ^ｆ２はそれぞれ独立に水素原子、アルキル基、フッ素原子又はフッ素化アルキル基であり、Ｒ^ｆ１、Ｒ^ｆ２のうち少なくとも１つはフッ素原子又はフッ素化アルキル基であり、ｐ０は１〜８の整数である。］

[Wherein, R ^f1 and R ^f2 are each independently a hydrogen atom, an alkyl group, a fluorine atom or a fluorinated alkyl group, and at least one of R ^f1 and R ^f2 is a fluorine atom or a fluorinated alkyl group, p0 is an integer of 1-8. ]

In the formula (a6a-r-11), R ^f1 and R ^f2 are each independently a hydrogen atom, an alkyl group, a fluorine atom or a fluorinated alkyl group, and at least one of R ^f1 and R ^f2 is fluorine. An atom or a fluorinated alkyl group.
As the alkyl group for R ^f1 and R ^f2 , an alkyl group having 1 to 5 carbon atoms is preferable. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group Group, pentyl group, isopentyl group, neopentyl group and the like.
Examples of the fluorinated alkyl group of ^{R f1,} R ^f2, group in which part or all of the hydrogen atoms of the alkyl group of the ^{R f1, R f2} is substituted with a fluorine atom is preferred.
R ^f1 and R ^f2 are preferably a fluorine atom or a fluorinated alkyl group.
In the formula (a6a-r-11), p0 is an integer of 1 to 8, preferably an integer of 1 to 4, and more preferably 1 or 2.

In the formula (a6a-r-2), examples of the hydrocarbon group for Ra ′ ⁶¹ include an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, and an aralkyl group.
The alkyl group in Ra ′ ⁶¹ preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and may be linear or branched. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and the like are preferable.
The monovalent alicyclic hydrocarbon group in Ra ′ ⁶¹ preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and may be polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon group, a group in which one or more hydrogen atoms have been removed from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclobutane, cyclopentane, and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 12 carbon atoms. Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.
The aryl group in Ra ′ ⁶¹ is preferably one having 6 to 18 carbon atoms, more preferably one having 6 to 10 carbon atoms, and particularly preferably a phenyl group.
A preferable example of the aralkyl group in Ra ′ ^{61 is one} in which an alkylene group having 1 to 8 carbon atoms is bonded to the above “aryl group in Ra ′ ⁶¹ ”. An aralkyl group in which an alkylene group having 1 to 6 carbon atoms and the above “aryl group in Ra ′ ⁶¹ ” are bonded is more preferable, and an alkylene group having 1 to 4 carbon atoms and the above “aryl group in Ra ′ ⁶¹ ” are bonded. Aralkyl groups are particularly preferred.
The hydrocarbon group in Ra ′ ⁶¹ may have a substituent, and part or all of the hydrogen atoms of the hydrocarbon group are preferably substituted with fluorine atoms, and the hydrogen atom of the hydrocarbon group It is more preferable that 30 to 100% of is substituted with a fluorine atom. Especially, it is especially preferable that it is the perfluoroalkyl group by which all the hydrogen atoms of the alkyl group mentioned above were substituted by the fluorine atom. In addition, in the hydrocarbon group in Ra ′ ⁶¹ , the methylene group (—CH ₂ —) may be substituted with a divalent group such as —CO— or —SO ₂ —.

In the formula (a6a-r-3), La ′ ^{63 to} La ′ ⁶⁵ are —SO ₂ — or a single bond, and Ra ′ ^{62 to} Ra ′ ⁶³ may each independently have a substituent. Good hydrocarbon group. Each of Ra ′ ^{62 to} Ra ′ ⁶³ is the same as the hydrocarbon group that may have the substituent of Ra ′ ⁶¹ .

  Preferred examples of the structural unit (a6a) include structural units represented by general formulas (a6a-1) to (a6a-8) shown below.

［式中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｒａ^６１は上記式（ａ６ａ−ｒ−１）で表される基であり、Ｒａ^６２は上記式（ａ６ａ−ｒ−２）または（ａ６ａ−ｒ−３）で表される基であり、Ｒａ^６３は上記式（ａ６ａ−ｒ−３）で表される基である。Ｒａ”^６１〜Ｒａ”^６４はそれぞれ独立に水素原子、フッ素原子、炭素数１〜５のアルキル基又はフッ素化アルキル基である。ｎ_ａ６１、ｎ_ａ６２はそれぞれ独立に１〜１０の整数であり、ｎ_ａ６３は０〜１０の整数である。Ｖａ”^６１は２価の環状の炭化水素基である。Ｌａ”^６１は−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、又は、−Ｏ−ＣＨ_２−Ｃ（＝Ｏ）−Ｏ−である。Ｖａ”^６２は２価の炭化水素基である。Ｒａ”^６５は水素原子または炭素数１〜５のアルキル基である。Ｌａ”^６２は−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、又は、−ＮＨ−Ｃ（＝Ｏ）−Ｏ−である。Ｙａ”^６１は環状炭化水素基を含む２価の連結基である。Ｖａ”^６３は２価の環状炭化水素基又は単結合である。ｍは１以上の整数であって、Ｍ^ｍ＋はそれぞれ独立にｍ価の有機カチオンである。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ra ⁶¹ is a group represented by the above formula (a6a-r-1), Ra ⁶² is a group represented by the above formula (a6a-r-2) or (a6a-r-3), and Ra ⁶³ Is a group represented by the above formula (a6a-r-3). Ra ″ ^{61 to} Ra ″ ⁶⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group. n _a61 and n _a62 are each independently an integer of 1 to 10, and _{na 63} is an integer of 0 to 10. Va ″ ⁶¹ is a divalent cyclic hydrocarbon group. La ″ ⁶¹ is —C (═O) —O—, —O—C (═O) —O—, or —O—CH ₂ —C. (= O) -O-. Va ″ ⁶² is a divalent hydrocarbon group. Ra ″ ⁶⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. La ″ ⁶² is —C (═O) —O—, —O—C (═O) —O—, or —NH—C (═O) —O—. Ya ″ ⁶¹ is a cyclic hydrocarbon group. Is a divalent linking group. Va ″ ⁶³ is a divalent cyclic hydrocarbon group or a single bond. M is an integer of 1 or more, and M ^{m +} is each independently an m-valent organic cation.]

In the formulas (a6a-1) to (a6a-8), R is the same as R in the formula (a1-1).
In the formulas (a6a-1) to (a6a-4), Ra ⁶¹ is each independently a group represented by the formula (a6a-r-1). In the formulas (a6a-5) to (a6a-7), Ra ⁶² is independently a group represented by the above formula (a6a-r-2) or (a6a-r-3). In the formula (a6a-8), Ra ⁶³ is a group represented by the formula (a6a-r-3).
In the formulas (a6a-2) and (a6a-5) to (a6a-7), Ra ″ ^{61 to} Ra ″ ⁶⁴ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or fluorine. Alkyl group. Examples of the fluorinated alkyl group for Ra ″ ^{61 to} Ra ″ ⁶⁴ include groups in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms have been substituted with fluorine atoms.
In the formulas (a6a-2), (a6a-5), and (a6a-6), _na61 are each independently an integer of 1 to 10, preferably an integer of 1 to 8, and an integer of 1 to 4 Is more preferable, and 1 or 2 is more preferable.
In the formula (a6a-6), n _a62 is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 4, and even more preferably 1 or 2. .
In the formula (a6a-7), _na63 is an integer of 0 to 10, an integer of 0 to 5 is preferable, an integer of 0 to 3 is more preferable, and 0 is still more preferable.

In the formula (a6a-3), Va ″ ⁶¹ is a divalent cyclic hydrocarbon group, and is exemplified in the description of Va ′ ⁶¹ in the formula (a6a-r-1). And the same as the aliphatic hydrocarbon group and aromatic hydrocarbon group containing a ring.
La ″ ⁶¹ is —C (═O) —O—, —O—C (═O) —O—, or —O—CH ₂ —C (═O) —O—.

In the formula (a6a-4), Va ″ ⁶² is a divalent hydrocarbon group, and the divalent carbonization exemplified in the description of Va ′ ⁶¹ in the formula (a6a-r-1). The thing similar to a hydrogen group is mentioned.
Ra ″ ⁶⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In the formula (a6a-6), La ″ ⁶² represents —C (═O) —O—, —O—C (═O) —O—, or —NH—C (═O) —O—. is there.
In the formula (a6a-7), Ya ″ ⁶¹ is a divalent linking group containing a cyclic hydrocarbon group, and description of the divalent linking group of Ya ²¹ in the general formula (a2-1) described above. , An aliphatic hydrocarbon group containing a ring in the structure, an aromatic hydrocarbon group, a divalent linking group containing a hetero atom (of these, an aliphatic hydrocarbon group containing a ring in the structure, Or the thing similar to the thing which has an aromatic hydrocarbon group) is mentioned.
In the formula ^{(a6a-8), Va "} 63 is a divalent cyclic hydrocarbon group or .Va a single ^bond" divalent cyclic hydrocarbon group in ^63, the formula (a6a-r-1) in And the same as the aliphatic hydrocarbon group and aromatic hydrocarbon group containing a ring in the structure exemplified in the description of Va ′ ⁶¹ .

In the formulas (a6a-1) to (a6a-8), m is an integer of 1 or more, and M ^{m +} is each independently an m-valent organic cation.
The organic cation of M ^{m +} is not particularly limited and is preferably an m-valent onium cation, more preferably a sulfonium cation or an iodonium cation, and the general formulas (ca-1) to (ca) described later. -4) is particularly preferable.

Specific examples of the structural unit represented by the formula (a6a-1) are shown below. (M ^{m +} ) _{1 / m} is the same as described above.

  Specific examples of the structural unit represented by the formula (a6a-2) are shown below.

  Specific examples of the structural unit represented by the formula (a6a-3) are shown below.

  Specific examples of the structural unit represented by the formula (a6a-4) are shown below.

  Specific examples of the structural unit represented by the formula (a6a-5) are shown below.

  Specific examples of the structural unit represented by the formula (a6a-6) are shown below.

  Specific examples of the structural unit represented by the formula (a6a-7) are shown below.

  Specific examples of the structural unit represented by the formula (a6a-8) are shown below.

Structural Unit (a6c) The structural unit (a6c) is a structural unit having in its side chain a cationic group that decomposes upon exposure.
It does not specifically limit as a cationic group decomposed | disassembled by exposure, The group represented by the following general formula (a6c-r-1) is preferable.

［式中、Ｒａ’^６１ｃ及びＲａ’^６２ｃ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、置換基を有していてもよいアルキル基、または置換基を有していてもよいアルケニル基を表す。Ｖａ’^６１ｃはアリーレン基、アルキレン基またはアルケニレン基を表す。ただし、Ｒａ’^６１ｃとＲａ’^６２ｃとＶａ’^６１ｃと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。］

[ ^Wherein , Ra ′ ^61c and Ra ′ ^62c are each independently an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl which may have a substituent. Represents a group. Va ′ ^61c represents an arylene group, an alkylene group or an alkenylene group. However, Ra ′ ^61c , Ra ′ ^62c and Va ′ ^61c may be bonded to each other to form a ring together with the sulfur atom in the formula. ]

In the formula (a6c-r-1), Ra ′ ^61c and Ra ′ ^62c are each independently an aryl group which may have a substituent, an alkyl group which may have a substituent, or a substituent. The alkenyl group which may have a group is represented. Ra ′ ^61c and Ra ′ ^62c are an aryl group which may have a substituent and an alkyl group which may have a substituent in R ^{201 to} R ²⁰³ in formula (ca-1) described later, Or the thing similar to the alkenyl group which may have a substituent is mentioned.
Va ′ ^61c represents an arylene group, an alkylene group or an alkenylene group, and examples thereof include a group in which one hydrogen atom has been removed from the aryl group, alkyl group or alkenyl group in the Ra ′ ^61c and Ra ′ ^62c .
However, Ra ′ ^61c , Ra ′ ^62c and Va ′ ^61c may be bonded to each other to form a ring together with the sulfur atom in the formula. Examples of the ring structure formed here include a group in which R ^{201 to} R ^{203 in} the formula (ca-1) described later are bonded to each other to remove one hydrogen atom from the ring formed together with the sulfur atom in the formula. It is done.

  Preferred examples of the structural unit (a6c) include structural units represented by general formulas (a6c-1) to (a6c-3) shown below.

［式中、Ｒは水素原子、炭素数１〜５のアルキル基又は炭素数１〜５のハロゲン化アルキル基である。Ｖａ^６１ｃはそれぞれ独立に炭素数１〜５のアルキレン基であり、Ｖａ^６２ｃ及びＶａ^６４ｃはそれぞれ独立に炭素数１〜１０のアルキレン基であり、Ｖａ^６３ｃは脂肪族環式基又は単結合であり、ｎａ^６１ｃは０〜２の整数であり、ｎａ^６２ｃは０または１であり、Ｒａ^６１ｃは上記式（ａ６ｃ−ｒ−１）で表される基である。Ａ⁻は対アニオンである。］

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Va ^61c is each independently an alkylene group having 1 to 5 carbon atoms, Va ^62c and Va ^64c are each independently an alkylene group having 1 to 10 carbon atoms, and Va ^63c is an aliphatic cyclic group or a single bond. , Na ^61c is an integer of 0 to 2, na ^62c is 0 or 1, and Ra ^61c is a group represented by the above formula (a6c-r-1). A ⁻ is a counter anion. ]

In the formulas (a6c-1) to (a6c-3), R is the same as R in the formula (a1-1). Ra ^61c is each independently a group represented by the above formula (a6c-r-1).
In the formulas (a6c-2) and (a6c-3), Va ^61c is independently an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group. .
In the formula (a6c-3), Va ^62c and Va ^64c are each independently an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 8 carbon atoms, and an alkylene group having 1 to 5 carbon atoms. Are more preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable.
In the formula (a6c-3), Va ^63c is an aliphatic cyclic group or a single bond. Examples of the aliphatic cyclic group for Va ^63c include the same aliphatic cyclic groups exemplified in the description of Va ′ ⁶¹ in the formula (a6a-r-1).
na ^61c is an integer of 0 to 2, and 1 or 2 is preferable.
na ^62c is 0 or 1.

In the formulas (a6c-1) to (a6c-3), A ⁻ is a counter anion.
The counter anion of A ⁻ is not particularly limited, and is represented by the general formula (b-1), (b-2) or (b-3) exemplified in the description of the component (B) described later. And the anion part of the onium salt acid generator represented by the general formula (b-1) is particularly preferable, among which fluorine having 1 to 8 carbon atoms. It is preferable that it is at least 1 sort (s) selected from the anion each represented by the alkyl sulfonate ion (preferably C1-C4) or the general formula (an-1)-(an-3) mentioned later.

Specific examples of the structural unit represented by the above formula (a6c-1), (a6c-2) or (a6c-3) are shown below. A ⁻ is the same as described above.

The structural unit (a6) contained in the component (A1) may be one type or two or more types.
As the structural unit (a6a), structural units represented by general formula (a6a-1) or (a6a-2) are preferable. As the structural unit (a6c), a structural unit represented by general formula (a6c-1) is preferable.
Among the above, the structural unit (a6) is preferably the structural unit (a6a).
In the component (A1), the proportion of the structural unit (a6) is preferably 0.5 to 30 mol%, and preferably 1 to 20 mol% with respect to the total of all the structural units constituting the component (A1). More preferably, it is particularly preferably 1.5 to 15 mol%.
By setting the proportion of the structural unit (a6) to the lower limit value or more, roughness is reduced and a good resist pattern shape is easily obtained. By setting it to the upper limit value or less, it is possible to balance with other structural units, and the lithography characteristics are further improved.

In such a resist composition, the component (A) includes the polymer compound (A1) having the structural unit (a0).
As the preferred component (A1), a polymer compound having a repeating structure of the structural unit (a0) and the structural unit (a2), a polymer compound having a repeating structure of the structural unit (a0) and the structural unit (a3), Polymer compound comprising a repeating structure of structural unit (a0) and structural unit (a6), polymer compound comprising a repeating structure of structural unit (a0), structural unit (a2) and structural unit (a3), structural unit Examples thereof include a polymer compound having a repeating structure of (a0), the structural unit (a2), the structural unit (a3), and the structural unit (a6). Among these, the structural unit (a0) and the structural unit (a2) And a polymer compound comprising a repeating structure of the structural unit (a3), a polymer compound comprising a repeating structure of the structural unit (a0), the structural unit (a2), the structural unit (a3) and the structural unit (a6). It is particularly preferred.

The mass average molecular weight (Mw) of the component (A1) (polystyrene conversion standard by gel permeation chromatography (GPC)) is not particularly limited, preferably 1000 to 50000, more preferably 1500 to 30000, 2000 to 2000 20000 is most preferred.
When the Mw of the component (A1) is less than or equal to the preferable upper limit value in this range, there is sufficient solubility in a resist solvent to be used as a resist. The resist pattern has a good cross-sectional shape.
The dispersity (Mw / Mn) of the component (A1) is not particularly limited, but is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and most preferably 1.0 to 3.0. . In addition, Mn shows a number average molecular weight.

As the component (A1), one type may be used alone, or two or more types may be used in combination.
The proportion of the component (A1) in the component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, still more preferably 75% by mass or more, and 100% by mass with respect to the total mass of the component (A). It may be. When the ratio is 25% by mass or more, in particular, the resolution of the pattern is improved, and it becomes easier to ensure lithography characteristics such as exposure margin (EL margin), line width roughness (LWR), and mask reproducibility.

Such a resist composition uses, as component (A), a base material component (hereinafter referred to as “component (A2)”) that does not correspond to the component (A1) and whose solubility in a developing solution is changed by the action of an acid. May be.
The component (A2) is not particularly limited, and many conventionally known base components for chemically amplified resist compositions (for example, for ArF excimer laser, for KrF excimer laser (preferably ArF excimer laser) For example, a base resin, a low molecular compound, etc.). (A2) A component may be used individually by 1 type and may be used in combination of 2 or more type.

In such a resist composition, the component (A) may be used alone or in combination of two or more.
In such a resist composition, the content of the component (A) may be adjusted according to the resist film thickness to be formed.

<Other ingredients>
Such a resist composition may further contain components other than the component (A) in addition to the component (A) described above. Examples of other components include the following (B) component, (D) component, (E) component, (F) component, and (S) component.

[(B) component: acid generator component]
Such a resist composition may further contain an acid generator component (hereinafter referred to as “component (B)”) in addition to the component (A).
The component (B) is not particularly limited, and those that have been proposed as acid generators for chemically amplified resists can be used.
Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators; diazomethanes such as bisalkyl or bisarylsulfonyldiazomethanes and poly (bissulfonyl) diazomethanes Acid generators: various types such as nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the like. Of these, it is preferable to use an onium salt acid generator.

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

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

[Wherein, R ¹⁰¹ and R ^{104 to} R ¹⁰⁸ each independently have a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. A chain alkenyl group which may be present. R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring. R ¹⁰² represents a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. V ^{101 to} V ¹⁰³ are each independently a single bond, an alkylene group or a fluorinated alkylene group. L ^{101 to} L ¹⁰² are each independently a single bond or an oxygen atom. L ^{103 to} L ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —. m is an integer of 1 or more, and M ′ ^{m +} is an m-valent onium cation. ]

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

Cyclic group which may have a substituent:
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

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

Examples of the cyclic aliphatic hydrocarbon group for R ¹⁰¹ include an aliphatic hydrocarbon group containing a ring in the structure.
As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group is linear or branched Examples thereof include a group bonded to the end of a chain aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group.
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 group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group in which one or more hydrogen atoms have been removed from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among these, the polycycloalkane includes polycycloalkanes having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; condensed ring systems such as a cyclic group having a steroid skeleton A polycycloalkane having a polycyclic skeleton is more preferable.
In the present specification, the “steroid skeleton” means a skeleton (st) represented by the following chemical formula in which three six-membered rings and one five-membered ring are connected.

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

The linear or branched aliphatic hydrocarbon group that may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 4 carbon atoms. Is more preferable, and 1-3 are most preferable.
As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

In addition, the cyclic hydrocarbon group for R ¹⁰¹ may contain a hetero atom such as a heterocyclic ring. Specifically, the lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), and the general formulas (a5-r-1) to (a5-r- -SO 2 respectively represented by 4) _- containing polycyclic group, heterocyclic group listed other less like.

Examples of the substituent in the cyclic group of R ¹⁰¹ include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group. Most preferred is an ethoxy group.
Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
As the halogenated alkyl group as a substituent, 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, a tert-butyl group, and the like And a group substituted with a halogen atom.
The carbonyl group as a substituent is a group that substitutes a methylene group (—CH ₂ —) constituting a cyclic hydrocarbon group.

A chain-like alkyl group which may have a substituent:
The chain alkyl group for 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 group Group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group and the like.
The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.

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

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

Among these, 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 group obtained by removing one or more hydrogen atoms from a phenyl group, a naphthyl group, or a polycycloalkane; each represented by the general formulas (a2-r-1) to (a2-r-7) Lactone-containing cyclic groups; —SO ₂ -containing cyclic groups represented by general formulas (a5-r-1) to (a5-r-4), respectively, are preferable.

In formula (b-1), Y ¹⁰¹ represents a single bond or a divalent linking group containing an oxygen atom.
When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, Y ¹⁰¹ may contain an atom other than an oxygen atom. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms.
Examples of the divalent linking group containing an oxygen atom include an oxygen atom (ether bond: —O—), an ester bond (—C (═O) —O—), and an oxycarbonyl group (—O—C (═O). )-), Amide bond (—C (═O) —NH—), carbonyl group (—C (═O) —), carbonate bond (—O—C (═O) —O—), etc. A combination of a non-hydrocarbon oxygen atom-containing linking group and an alkylene group; and the like. A sulfonyl group (—SO ₂ —) may be further linked to this combination. Examples of the divalent linking group containing an oxygen atom include linking groups represented by the following general 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 is a single bond or an alkylene group having 1 to 5 carbon atoms, and V ′ ¹⁰² is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms. ]

The divalent saturated hydrocarbon group for V ′ ¹⁰² is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 1 to 5 carbon atoms. More preferably.

The alkylene group for V ′ ¹⁰¹ and V ′ ¹⁰² may be a linear alkylene group or a branched alkylene group, and a linear alkylene group is preferred.
Specific examples of the alkylene group in V ′ ¹⁰¹ and V ′ ¹⁰² include a methylene group [—CH ₂ —]; —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as ethylene Groups [—CH ₂ CH ₂ —]; —CH (CH ₃ ) CH ₂ —, —CH (CH ₃ ) CH (CH ₃ ) —, —C (CH ₃ ) ₂ CH ₂ —, —CH (CH ₂ CH - ₃₎ CH ₂ alkyl groups such as, trimethylene group (n- propylene _{group) [- CH 2 CH 2 CH} 2 -]; - CH (CH 3) CH 2 CH 2 -, - CH 2 CH (CH 3) CH ₂ - and the like alkyl trimethylene group; tetramethylene _{[-CH 2 CH 2 CH 2 CH} 2 -]; - CH (CH 3) CH 2 CH 2 CH 2 -, - CH 2 CH (CH 3) CH 2 CH 2 - alkyl tetramethylene group and the like; pentamethylene group _{[-CH 2 CH 2 CH 2 CH} 2 CH 2 -] , and the like.
Moreover, some methylene groups in the alkylene group in V ′ ¹⁰¹ or V ′ ¹⁰² may be substituted with a C 5-10 divalent aliphatic cyclic group. The aliphatic cyclic group is a cyclic aliphatic hydrocarbon group of Ra ′ ^{3 in} the formula (a1-r-1) (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group). ) Is preferably a divalent group in which one hydrogen atom is further removed, more preferably a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group.

Y ¹⁰¹ is preferably a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, each represented by the above formulas (y-al-1) to (y-al-5). A linking group is more preferred.

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

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

(B-1) Specific examples of the anion moiety of the component, for example, if the Y ¹⁰¹ is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethane sulfonate anion or perfluorobutane sulfonate anion can be exemplified; Y ¹⁰¹ is In the case of a divalent linking group containing an oxygen atom, anions represented by any one of the following formulas (an-1) to (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、前記一般式（ａ２−ｒ−１）〜（ａ２−ｒ−７）でそれぞれ表されるラクトン含有環式基、又は前記一般式（ａ５−ｒ−１）〜（ａ５−ｒ−４）でそれぞれ表される−ＳＯ_２−含有環式基であり；Ｒ”^１０３は、置換基を有していてもよい芳香族環式基、置換基を有していてもよい脂肪族環式基、又は置換基を有していてもよい鎖状のアルケニル基であり；ｖ”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、ｔ”は１〜３の整数であり、ｎ”は０または１である。］

[Wherein R ″ ¹⁰¹ represents an aliphatic cyclic group which may have a substituent, a group represented by each of the above formulas (r-hr-1) to (r-hr-6), or a substituent. A chain-like alkyl group which may have a group; R ″ ¹⁰² represents an aliphatic cyclic group which may have a substituent, the above-mentioned general formulas (a2-r-1) to (a2- a lactone-containing cyclic group represented by each of r-7), or a —SO ₂ -containing cyclic group represented by each of the general formulas (a5-r-1) to (a5-r-4); R ″ ¹⁰³ is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent. V ″ is independently an integer from 0 to 3, q ″ is independently an integer from 1 to 20, t ″ is an integer from 1 to 3, and n ″ is 0. The other is 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 that may be substituted for the cyclic aliphatic hydrocarbon group in R ¹⁰¹ .

The aromatic cyclic group which may have a substituent in R ″ ¹⁰³ is preferably the group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R ¹⁰¹ . , R ¹⁰¹ and the same substituents that may be substituted for the aromatic hydrocarbon group.

The chain alkyl group which may have a substituent in R ″ ¹⁰¹ is preferably the group exemplified as the chain alkyl group in R ^101. The chain in R ″ ¹⁰³ has a substituent. The good chain alkenyl group is preferably the group exemplified as the chain alkenyl group in R ¹⁰¹ .

-Anion part of component (b-2) In formula (b-2), R ¹⁰⁴ and R ¹⁰⁵ may each independently have a cyclic group which may have a substituent or a substituent. Examples thereof include a good chain alkyl group or a chain alkenyl group which may have a substituent, and examples thereof include the same as those described above for R ¹⁰¹ in 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 a chain alkyl group which may have a substituent, and are a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. It is more preferable.
The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and still more preferably 1 to 3 carbon atoms. The number of carbon atoms of the chain alkyl group of R ¹⁰⁴ and R ¹⁰⁵ is preferably as small as possible because the solubility in a resist solvent is good within the range of the carbon number. In addition, in the chain alkyl group of R ¹⁰⁴ and R ^105, the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and against high-energy light and electron beams of 200 nm or less Since transparency improves, it is preferable. The proportion 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. Perfluoroalkyl group.
In formula (b-2), V ¹⁰² and V ¹⁰³ are each independently a single bond, an alkylene group, or a fluorinated alkylene group, and each of them is the same as V ¹⁰¹ in formula (b-1). Can be mentioned.
In formula (b-2), L ¹⁰¹ and L ¹⁰² each independently represent a single bond or an oxygen atom.

-Anion part of (b-3) component In formula (b-3), R < ¹⁰⁶ > -R < ¹⁰⁸ > may have the cyclic group which may have a substituent, and a substituent each independently. Examples thereof include a good chain alkyl group or a chain alkenyl group which may have a substituent, and examples thereof include those similar to R ¹⁰¹ in formula (b-1).
L ^{103 to} L ¹⁰⁵ are each independently a single bond, —CO— or —SO ₂ —.

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

［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、置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、又は置換基を有していてもよい−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。］

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

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

［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、置換基を有していてもよい鎖状のアルキル基、又は置換基を有していてもよい鎖状のアルケニル基である。］

[Wherein, each R ′ ²⁰¹ independently has a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It may be a chain alkenyl group. ]

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

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

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. 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.
The aryl group in R ^210, include unsubstituted aryl group having 6 to 20 carbon atoms, a phenyl group, a naphthyl group.
The alkyl group for R ²¹⁰ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
The alkenyl group for R ²¹⁰ preferably has 2 to 10 carbon atoms.
^Examples of the —SO ₂ — containing cyclic group which may have a substituent in R ²¹⁰ include those similar to the aforementioned “—SO ₂ — containing cyclic group”, and among these, the general formula ( The group represented by a5-r-1) is preferred.

Y ²⁰¹ each independently represents an arylene group, an alkylene group or an alkenylene group.
Examples of the arylene group for Y ²⁰¹ include a group in which one hydrogen atom has been removed from the aryl group exemplified as the aromatic hydrocarbon group for R ¹⁰¹ in the aforementioned formula (b-1).
Examples of the alkylene group and alkenylene group in Y ²⁰¹ include a group in which one hydrogen atom has been removed from the groups exemplified as the chain alkyl group and chain alkenyl group in R ¹⁰¹ in the aforementioned formula (b-1). .

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

  Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-67).

［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。］

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

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

[Wherein, R ″ ²⁰¹ is a hydrogen atom or a substituent, and the substituent is the same as those exemplified as the substituent that R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have. Is.]

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

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

Among these, the cation part [(M ′ ^{m +} ) _{1 / m} ] is preferably a cation represented by the general formula (ca-1), and represented by the formulas (ca-1-1) to (ca-1-67). Cations represented respectively are more preferred.

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

[(D) component: acid diffusion controlling agent component]
Such a resist composition contains an acid diffusion controller component (hereinafter referred to as “component (D)”) in addition to the component (A) or in addition to the components (A) and (B). May be. The component (D) acts as a quencher (acid diffusion controller) that traps acid generated by exposure in the resist composition.
The component (D) may be a photodegradable base (D1) (hereinafter referred to as “component (D1)”) which is decomposed by exposure and loses acid diffusion controllability, and includes a component not corresponding to the component (D1). It may be a nitrogen organic compound (D2) (hereinafter referred to as “component (D2)”).

-About (D1) component By forming it as a resist composition containing (D1) component, when forming a resist pattern, the contrast of an exposed part and an unexposed part can be improved.
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 referred to as “(d1-1) component”). ), A compound represented by the following general formula (d1-2) (hereinafter referred to as “(d1-2) component”) and a compound represented by the following general formula (d1-3) (hereinafter referred to as “(d1- One or more compounds selected from the group consisting of “3) component”) are preferred.
The components (d1-1) to (d1-3) decompose in the exposed part of the resist film and lose acid diffusion controllability (basicity), and thus do not act as a quencher, and act as a quencher in an unexposed part. To do.

［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、又は置換基を有していてもよい鎖状のアルケニル基である。但し、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は単結合又は２価の連結基である。ｍは１以上の整数であって、Ｍ^ｍ＋はそれぞれ独立にｍ価の有機カチオンである。］

[Wherein, Rd ^{1 to} Rd ⁴ are 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. Of the alkenyl group. However, a fluorine atom is not bonded to a carbon atom adjacent to the S atom in Rd ² in the formula (d1-2). Yd ¹ is a single bond or a divalent linking group. m is an integer of 1 or more, and M ^{m +} is each independently an m-valent organic cation. ]

{(D1-1) component}
.. Anion moiety In formula (d1-1), Rd ¹ has a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. And a chain alkenyl group which may be the same as R ¹⁰¹ in the formula (b-1).
Among these, Rd ¹ may have an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a substituent. A chain alkyl group is preferred. Examples of the substituent that these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, and the above general formulas (a2-r-1) to (a2-r- Examples thereof include lactone-containing cyclic groups represented by 7), ether bonds, ester bonds, or combinations thereof. When an ether bond or an ester bond is included as a substituent, an alkylene group may be interposed. In this case, the substituent is represented by the above formulas (y-al-1) to (y-al-5), respectively. The linking group is preferred.
As the aromatic hydrocarbon group, a phenyl group or a naphthyl group is more preferable.
The aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
The chain alkyl group preferably has 1 to 10 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Linear alkyl groups such as nonyl and decyl; 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl A branched alkyl group such as a group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group.

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

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

..Cation part In the formula (d1-1), M ^{m +} is an m-valent organic cation.
As the organic cation of M ^{m +} , those similar to the cations represented by the general formulas (ca-1) to (ca-4) are preferably exemplified, and represented by the general formula (ca-1). A cation is more preferable, and a cation represented by each of the formulas (ca-1-1) to (ca-1-67) is more 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}
.. Anion moiety In 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. A chain alkenyl group that may be present, and examples thereof include the same groups as those described above for R ^{101 in} formula (b-1).
However, a fluorine atom is not bonded to a carbon atom adjacent to the S atom in Rd ² (not fluorine-substituted). Thereby, the anion of (d1-2) component turns into a moderate weak acid anion, and the quenching ability as (D) component improves.
Rd ² is preferably a chain alkyl group which may have a substituent, or an aliphatic cyclic group which may have a substituent. The chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. As the aliphatic cyclic group, a group in which one or more hydrogen atoms are removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane or the like (which may have a substituent); one from camphor or the like A group excluding the above hydrogen atoms is more preferable.
The hydrocarbon group of Rd ² may have a substituent, and examples of the substituent include a hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group) in Rd ¹ of the formula (d1-1). Examples thereof include the same substituents that the chain-like alkyl group may have.

  Preferred specific examples of the anion moiety of the component (d1-2) are shown below.

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

{(D1-3) component}
.. Anion moiety In 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. A chain alkenyl group which may be the same as R ^{101 in} formula (b-1), and includes a cyclic group containing a fluorine atom, a chain alkyl group, or a chain alkenyl group. It is preferable that Among them, a fluorinated alkyl group is preferable, and the same as the fluorinated alkyl group for 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. Examples of the chain alkenyl group include those similar to R ¹⁰¹ in the formula (b-1).
Among these, an alkyl group, an alkoxy group, an alkenyl group, or a cyclic group that may have a substituent is preferable.
The alkyl group in Rd ⁴ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group. Tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. A part of the hydrogen atoms of the alkyl group of Rd ⁴ may be substituted with a hydroxyl group, a cyano group, or the like.
The alkoxy group in Rd ⁴ is preferably an alkoxy group having 1 to 5 carbon atoms. Specific examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n- Examples include butoxy group and tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferable.

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

Examples of the cyclic group for Rd ⁴ include those similar to R ¹⁰¹ in the above formula (b-1), such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. An alicyclic group excluding one or more hydrogen atoms, or an aromatic group such as a phenyl group or a naphthyl group is preferred. When Rd ⁴ is an alicyclic group, the resist composition is well dissolved in an organic solvent, whereby the lithography properties are improved. In addition, when Rd ⁴ is an aromatic group, in lithography using EUV or the like as an exposure light source, the resist composition is excellent in light absorption efficiency, and sensitivity and lithography characteristics are good.

In formula (d1-3), Yd ¹ represents a single bond or a divalent linking group.
The divalent linking group in Yd ¹ is not particularly limited, but may be a divalent hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group) which may have a substituent, or a hetero atom containing 2 Valent linking groups and the like. Each of these includes a divalent hydrocarbon group which may have a substituent and a hetero atom which are mentioned in the description of the divalent linking group of Ya ²¹ in the formula (a2-1). The thing similar to a valent coupling group is mentioned.
Yd ¹ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. The alkylene group is preferably a linear or branched alkylene group, and more preferably a methylene group or an ethylene group.

  Preferred specific examples of the anion moiety of the component (d1-3) are shown below.

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

As the component (D1), only one of the above components (d1-1) to (d1-3) may be used, or two or more may be used in combination.
When the resist composition contains the component (D1), the content of the component (D1) is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A), and 0.5 to More preferably, it is 8 mass parts, and it is still more preferable that it is 1-8 mass parts.
When the content of the component (D1) is equal to or more than the preferable lower limit value, particularly good lithography characteristics and a resist pattern shape are easily 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.

(D1) Component production method:
The manufacturing method of said (d1-1) component and (d1-2) component is not specifically limited, It can manufacture by a well-known method.
Moreover, the manufacturing method of (d1-3) component is not specifically limited, For example, it manufactures similarly to the method of US2012-0149916 gazette.

-About (D2) component As an acid diffusion controlling agent component, you may contain the nitrogen-containing organic compound component (henceforth "(D2) component") which does not correspond to said (D1) component.
The component (D2) is not particularly limited as long as it functions as an acid diffusion controller and does not correspond to the component (D1), and any known component may be used. Of these, aliphatic amines are preferable, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferable.
An aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 12 carbon atoms.
Examples of the aliphatic amine include an amine (alkyl amine or alkyl alcohol amine) or a cyclic amine in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms.
Specific examples of alkylamines and alkyl alcohol 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 , Trialkylamines such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, Li isopropanolamine, di -n- octanol amines, alkyl alcohol amines tri -n- octanol amine. Among these, a trialkylamine having 5 to 10 carbon atoms is more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

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

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

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

(D2) A component may be used independently and may be used in combination of 2 or more type.
When the resist composition contains the component (D2), the component (D2) is usually used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A). By setting the content in the above range, the resist pattern shape, the stability over time, and the like are improved.

[Component (E): at least one compound selected from the group consisting of organic carboxylic acids and phosphorus oxo acids and derivatives]
Such a resist composition includes, as an optional component, from the group consisting of an organic carboxylic acid, a phosphorus oxo acid, and derivatives thereof for the purpose of preventing sensitivity deterioration, improving the resist pattern shape, stability over time, and the like. At least one selected compound (E) (hereinafter referred to as “component (E)”) can be contained.
As the organic carboxylic acid, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
Examples of phosphorus oxo acids include phosphoric acid, phosphonic acid, and phosphinic acid. Among these, phosphonic acid is particularly preferable.
Examples of the oxo acid derivative of phosphorus include esters in which the hydrogen atom of the oxo acid is substituted with a hydrocarbon group, and the hydrocarbon group includes an alkyl group having 1 to 5 carbon atoms and 6 to 6 carbon atoms. 15 aryl groups and the like.
Examples of phosphoric acid derivatives include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.
Examples of phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester.
Examples of phosphinic acid derivatives include phosphinic acid esters and phenylphosphinic acid.
(E) A component may be used individually by 1 type and may use 2 or more types together.
When a resist composition contains (E) component, (E) component is normally used in 0.01-5 mass parts with respect to 100 mass parts of (A) component.

[(F) component: fluorine additive component]
Such a resist composition may contain a fluorine additive component (hereinafter referred to as “component (F)”) in order to impart water repellency to the resist film.
Examples of the component (F) include those described in JP 2010-002870 A, JP 2010-032994 A, JP 2010-277043 A, JP 2011-13569 A, and JP 2011-128226 A. These fluorine-containing polymer compounds can be used.
More specifically, examples of the component (F) include a polymer having a structural unit (f1) represented by the following formula (f1-1). Examples of the polymer include a polymer (homopolymer) composed only of the structural unit (f1) represented by the following formula (f1-1); a copolymer of the structural unit (f1) and the structural unit (a1). A copolymer of the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1). Here, the structural unit (a1) copolymerized with the structural unit (f1) is preferably a structural unit derived from 1-ethyl-1-cyclooctyl (meth) acrylate.

［式中、Ｒは前記と同様であり、Ｒｆ^１０２およびＲｆ^１０３はそれぞれ独立して水素原子、ハロゲン原子、炭素数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。］

[Wherein, R is the same as defined above, and Rf ¹⁰² and Rf ¹⁰³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, 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 bonded to the α-position carbon atom is the same as described above. R is preferably a hydrogen atom or a methyl group.
In formula (f1-1), examples of the halogen atom for Rf ¹⁰² and Rf ¹⁰³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. Examples of the alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include the same as the alkyl group having 1 to 5 carbon atoms of R, and a methyl group or an ethyl group is preferable. Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include groups in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Be Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. The inter alia ^{Rf 102} and ^{Rf 103,} a hydrogen atom, a fluorine atom, or an alkyl group of 1 to 5 carbon atoms is preferable, a hydrogen atom, a fluorine atom, a methyl group or an ethyl group, preferred.
In formula (f1-1), nf ¹ is an integer of ¹ to 5, an integer of 1 to 3 is preferable, and 1 or 2 is more preferable.

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

(F) As for the mass mean molecular weight (Mw) (polystyrene conversion reference | standard by gel permeation chromatography), 1000-50000 are preferable, 5000-40000 are more preferable, and 10000-30000 are the most preferable. If it is below the upper limit of this range, it has sufficient solubility in a resist solvent for use as a resist, and if it is above the lower limit of this range, the dry etching resistance and resist pattern cross-sectional shape are good. .
The dispersity (Mw / Mn) of the component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5.

(F) A component may be used individually by 1 type and may use 2 or more types together.
When a resist composition contains (F) component, (F) component is normally used in the ratio of 0.5-10 mass parts with respect to 100 mass parts of (A) component.

  Such resist compositions further contain miscible additives as desired, such as additional resins for improving the performance of resist films, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, and the like. Can be added and contained as appropriate.

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

The resist composition described above includes, as a base resin, a polymer compound (A1) having a structural unit (a0) containing “—Va ⁰¹ -La ⁰ -Va ⁰² —C (═O) O—Ra ⁰ ” in the side chain. Containing. In the structural unit (a0), Ra ⁰ which is an acid dissociable group is located away from the polymer main chain. Therefore, the ratio of contact with the developer is high during development in resist pattern formation. Thereby, if the developer is an alkali developer, the solubility of the resist film exposed portion is increased, and if the developer is an organic developer, the solubility of the resist film unexposed portion is increased. In either case, the dissolution contrast between the exposed portion and the unexposed portion is increased. As a result, it is possible to obtain an effect that the lithography characteristics are further improved and a resist pattern having an excellent shape can be formed.
The polymer main chain and the acid dissociable group Ra ⁰ are appropriately separated from each other, so that the effect of improving the lithography properties can be obtained. On the other hand, if both are separated too much, the lithography properties tend to be lowered. is there. In such a resist composition, a specific structure “-Va ⁰¹ -La ⁰ -Va ⁰² -C () is formed such that the polymer main chain and the acid dissociable group Ra ⁰ are located at an appropriate distance. = O) O-Ra ⁰ "is introduced into the side chain of the base resin, and the polymer compound (A1) is used. Thereby, said effect is exhibited notably.

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

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

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

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

  Examples of the alkali developer used for the development treatment in the alkali development process include a 0.1 to 10% by mass tetramethylammonium hydroxide (TMAH) aqueous solution.

The organic solvent contained in the organic developer used in the development process in the solvent development process is not particularly limited as long as it can dissolve the component (A1) (component (A1) before exposure). It can be selected as appropriate. Specific examples include ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, ether solvents, and other polar solvents, hydrocarbon solvents, and the like.
The ketone solvent is an organic solvent containing C—C (═O) —C in the structure. The ester solvent is an organic solvent containing C—C (═O) —O—C in the structure. The alcohol solvent is an organic solvent containing an alcoholic hydroxyl group in the structure, and “alcoholic hydroxyl group” means a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. A nitrile solvent is an organic solvent containing a nitrile group in its structure. The amide solvent is an organic solvent containing an amide group in the structure. The ether solvent is an organic solvent containing C—O—C in the structure.
Among organic solvents, there are organic solvents that contain multiple types of functional groups that characterize each of the above solvents in the structure, but in that case, any of the solvent types that contain the functional groups of the organic solvent is applicable. Shall. For example, diethylene glycol monomethyl ether shall correspond to both of the alcohol solvent and the ether solvent in the above classification.
The hydrocarbon solvent is a hydrocarbon solvent made of a hydrocarbon which may be halogenated and having no substituent other than a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
Among these, the organic solvent contained in the organic developer is preferably a polar solvent, and is preferably a ketone solvent, an ester solvent, a nitrile solvent, or the like. Specific examples of each solvent are shown below.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl ethyl ketone. , Methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone) and the like.
As the ketone solvent, methyl amyl ketone (2-heptanone) is preferable.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Propyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene Recall monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxy Nethyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, pyrubin Methyl acid, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, 2-hydroxypropionate Examples include ethyl acid, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate.
As the ester solvent, butyl acetate is preferred.

  Examples of the nitrile solvent include acetonitrile, propionitryl, valeronitrile, butyronitryl and the like.

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

  The development process can be performed by a known development method. For example, a method in which a support is immersed in a developer for a certain period of time (dip method), a developer is raised on the surface of the support by surface tension, and is left for a certain period of time. (Paddle method), spraying developer on the surface of the support (spray method), coating the developer while scanning the developer coating nozzle at a constant speed on the support rotating at a constant speed The method of continuing (dynamic dispensing method) etc. are mentioned.

As the organic solvent contained in the rinsing liquid used for the rinsing process after the development process in the solvent developing process, for example, an organic solvent that is difficult to dissolve the resist pattern is selected as appropriate from the organic solvents used as the organic solvent used in the organic developer. Can be used. Usually, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. Among these, at least one selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents and amide solvents is preferable, and at least one selected from alcohol solvents and ester solvents is preferable. More preferred are alcohol solvents.
The alcohol solvent used in the rinse liquid is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched or cyclic. Specific examples include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. It is done. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferable, and 1-hexanol and 2-hexanol are more preferable.
Any one of these organic solvents may be used alone, or two or more thereof may be mixed and used. Moreover, you may mix and use organic solvents and water other than the above. However, in consideration of development characteristics, the amount of water in the rinsing liquid is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, more preferably 3% by mass with respect to the total amount of the rinsing liquid. The following are particularly preferred:
A well-known additive can be mix | blended with a rinse liquid as needed. Examples of the additive include a surfactant. Examples of the surfactant are the same as those described above, and a nonionic surfactant is preferable, and a fluorine-based surfactant or a silicon-based surfactant is more preferable.
When the surfactant is blended, the blending amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and 0.01 to 0.5% by mass with respect to the total amount of the rinse liquid. % Is more preferable.

  The rinse treatment (washing treatment) using the rinse liquid can be performed by a known rinse method. Examples of the method include a method of continuously applying a rinsing liquid on a support rotating at a constant speed (rotary coating method), a method of immersing the support in a rinsing liquid for a predetermined time (dip method), and the surface of the support. And a method of spraying a rinse liquid (spray method).

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

<Production of compound>
(Example 1: Compound (01))
Under a nitrogen atmosphere, oxalyl chloride (33 g) and dichloromethane (165 g) were added to a three-necked flask and cooled to 5 ° C. Thereto was added dropwise a solution of compound (0-i) (50 g) in dichloromethane (500 g) at the same temperature over 1 hour. Then, DMF (0.79g) was added, and it heated up to room temperature, and stirred for 2 hours. Subsequently, the reaction solution was concentrated to obtain 54 g of the target compound (0-ii) as an oily compound.
The obtained compound (0-ii) was subjected to NMR measurement, and its structure was identified from the following results.
¹ H-NMR (400 MHz, CDCl ₃ ): δ (ppm) = 6.11 (m, 1H), 5.54 (m, 1H), 4.28 (s, 4H), 3.10 (t, 2H) ), 2.58 (t, 2 H), 1.91 (m, 3H).

Next, under a nitrogen atmosphere, compound (01-1) (10.67 g), dibutylaniline (DBA) (22.8 g) as a base, and acetonitrile (52.0 g) were added to a three-necked flask, and 5 Cooled to ° C. Thereto, a solution of compound (0-ii) (23.0 g) in acetonitrile (52.0 g) was added dropwise at the same temperature over 1 hour, followed by stirring at 70 ° C. for 8 hours. Thereafter, hexane was added to the reaction solution, and the whole was washed with 10% by mass hydrochloric acid, and then washed with 1% by mass ammonia water. Thereafter, the obtained organic phase was concentrated to obtain 17.5 g of the final target compound (01) as an oily compound.
The obtained compound (01) was subjected to NMR measurement, and its structure was identified from the following results.
¹ H-NMR (400 MHz, DMSO-d6): δ (ppm) = 6.08 (m, 1H), 5.66 (m, 1H), 4.31 (s, 4H), 2.62 (septet, 1H), 2.59-2.45 (m, 4H), 2.00-1.50 (m, 11H), 0.83 (d, 6H).

(Example 2, Comparative Examples 1-7)
In the production methods of Example 2 and Comparative Examples 1 to 7, the base (DBA) used in Example 1 was changed to the compounds listed below (DMA, DABCO, TEA, DIPEA, Pyridine, DMAP, DBU, LDA). Compound (01) was produced in the same manner as in the production method of Example 1, except that each was changed. The results are shown in Table 1.
In Table 1, “pKa of conjugate acid of base” indicates a calculated value using “Software V11.02 (1994-2013 ACD / Labs)” (trade name, manufactured by Advanced Chemistry Development).

From the results shown in Table 1, the production methods of Examples 1 and 2 to which the present invention was applied, that is, a compound represented by the general formula (ca), and a tertiary amine having a pKa of a conjugate acid of 7 or less ( However, in the presence of the compound (0-ii) and the compound in the presence of the nitrogen atom to which R ^ca1 , R ^ca2 and R ^{ca3 in} General Formula (ca) are bonded is part of an aromatic ring) It can be confirmed that the desired compound (01) can be obtained by reacting with (01-1).

On the other hand, although it is a compound represented by the general formula (ca), the compound (0-ii) and the compound (01-1) are reacted in the presence of a tertiary amine in which the pKa of the conjugate acid is more than 7. In any of the production methods of Comparative Examples 1 to 3 and 5 to 7, the target compound (01) was not obtained.
In addition, although the pKa of the conjugate acid is 7 or less, the compound (0-ii) and the compound (01-1) are combined in the presence of a compound (pyridine) different from the compound represented by the general formula (ca). The target compound (01) was not obtained even in the production method of Comparative Example 4 which was reacted.

(Example 3: Compound (02))
In a nitrogen atmosphere, compound (02-1) (9.43 g), dibutylaniline (DBA) (19.8 g) as a base, and acetonitrile (45.0 g) were added to a three-necked flask and cooled to 5 ° C. did. Thereto, a solution of compound (0-ii) (20.0 g) in acetonitrile (45.0 g) was added dropwise over 1 hour at the same temperature, followed by stirring at 70 ° C. for 8 hours. Thereafter, hexane was added to the reaction solution, and the whole was washed with 10% by mass hydrochloric acid, and then washed with 1% by mass ammonia water. Thereafter, the obtained organic phase was concentrated to obtain 14.4 g of the final target compound (02) as an oily compound.
The obtained compound (02) was subjected to NMR measurement, and its structure was identified from the following results.
¹ H-NMR (400 MHz, DMSO-d6): δ (ppm) = 6.03 (m, 1H), 5.70 (m, 1H), 4.27 (s, 4H), 2.60-2. 45 (m, 4H), 2.20 (septet, 2H), 1.88 (s, 3H), 1.30 (s, 3H), 0.89-0.86 (m, 12H).

<Manufacture of polymer compounds>
(Example 4: polymer compound (A1-1))
The compound (21) (10.0 g), the compound (01) (9.2 g), and the compound (31) (4.1 g) were dissolved in methyl ethyl ketone (MEK), and then there as a polymerization initiator. Dimethyl azobisisobutyrate (V-601) (2.48 g) was added and dissolved to prepare a dropping solution. Next, MEK (12.4 g) was added to a separable flask connected with a thermometer, a reflux tube and a nitrogen introduction tube, and heated to 80 ° C. Then, the said dripping solution was dripped here over 4 hours at the same temperature and nitrogen atmosphere. After completion of dropping, the reaction solution was stirred at the same temperature for 1 hour. Thereafter, the reaction solution was cooled to room temperature. The obtained reaction solution was dropped into a large amount of methanol, and a polymer was precipitated. The precipitated white powder was filtered off, washed with methanol and dried, and the target polymer compound (A1) -1) 11.5 g was obtained.
About this high molecular compound (A1-1), the mass mean molecular weight (Mw) of standard polystyrene conversion calculated | required by GPC measurement was 7000, and molecular weight dispersion degree (Mw / Mn) was 1.62. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz — ¹³ C-NMR) is 1 / m / n = 51.1 / It was 30.9 / 18.0.

(Example 5: polymer compound (A1-2))
The compound (21) (10.0 g), the compound (02) (9.2 g), and the compound (31) (4.1 g) were dissolved in methyl ethyl ketone (MEK), and then there as a polymerization initiator. Dimethyl azobisisobutyrate (V-601) (2.48 g) was added and dissolved to prepare a dropping solution. Next, MEK (15.78 g) was added to a separable flask connected with a thermometer, a reflux tube and a nitrogen introduction tube, and heated to 80 ° C. Then, the said dripping solution was dripped here over 4 hours at the same temperature and nitrogen atmosphere. After completion of dropping, the reaction solution was stirred at the same temperature for 1 hour. Thereafter, the reaction solution was cooled to room temperature. The obtained reaction solution was dropped into a large amount of methanol, and a polymer was precipitated. The precipitated white powder was filtered off, washed with methanol and dried, and the target polymer compound (A1) -2) 11.5 g was obtained.
With respect to this polymer compound (A1-2), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 6500, and the molecular weight dispersity (Mw / Mn) was 1.65. The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz — ¹³ C-NMR) is 1 / m / n = 51.7 / It was 29.5 / 18.8.

(Example 6: polymer compound (A1-3))
In addition to the compound (21), the compound (01) and the compound (31) as a monomer, the polymerization is performed in the same manner as in Example 4 except that the compound (61) shown below is used in combination. As a result, the target polymer (A1-3) was obtained.
With respect to this polymer compound (A1-3), the mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 7100, and the molecular weight dispersity (Mw / Mn) was 1.71. The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by carbon-13 nuclear magnetic resonance spectrum (600 MHz — ¹³ C-NMR) is 1 / m / n / o = 50. It was 4 / 24.3 / 20.6 / 4.7.

(Example 7: polymer compound (A1-4))
Polymerization or the like was performed in the same manner as in Example 4 except that the compound (01) was changed to the compound (03) shown below to obtain the target polymer compound (A1-4).
With respect to this polymer compound (A1-4), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 6800, and the molecular weight dispersity (Mw / Mn) was 1.67. The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz — ¹³ C-NMR) is 1 / m / n = 51.1 / It was 30.2 / 18.7.

<Preparation of resist composition>
(Test Examples 1 to 10)
The resist composition of each example was prepared by mixing and dissolving each component shown in Table 2.
As the base resins of the resist compositions of Test Examples 1 to 5 and 10, polymer compounds obtained by a production method not applying the present invention were used.
As the base resins of the resist compositions of Test Examples 6 to 9, polymer compounds obtained by the production method to which the present invention was applied were used.

In Table 2, each abbreviation has the following meaning. The numerical value in [] is a compounding amount (part by mass).
(A) -1: the polymer compound (A1-1).
(A) -2: The polymer compound (A1-2).
(A) -3 to (A) -6: polymer compounds represented by the following chemical formulas (A) -3 to (A) -6, respectively.
(A) -3: a polymer compound represented by the following chemical formula (A) -3. The mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 7100, and the molecular weight dispersity (Mw / Mn) is 1.66. ^The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by ¹³ C-NMR was 1 / m / n = 48.6 / 30.3 / 21.1.
(A) -4: a polymer compound represented by the following chemical formula (A) -4. The mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 6800, and the molecular weight dispersity (Mw / Mn) is 1.51. ^The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by ¹³ C-NMR was 1 / m / n = 50.5 / 29.3 / 20.2.
(A) -5: a polymer compound represented by the following chemical formula (A) -5. The mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 7200, and the molecular weight dispersity (Mw / Mn) is 1.59. ^The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by ¹³ C-NMR was 1 / m / n = 50.8 / 30.1 / 19.1.
(A) -6: a polymer compound represented by the following chemical formula (A) -6. The mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 6900, and the molecular weight dispersity (Mw / Mn) is 1.68. ^The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by ¹³ C-NMR was 1 / m / n = 50.3 / 30.9 / 18.8.
(A) -7: The polymer compound (A1-3).
(A) -8: a polymer compound represented by the following chemical formula (A) -8. The mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 7400, and the molecular weight dispersity (Mw / Mn) is 1.75. ^The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by ¹³ C-NMR was 1 / m / n / o = 50.4 / 24.9 / 20.0 / 4.7. .
(A) -9: The polymer compound (A1-4).
(A) -10: a polymer compound represented by the following chemical formula (A) -10. The mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 6800, and the molecular weight dispersity (Mw / Mn) is 1.68. ^The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by ¹³ C-NMR was 1 / m / n = 50.3 / 29.8 / 19.9.

(B) -1: a compound represented by the following chemical formula (B) -1.
(D) -1: A compound represented by the following chemical formula (D) -1.
(E) -1: salicylic acid.
(F) -1: A fluorine-containing polymer compound represented by the following chemical formula (F) -1. The weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement is 23100, and the molecular weight dispersity (Mw / Mn) is 1.78. ^The copolymer composition ratio (ratio of each structural unit in the structural formula (molar ratio)) determined by ¹³ C-NMR is 1 / m = 77/23.
(S) -1: γ-butyrolactone.
(S) -2: Mixed solvent of PGMEA / PGME / cyclohexanone (mass ratio 45/30/25).

<Formation of resist pattern (1): positive development process>
An organic antireflective coating composition “ARC95” (trade name, manufactured by Brewer Science) was applied onto a 12-inch silicon wafer using a spinner, baked at 205 ° C. for 60 seconds, and dried. As a result, an organic antireflection film having a thickness of 90 nm was formed.
Each of the resist compositions of Test Examples 1 to 10 was applied on the organic antireflection film, and prebaked (PAB) at 110 ° C. for 60 seconds on a hot plate and dried. A 90 nm resist film was formed.
Next, immersion ArF exposure apparatus NSR-S609B [Nikon Corporation; NA (numerical aperture) 1.07, Dipole 0.97 / 0.78 w / P, immersion medium: water] Then, ArF excimer laser (193 nm) was selectively irradiated through a photomask.
Thereafter, a post-exposure heating (PEB) treatment at 95 ° C. for 60 seconds was performed.
Subsequently, alkali development was performed for 10 seconds at 23 ° C. 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 was formed in any of the examples.
In both examples, a line and space pattern having a line width of 50 nm / pitch of 100 nm was formed.

[Evaluation of optimum exposure (EOP)]
The optimum exposure dose EOP (mJ / cm ² ) at which a line-and-space pattern having a target size (line width 50 nm / pitch width 100 nm) was formed by the formation of the resist pattern (1) was determined. The results are shown in Table 3 as “EOP (mJ / cm ² )”.

[Evaluation of exposure margin (EL margin)]
In the formation of the resist pattern (1), the exposure amount when the line width of the line and space pattern is formed within a range of about ± 5% of the target dimension (line width 50 nm) is obtained, and the EL margin ( Unit:%). The results are shown in Table 3 as “5% EL (%)”.
EL margin (%) = (| E1-E2 | / EOP) × 100
E1: Exposure amount (mJ / cm ² ) when a line and space pattern having a line width of 47.5 nm was formed
E2: exposure amount (mJ / cm ² ) when a line and space pattern having a line width of 52.5 nm was formed
Note that the larger the value of the EL margin, the smaller the change amount of the pattern size accompanying the change in the exposure amount.

[Evaluation of LWR (Line Width Roughness)]
In a line and space pattern with a line width of 50 nm / pitch width of 100 nm formed by the formation of the resist pattern (1), a length measurement SEM (scanning electron microscope, acceleration voltage of 300 V, trade name: S-9380, Hitachi High-Technologies) The product was measured at 400 points in the longitudinal direction of the line, and from that result, the triple value (3s) of the standard deviation (s) was obtained, and the average value for 3s at 400 points was calculated as LWR. Calculated as a measure of indication. The results are shown in Table 3 as “LWR (nm)”.
The smaller the value of 3s, the smaller the roughness of the line width, which means that a line-and-space pattern with a more uniform width was obtained.

[Evaluation of mask error factor (MEEF)]
In accordance with the same procedure as the formation of the resist pattern (1), each mask pattern having a target size (line width) of 45 to 55 nm (1 nm increments, total of 11 points) is used, and each line and space pattern having a pitch of 100 nm is subjected to the same exposure. Formed in quantity.
At that time, the slope of the straight line (MEEF) when the target size (nm) was plotted on the horizontal axis and the line width (nm) of the pattern formed on the resist film using each mask pattern was plotted on the vertical axis was calculated. The results are shown in Table 3 as “MEEF”.
MEEF (straight line) means that the closer the value is to 1, the better the mask reproducibility.

  From the results shown in Table 3, in the resist pattern formation by the positive development process, the resist compositions of Test Examples 6 to 9 containing the polymer compound produced by applying the present invention are manufactured outside the scope of the present invention. Compared to the resist compositions of Test Examples 1 to 5 and 10 containing the polymer compound produced by the method, it can be seen that a resist pattern having excellent lithography characteristics and a good shape can be formed.

<Formation of resist pattern (2): negative development process>
An organic antireflection film having a thickness of 72 nm was formed on a 12-inch silicon wafer, and then an inorganic antireflection film having a thickness of 14 nm was laminated on the organic antireflection film.
On the inorganic antireflection film, each of the resist compositions of Test Examples 6, 7, 9 and Test Examples 1 to 4, 10 was applied using a spinner, and was heated on a hot plate at 110 ° C. for 50 seconds. A resist film having a film thickness of 85 nm was formed by performing pre-baking (PAB) treatment and drying.
Next, a photomask is applied to the resist film using an immersion ArF exposure apparatus NSR-S609B [manufactured by Nikon; NA (numerical aperture) = 1.07, Annular 0.78 / 0.97 w / o P]. Was selectively irradiated with an ArF excimer laser (193 nm).
Thereafter, a post-exposure heating (PEB) treatment was performed at 90 ° C. for 50 seconds.
Subsequently, solvent development was performed for 31 seconds with butyl acetate at 23 ° C., and then shaken and dried.
As a result, in each of the examples, a space-and-line resist pattern (hereinafter also referred to as “SL pattern”) having a space width of 47 nm / pitch of 110 nm was formed.

[Evaluation of optimum exposure (EOP)]
The optimum exposure dose EOP (mJ / cm ² ) at which the SL pattern having the target size (space width 47 nm / pitch width 110 nm) was formed by the formation of the resist pattern (2) was determined. The results are shown in Table 4 as “EOP (mJ / cm ² )”.

[Evaluation of exposure margin (EL margin)]
In the formation of the resist pattern (2), an exposure amount when the space width of the SL pattern is formed within a range of about ± 5% of the target dimension (space width 47 nm) is obtained, and an EL margin (unit: %). The results are shown in Table 4 as “5% EL (%)”.
EL margin (%) = (| E3-E4 | / EOP) × 100
E3: exposure amount (mJ / cm ² ) when an SL pattern having a space width of 44.65 nm was formed
E4: exposure amount (mJ / cm ² ) when an SL pattern having a space width of 49.35 nm was formed

[Evaluation of LWR (Line Width Roughness)]
In the SL pattern having a space width of 47 nm / pitch width of 110 nm formed by the formation of the resist pattern (2), a length measurement SEM (scanning electron microscope, acceleration voltage 300 V, product name: S-9380, manufactured by Hitachi High-Technologies Corporation) ), The space width was measured at 400 locations in the longitudinal direction of the space, and the standard deviation (s) was tripled (3 s) from the result, and the average value for 3 locations at 400 locations was measured as a measure of LWR. Calculated as The results are shown in Table 4 as “LWR (nm)”.

[Evaluation of mask error factor (MEEF)]
In accordance with the same procedure as the formation of the resist pattern (2), each mask pattern having a target size (space width) of 42 to 52 nm (1 nm increments, a total of 11 points) is used, and each SL pattern with a pitch of 110 nm is set to the same exposure amount. Formed.
At that time, the slope of the straight line (MEEF) when the target size (nm) was plotted on the horizontal axis and the space width (nm) of the pattern formed on the resist film using each mask pattern was plotted on the vertical axis was calculated. The results are shown in Table 4 as “MEEF”.

  From the results shown in Table 4, the resist compositions of Test Examples 6, 7, and 9 containing polymer compounds produced by applying the present invention in resist pattern formation by a negative development process are outside the scope of the present invention. It can be seen that, compared with the resist compositions of Test Examples 1 to 4, and 10 containing the polymer compound produced by this production method, a resist pattern having excellent lithography properties and a good shape can be formed.

Claims (2)

A compound represented by the following general formula (m0-1);
A tertiary alcohol represented by the following general formula (m0-2),
A tertiary amine having a compound represented by the following general formula (ca) and having an acid dissociation constant (pKa) of a conjugate acid of 7 or less (provided that R ^ca1 , R ^ca2 in the general formula (ca) and R ⁰¹ represented by the following general formula (m0) is used as an acid-dissociable group by reacting in the presence of a nitrogen atom to which R ^ca3 is bonded (excluding a nitrogen atom that is part of an aromatic ring). A method for producing a compound, comprising obtaining the compound.

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Va ⁰¹ and Va ⁰² are each independently a hydrocarbon group having 2 to 10 carbon atoms. Va ⁰¹ -La ⁰ -is Va ⁰¹ -C (= O) O- or Va ⁰¹ -OC (= O)-. n _a0 is an integer of 1 to 5. Ra ⁰¹ is a chain hydrocarbon group having a tertiary carbon atom having 5 or more carbon atoms or a cyclic hydrocarbon group having a tertiary carbon atom having 4 or more carbon atoms. ]

[Wherein, R ^ca1 , R ^ca2 and R ^ca3 each independently represent a hydrocarbon group which may have a substituent; two or more of R ^ca1 , R ^ca2 and R ^ca3 are bonded to form a ring. To form a tertiary amine. ] Step (I) for obtaining a compound represented by the general formula (m0) by the method for producing a compound according to claim 1 ;
And step (II) polymerizing the compound represented by the step resulting et the above general formula (I) (m0),
A process for producing a polymer compound, comprising: