KR20140011293A - Resist composition, method of forming resist pattern and compound - Google Patents

Abstract

The present invention provides a compound useful for a resist composition, a resist composition including the compound, and a method for forming a resist pattern using the resist composition. The present invention provides a base material (A) in which the solubility for a developer is changed according to the actions of the acid, a resist composition including compounds (D0) represented by general formula (d0-1), and a method for forming a resist pattern using the same. In the formula, Y^1 indicates a single bond or bivalent coupler, V^1 indicates a single bond or bivalent cyclic group which may have substituents, R^1 indicates a monovalent group represented by formula (r-d0) (* indicates the number of bonds), and R^2 indicates a hydrogen atom or an alkyl group having 1-5 carbons which may have substituents. n indicates 0 or 1, and when n indicates 0, V^1 cannot make a single bond. m indicates an integer of 1 or higher, and M^m+ indicates m valence organic cation.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a resist composition,

The present invention relates to a compound useful as a resist composition, a resist composition containing the compound, and a method of forming a resist pattern using the resist composition.

In lithography, for example, a resist film of a predetermined shape is formed on the resist film by forming a resist film of resist material on the substrate, selectively exposing the resist film, and performing development processing . A resist material in which a resist material in which the exposed portion of the resist film changes in a property dissolving in a developing solution is changed to a property that does not dissolve in the developing solution is called a negative type.

2. Description of the Related Art In recent years, miniaturization of patterns has been progressing rapidly in the manufacture of semiconductor devices and liquid crystal display devices by the progress of lithography technology. As a method of refinement, generally, the exposure light source is shortened in wavelength (high energy). Specifically, conventionally, ultraviolet rays represented by g-line and i-line have been used, but at present, mass production of semiconductor devices using KrF excimer laser or ArF excimer laser has been started. In addition, EUV (extreme ultraviolet), EB (electron beam), X-ray and the like having a shorter wavelength (high energy) than these excimer lasers have also been studied.

Resist materials are required to have lithography characteristics such as sensitivity to an exposure light source and resolving ability to reproduce a pattern of fine dimensions.

As a resist material satisfying such a demand, a chemically amplified resist composition containing a base component whose solubility in a developer is changed by the action of an acid and an acid generator component which generates an acid by exposure is conventionally used.

For example, when the developer is an alkali developing solution (alkali developing process), a positive chemical amplification type resist composition includes a resin component (base resin) that increases solubility in an alkali developing solution by the action of an acid, Is generally used. When a resist film formed using such a resist composition is subjected to selective exposure at the time of forming a resist pattern, acid is generated from the acid generator component in the exposed portion, the polarity of the base resin is increased by the action of the acid, It becomes soluble in an additional alkali developing solution. For this reason, by the alkali development, a positive pattern in which the unexposed portion remains as a pattern is formed.

On the other hand, when such a chemically amplified resist composition is applied to a solvent developing process using a developing solution (organic developing solution) containing an organic solvent, the solubility of the organic developing solution relatively decreases as the polarity of the base resin increases, A negative resist pattern is formed in which the unexposed portion of the resist film is dissolved or removed by an organic developer to leave an exposed pattern as a pattern. The solvent developing process for forming a negative resist pattern is sometimes referred to as a negative developing process (see, for example, Patent Document 1).

The base resin used in the chemically amplified resist composition generally has a plurality of constituent units in order to improve the lithography characteristics and the like. For example, in the case of a resin component whose solubility in an alkali developing solution increases due to the action of an acid, a constitutional unit containing an acid-decomposable group decomposing by the action of an acid generated from an acid generator or the like and having an increased polarity is used , A structural unit containing a lactone-containing cyclic group, and a structural unit containing a polar group such as a hydroxyl group, etc. (see, for example, Patent Document 2).

As the acid generator used in the chemically amplified resist composition, various and various ones have been proposed so far. For example, onium salt acid generators, oxime sulfonate acid generators, diazomethane acid generators, Nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators.

A resist material using a sulfonium salt having an anion moiety having a bulky structure as an onium salt-based acid generator has been proposed (see, for example, Patent Document 3).

[Patent Document 1] Patent Publication No. 2009-025723 [Patent Document 2] Japanese Unexamined Patent Publication No. 2003-241385 [Patent Document 3] Specification No. 2010-155824

In recent years, along with progress of miniaturization of patterns, resist materials are required to have various lithography characteristics such as roughness reduction, mask reproducibility, process margin, and new improvements in resist pattern shape.

However, in conventional resist materials such as those described in Patent Document 3, the required lithography characteristics and resist pattern shapes are still insufficient.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a compound useful as a resist composition, a resist composition containing the compound, and a method of forming a resist pattern using the resist composition.

A first aspect of the present invention for solving the above problems is a resist composition which generates an acid upon exposure to light and changes the solubility in a developer by the action of an acid and is characterized in that the solubility in the developer is changed by the action of an acid , And a compound (D0) represented by the following general formula (d0-1).

Wherein Y ¹ is a single bond or a divalent linking group. V ¹ is a single bond or a divalent cyclic group which may have a substituent. R ¹ is a monovalent group represented by the formula (r-d0), and * in the formula (r-d0) represents the number of bonds (bonds). R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. n is 0 or 1, and when n is 0, V ¹ is not a single bond. m is an integer of 1 or more, and M ^{m +} is an organic cation of m.

A second aspect of the present invention is a resist pattern forming method comprising the steps of forming a resist film on a support using the resist composition of the first aspect, exposing the resist film, and developing the resist film to form a resist pattern, Pattern forming method.

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

Wherein Y ¹ is a single bond or a divalent linking group. V ¹ is a single bond or a divalent cyclic group which may have a substituent. R ¹ is a monovalent group represented by the formula (r-d0), and * in the formula (r-d0) represents a bond. R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. n is 0 or 1, and when n is 0, V ¹ is not a single bond. m is an integer of 1 or more, and M " ^{m +} is a cation of m valency.

According to the present invention, a compound useful as a resist composition, a resist composition containing the compound, and a method of forming a resist pattern using the resist composition can be provided. By using the above-mentioned resist composition, it is possible to form a resist pattern having a good shape and excellent in lithography characteristics with high sensitivity.

In the present specification and claims, the term " aliphatic " is defined as meaning a group, compound, or the like having no aromaticity as a relative concept to an aromatic.

The "alkyl group" includes straight-chain, branched chain and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group.

The "alkylene group" includes straight-chain, branched chain and cyclic divalent saturated hydrocarbon groups unless otherwise specified.

The "halogenated alkyl group" is a group in which a 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.

The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which a part or all of hydrogen atoms of an alkyl group or an alkylene group are substituted with a fluorine atom.

"Constituent unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).

Includes the case where the hydrogen atom (-H) is substituted with a monovalent group and the case where the methylene group (-CH ₂ -) is substituted with a di-valent group when describing "may have a substituent"

&Quot; Exposure " is a concept including the entire irradiation of radiation.

The term "structural unit derived from an acrylate ester" means a structural unit constituted by cleavage of an ethylenic double bond of an acrylate ester.

"Acrylic acid ester" is a compound in which a hydrogen atom at the carboxyl terminal end of acrylic acid (CH ₂ ═CH-COOH) is substituted with an organic group.

The acrylate ester may have a hydrogen atom bonded to the carbon atom at the? -Position thereof substituted with a substituent. The substituent (R ^{? 0} ) for substituting a hydrogen atom bonded to the carbon atom at the? ^-Position is an atom or a group other than a hydrogen atom, and examples thereof include an alkyl group having 1 to 5 carbon atoms and a halogenated alkyl group having 1 to 5 carbon atoms have. Also, itaconic acid diesters in which the substituent (R ^{? 0} ) is substituted with a substituent containing an ester bond or ^? Hydroxyacrylic ester in which the substituent (R ^{? 0} ) is substituted with a hydroxyalkyl group or a group having a hydroxyl group- do. The carbon atom at the? -Position of the acrylate ester is a carbon atom to which a carbonyl group of acrylic acid is bonded, unless otherwise specified.

Hereinafter, an acrylic acid ester in which a hydrogen atom bonded to a carbon atom at the? -Position is substituted with a substituent is referred to as? -Substituted acrylate ester. In some cases, an acrylic acid ester and an? -Substituted acrylic acid ester are collectively referred to as "(? -Substituted) acrylic acid ester".

The term " structural unit derived from acrylamide " means a constituent unit in which an ethylenic double bond of acrylamide is cleaved.

The acrylamide may have a hydrogen atom bonded to the carbon atom at the? -Position, or may be substituted with a substituent at one or both of the hydrogen atoms of the amino group of the acrylamide. The carbon atom at the? -Position of acrylamide is a carbon atom to which a carbonyl group of acrylamide is bonded, unless otherwise specified.

Examples of the substituent for substituting the hydrogen atom bonded to the carbon atom at the? -Position of the acrylamide include the same substituent as the substituent at the? ^-Position (substituent (R ^{? 0} )) in the? -Substituted acrylate ester.

The term "structural unit derived from a hydroxystyrene or hydroxystyrene derivative" means a structural unit composed of an ethylene double bond of a hydroxystyrene or a hydroxystyrene derivative formed by cleavage.

The term " hydroxystyrene derivative " includes not only hydrogen atoms at the alpha -position of hydroxystyrene substituted with other substituents such as alkyl groups and halogenated alkyl groups, and derivatives thereof. Examples of the derivatives thereof include those in which the hydrogen atom of the hydroxyl group of the hydroxystyrene, in which the hydrogen atom at the? -Position may be substituted with a substituent, is replaced with an organic group; those in which a substituent other than a hydroxyl group is bonded to a benzene ring of hydroxystyrene in which a hydrogen atom at the? -position may be substituted with a substituent, and the like. The? Position (carbon atom at?) 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? -Position of hydroxystyrene include the same substituents as the substituent at the? -Position in the? -Substituted acrylate ester.

The term "structural unit derived from a vinylbenzoic acid or a vinylbenzoic acid derivative" means a structural unit constituted by cleavage of an ethylenic double bond of a vinylbenzoic acid or a vinylbenzoic acid derivative.

The term " vinylbenzoic acid derivative " includes the concept that the hydrogen atom at the? -Position of vinylbenzoic acid is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. Examples of these derivatives include those in which the hydrogen atom of the carboxyl group of vinylbenzoic acid, in which the hydrogen atom at the? -Position may be substituted with a substituent, is replaced with an organic group; and a benzene ring of a vinylbenzoic acid in which a hydrogen atom at a position may be substituted with a substituent is bonded to a substituent other than a hydroxyl group and a carboxy group. The? Position (carbon atom at?) Refers to a carbon atom to which a benzene ring is bonded unless otherwise specified.

The term " styrene " includes the concept that hydrogen atoms at the [alpha] -position of styrene and styrene are substituted with other substituents such as an alkyl group and a halogenated alkyl group.

"Constituent unit derived from styrene" and "constituent unit derived from styrene derivative" means a constituent unit in which an ethylene double bond of styrene or a styrene derivative is cleaved.

The alkyl group as the? -Position substituent is preferably a linear or branched alkyl group. Specifically, the alkyl group having 1 to 5 carbon atoms (such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group).

Specific examples of the halogenated alkyl group as the substituent at the? -Position include a group obtained by substituting a part or all of the hydrogen atoms of the alkyl group as the substituent at the? -Position with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

Specific examples of the hydroxyalkyl group as the substituent at the? -Position include groups in which a part or all of the hydrogen atoms of the "alkyl group as the substituent at the? -Position" are substituted with hydroxyl groups. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

&Quot; Resist composition &

The resist composition of the present invention is a resist composition which generates an acid upon exposure and changes its solubility in a developing solution by the action of an acid, wherein the base component (A) (Hereinafter referred to as "component (A)") and the compound (D0) represented by the above formula (d0-1) (hereinafter referred to as "component (D0)").

When a resist film is formed using such a resist composition and selectively exposed to the resist film, an acid is generated in the exposed portion, and the solubility of the component (A) in the developer is changed by the action of the acid, In the light portion, since the solubility of the component (A) in the developer does not change, a difference in solubility in the developer occurs between the exposed portion and the unexposed portion. Therefore, when the resist film is developed, when the resist composition is a positive type, the exposed portion is dissolved and removed to form a positive resist pattern. When the resist composition is negative, the unexposed portion is dissolved and removed to form a negative A resist pattern is formed.

In the present specification, a resist composition which forms a positive resist pattern by dissolving or removing an exposed portion is referred to as a positive resist composition, and a negative resist composition for forming a negative resist pattern to which the unexposed portion is dissolved or removed is referred to as a negative resist composition do.

The resist composition of the present invention may be a positive resist composition or a negative resist composition.

The resist composition of the present invention may be used for an alkali developing process using an alkali developing solution for developing treatment at the time of forming a resist pattern and for a solvent developing process using a developing solution (organic developing solution) containing an organic solvent for the developing treatment .

The resist composition of the present invention has an acid-generating ability to generate an acid upon exposure, and the component (A) may generate an acid upon exposure, and the additive component separately formulated from the component (A) An acid may be generated.

Specifically, in the resist composition of the present invention,

(1) an acid generator component (B) which generates an acid upon exposure (hereinafter referred to as " component (B) ");

(2) the component (A) may be a component which generates an acid upon exposure;

(3) The component (A) is a component which generates an acid upon exposure and further contains the component (B).

That is, in the cases of (2) and (3) above, the component (A) becomes a base component which generates an acid upon exposure and has a solubility in the developer changed by the action of an acid. (A) is a base component which generates an acid upon exposure and the solubility in a developing solution changes by the action of an acid, the component (A1) described later generates an acid by exposure, It is preferable that the polymer compound is a polymer compound whose solubility in a developing solution changes by the action of the polymer. As such a polymer compound, a resin having a constituent unit capable of generating an acid upon exposure can be used. As the constituent unit for generating an acid upon exposure, known ones can be used.

It is particularly preferable that the resist composition of the present invention is the resist composition (1).

≪ Component (A) >

In the present invention, the "base component" is an organic compound having film-forming ability, preferably an organic compound having a molecular weight of 500 or more. When the molecular weight of the organic compound is 500 or more, the film forming ability improves, and a nano-level resist pattern is easily formed.

The organic compound used as the base component is roughly divided into a non-polymer and a non-polymer.

As the non-polymeric substance, those having a molecular weight of 500 or more and less than 4000 are generally used. [0052] Hereinafter, the term " low molecular weight compound " refers to a non-polymeric substance 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 generally used. Hereinafter, the term " resin " refers to a polymer having a molecular weight of 1000 or more.

As the molecular weight of the polymer, the mass average molecular weight in terms of polystyrene by GPC (Gel Permeation Chromatography) is used.

As the component (A), a resin may be used, a low molecular weight compound may be used, or a combination thereof may be used.

The component (A) may be such that the solubility in the developer is increased by the action of an acid, and the solubility in the developer is decreased by the action of an acid.

In the present invention, the component (A) may be one which generates an acid by exposure.

In the case where the resist composition of the present invention is a " negative resist composition for alkali development process " in which a negative resist pattern is formed in an alkali development process, or a " positive resist composition for negative solvent development process " (A-2) (hereinafter referred to as "component (A-2)") is preferably used as the component (A) do. In the resist composition, when an acid is generated by exposure, the acid acts to cause crosslinking between the component (A-2) and the crosslinking agent component, and as a result, the solubility in an alkali developing solution decreases (solubility in an organic developing solution increases) do. Therefore, in the formation of a resist pattern, when the resist film obtained by applying the resist composition on a support is selectively exposed, the exposed portion is changed to an insoluble (soluble in an organic developer) to an alkaline developer while the unexposed portion is changed to an alkaline developer The resist pattern does not change with solubility (poorly soluble in an organic developer), and therefore, a negative resist pattern can be formed by developing with an alkaline developer. At this time, a positive resist pattern can be formed by developing with an organic developer.

As the component (A-2), a resin soluble in an alkali developing solution (hereinafter referred to as "alkali-soluble resin") is used.

Examples of the alkali-soluble resin include an alkylester of? - (hydroxyalkyl) acrylic acid or? - (hydroxyalkyl) acrylic acid (preferably having 1 to 5 carbon atoms An alkyl ester); An acrylic resin or a polycycloolefin resin disclosed in U.S. Patent No. 6949325 in which a hydrogen atom bonded to the carbon atom at the alpha position having a sulfonamide group may be substituted with a substituent; An acrylic resin containing a fluorinated alcohol as disclosed in U.S. Patent No. 6949325, No. 2005-336452, and No. 2006-317803, in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent; A polycycloolefin resin having a fluorinated alcohol or the like disclosed in JP-A-2006-259582 is preferable in that a good resist pattern with little swelling can be formed.

Further, the? - (hydroxyalkyl) acrylic acid may be an acrylic acid in which a hydrogen atom is bonded to a carbon atom at an? Position to which a carboxy group is bonded in an acrylic acid in which a hydrogen atom bonded to a carbon atom at? Hydroxyalkyl acrylate in which a hydroxyalkyl group (preferably a hydroxyalkyl group having 1 to 5 carbon atoms) is bonded to a carbon atom of the? -Hydroxyalkylacrylic acid.

As the crosslinking agent component, it is preferable to use, for example, an amino-based crosslinking agent such as glyceryl having a methylol group or an alkoxymethyl group, or a melamine-based crosslinking agent, because a good resist pattern with less swelling can be formed. The blending amount of the crosslinking agent component is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.

When the resist composition of the present invention forms a positive pattern in the alkali development process and is a "positive resist composition for alkali development process" which forms a negative pattern in the solvent development process, or when the resist composition of the negative type (Hereinafter referred to as " component (A-1)) " (hereinafter referred to as " component (A)) " Is used. By using the component (A-1), the polarity of the base component changes before and after the exposure, so that a good development contrast can be obtained not only in the alkali developing process but also in the solvent developing process.

In the case of applying the alkali developing process, the component (A-1) is poorly soluble in an alkali developing solution before exposure, and when an acid is generated by exposure, the polarity increases due to the action of the acid, . Therefore, in the formation of the resist pattern, when the resist composition obtained by applying the resist composition on a support is selectively exposed to light, the exposed portion changes from poorly soluble to soluble with respect to the alkaline developer, while the unexposed portion has an alkali- The positive type pattern can be formed by alkali development.

On the other hand, in the case of applying the solvent developing process, the component (A-1) is highly soluble in an organic developing solution before exposure and when an acid is generated by exposure, the polarity is increased by the action of the acid, . Therefore, in forming a resist pattern, when the resist composition obtained by applying the resist composition on a support is selectively exposed to light, the exposed portion changes from soluble to poorly soluble in the organic developer, while the unexposed portion remains soluble Therefore, by developing with an organic developing solution, a contrast can be given between the exposed portion and the unexposed portion, and a negative pattern can be formed.

In the resist composition of the present invention, the component (A) is preferably the component (A-1).

[Polymer compound (A1)]

(A1) having a structural unit (a1) containing an acid-decomposable group whose polarity is increased by the action of an acid (hereinafter referred to as " (Hereinafter also referred to as " component (A1) ").

(Constituent unit (a1))

The "acid-decomposable group" is a group having acid decomposability capable of cleaving at least part of bonds in the structure of the acid decomposable group by the action of an acid.

The acid decomposable group whose polarity is increased by the action of an acid includes, for example, a group capable of decomposing 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, and a sulfo group (-SO ₃ H). Among them, a polar group containing -OH in the structure (hereinafter also referred to as "OH-containing polar group" in some cases) is preferable, a carboxyl group or a hydroxyl group is more preferable, and a carboxyl group is particularly preferable.

More specific examples of the acid decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected with an acid dissociable group).

Herein, the term " acid dissociable group " means an acid dissociable group capable of cleaving a bond between the acid dissociable group and the atoms adjacent to the acid dissociable group by the action of an acid, or (ii) Refers to both of a group in which a bond between an acid dissociable group and an atom adjacent to the acid dissociable group can be cleaved by further decarboxylation reaction after cleavage of a part of bonds due to the action of the acid dissociable group.

The acid-dissociable group constituting the acid-decomposable group should be a group having a lower polarity than the polar group generated by the dissociation of the acid-dissociable group, whereby when the acid-dissociable group is dissociated by the action of an acid, Polarity with higher polarity is generated than dissociation penis, and polarity increases. As a result, the polarity of the entire component (A1) increases. As the polarity increases, the solubility in the developer relatively changes. When the developer is an alkaline developer, the solubility increases. When the developer is an organic developer, the solubility decreases.

The acid dissociable group is not particularly limited, and any acid dissociable group of a base resin for a chemically amplified resist can be used.

As the acid dissociable group for protecting the carboxyl group or the hydroxyl group in the polar group, for example, an acid dissociable group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as an "acetal type acid dissociable group" .

Wherein Ra ' ¹ and Ra' ² are each a hydrogen atom or an alkyl group, and Ra ' ³ is a hydrocarbon group, and Ra' ³ may be bonded to any one of Ra ' ¹ and Ra' ² to form a ring. ]

Formula (a1-r-1) wherein the Ra ^'1 and Ra' ^2, preferably at least one is hydrogen atom, and both are more preferably a hydrogen atom.

When Ra ' ¹ or Ra' ² is an alkyl group, examples of the alkyl group include the same alkyl groups as the substituent which may be bonded to the carbon atom at the α-position in the description of the α-substituted acrylate ester. Alkyl groups are preferred. Specifically, straight-chain or branched alkyl groups are preferred. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl and neopentyl. More preferably a methyl group is particularly preferable.

In the formula (a1-r-1), examples of the hydrocarbon group of Ra ' ³ include a straight chain or branched chain alkyl group and a cyclic hydrocarbon group.

The straight-chain alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group and an n-pentyl group. Of these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

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

When Ra ' ³ is a cyclic hydrocarbon group, the hydrocarbon group may be aliphatic or aromatic, and may be a polycyclic group or a monocyclic group.

As the monocyclic alicyclic hydrocarbon group, a group in which one hydrogen atom is excluded from the monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, and the like.

The polycyclic alicyclic hydrocarbon group is preferably a group excluding one hydrogen atom in the polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically includes adamantane, norbornane, isobonane , Tricyclodecane, tetracyclododecane and the like.

When the cyclic hydrocarbon group of Ra ' ³ is an aromatic hydrocarbon group, specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene and phenanthrene; And aromatic heterocyclic rings in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom and a nitrogen atom.

Specific examples of the aromatic hydrocarbon group include a group (aryl group) in which one hydrogen atom is removed from the aromatic hydrocarbon ring; A group in which one hydrogen atom of the aryl group is substituted with an alkylene group (e.g., a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, Arylalkyl groups of 1 to 20 carbon atoms). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

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

Examples of the acid dissociable group for protecting the carboxyl group in the polar group include an acid dissociable group represented by the following general formula (a1-r-2). Furthermore, in the acid dissociable group represented by the following formula (a1-r-2), those constituted by an alkyl group may be referred to as a "tertiary alkyl ester-type acid dissociable group" for convenience.

[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]

As the hydrocarbon group Ra ^'4 ~ Ra' ^6, can be given as the Ra ^'3.

Ra ' ⁴ is preferably an alkyl group having 1 to 5 carbon atoms. When Ra ' ⁵ and Ra' ⁶ are bonded to each other to form a ring, there may be mentioned a group represented by the following general formula (a1-r2-1). On the other hand, when Ra ' ⁴ to Ra' ⁶ are not bonded to each other and are independent hydrocarbon groups, there may be mentioned groups represented by the following general formula (a1-r2-2).

[Wherein, Ra 'group to form an aliphatic cyclic group together with the carbon atom ¹⁰ bonded, Ra'^'10 is an alkyl group, Ra of 1 to 10 carbon atoms, ¹¹ Ra ¹² ~ Ra' ¹⁴ are each independently a hydrocarbon group .]

Equation (a1-r2-1) of, Ra is preferably an alkyl group as either "alkyl group having 1 to 10 carbon atoms of ^10, the formula (a1-r-1) of the Ra in the" in ^three of straight or branched chain. Equation (a1-r2-1) of Ra 'is Ra ^{11' 10} cycloaliphatic group which is formed together with the carbon atoms bonded to the formula (a1-r-1) all groups are preferable as the cyclic alkyl group for Ra ^'3 in Do.

Equation (a1-r2-2) of, Ra ', and Ra ^{12' 14} are each independently preferably an alkyl group of 1 to 10 carbon atoms, and the alkyl group, in the formula (a1-r-1) Ra ' of ³ More preferably a straight chain or branched chain alkyl group, more preferably a straight chain alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group or an ethyl group.

In the formula (a1-r2-2), Ra is preferably a ^"13 is the formula (a1-r-1) Ra of the" alkyl group having a straight chain, branched chain or cyclic hydrocarbon group exemplified as the group of ^three. Of these, it is more preferable that R < ³ > is a cyclic alkyl group.

Specific examples of the group represented by the formula (a1-r2-1) are shown below. In the present specification, the * in the formula represents the number of bonds.

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

Examples of the acid dissociable group for protecting the hydroxyl group in the polar group include an acid dissociable group represented by the following general formula (a1-r-3) (hereinafter, also referred to as a "tertiary alkyloxycarbonyl acid dissociable group" ).

Wherein Ra ' ⁷ to Ra' ⁹ each represent an alkyl group.

In the formula (a1-r-3), Ra ' ⁷ to Ra' ⁹ are each preferably an alkyl group having 1 to 5 carbon atoms, more preferably 1 to 3.

The total number of carbon atoms in each alkyl group is preferably from 3 to 7, more preferably from 3 to 5, and most preferably from 3 to 4.

Examples of the structural unit (a1) include a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the [alpha] -position may be substituted with a substituent, and having an acid-decomposable group whose polarity is increased by the action of an acid; A structural unit derived from acrylamide having an acid-decomposable group whose polarity is increased by the action of an acid; A constituent unit in which at least a part of the hydrogen atoms in the hydroxyl group of the constituent unit derived from a hydroxystyrene or hydroxystyrene derivative is protected by a substituent comprising the acid-decomposable group; Structural units in which at least a part of hydrogen atoms in -C (= O) -OH of the constituent unit derived from a vinylbenzoic acid or a vinylbenzoic acid derivative is protected by a substituent including the acid-decomposable group.

As the structural unit (a1), a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the? -Position may be substituted with a substituent is preferable.

Specific preferred examples of the structural unit (a1) include structural units represented by the following general formula (a1-1) or (a1-2).

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. Va ¹ is a divalent hydrocarbon group which may have an ether bond, n _a1 is 0 to 2, and Ra ¹ is an acid dissociable group represented by the formula (a1-r-1) or (a1-r-2). Ra ¹ is an acid dissociable group represented by the above formula (a1-r-1) or (a1-r-3). Wa ¹ is an n _a2 +1 valent hydrocarbon group, n _a2 is 1 to 3,

In the formula (a1-1), the alkyl group having 1 to 5 carbon atoms for R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an 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 is a group in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, and a hydrogen atom or a methyl group is most preferable for industrial availability.

The hydrocarbon group of Va ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group as the divalent hydrocarbon group represented by Va ¹ may be saturated or unsaturated, and is preferably saturated.

More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group containing a ring in the structure.

As Va ¹ , an ether bond (-O-) may be present between the carbon atoms of the above-mentioned divalent hydrocarbon group. The number of ether bonds present in Va ¹ may be one or two or more.

The straight-chain or branched-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.

Examples of the aliphatic hydrocarbon group in a straight chain, and an alkylene group of preferably straight chain, 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.

As the aliphatic hydrocarbon group branched-chain, and an alkylene group of preferably branched chain, _{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 ) -, and -C (CH ₂ CH ₃ ) 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 -, -C (CH ₂ CH _{3) 2} -CH ₂ - alkyl group such as ethylene; _{-CH (CH 3) CH 2 CH} 2 -, -CH 2 CH (CH 3) CH 2 - alkyl trimethylene group and the like; And alkyl alkylene groups such as alkyltetramethylene groups such as -CH (CH ₃ ) CH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) CH ₂ CH ₂ - and the like. As the alkyl group in the alkyl alkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

Examples of the aliphatic hydrocarbon group having a ring in the structure include alicyclic hydrocarbon groups (groups in which two hydrogen atoms are removed from an aliphatic hydrocarbon ring), groups in which alicyclic hydrocarbon groups are bonded to the ends of straight chain or branched chain aliphatic hydrocarbon groups, And groups in which the hydrocarbon group is interposed in the straight chain or branched chain aliphatic hydrocarbon group. Examples of the straight chain or branched chain aliphatic hydrocarbon group include the same groups as described above.

The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, 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 two hydrogen atoms are removed from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, and the like.

As the polycyclic alicyclic hydrocarbon group, a group excluding two hydrogen atoms in the polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms. Specific examples thereof include adamantane, norbornane, isobonane, Tricyclodecane, tetracyclododecane, and the like.

The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring.

The aromatic hydrocarbon group as a divalent hydrocarbon group in Va ¹ preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 ~ 10 is most preferred. Provided that the number of carbon atoms does not include the number of carbon atoms in the substituent group.

Specific examples of the aromatic ring of the aromatic hydrocarbon group include aromatic rings such as benzene, biphenyl, fluorene, naphthalene, anthracene and phenanthrene; And aromatic heterocyclic rings in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom and a nitrogen atom.

Specific examples of the aromatic hydrocarbon group include groups in which two hydrogen atoms are removed from the aromatic hydrocarbon ring (arylene group); A group in which one hydrogen atom of a group (aryl group) excluding one hydrogen atom in the aromatic hydrocarbon ring is substituted with an alkylene group (e.g., a benzyl group, a phenethyl group, a 1-naphthylmethyl group, , A 1-naphthylethyl group, a 2-naphthylethyl group, and other arylalkyl groups, and a group in which one hydrogen atom is further removed from the aryl group. The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

In the formula (a1-2), the hydrocarbon group of n _a2 + ¹ in Wa ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated, usually saturated. Examples of the aliphatic hydrocarbon group include a straight chain or branched chain aliphatic hydrocarbon group, a ring-containing aliphatic hydrocarbon group in the structure, or a combination of a straight chain or branched chain aliphatic hydrocarbon group and a ring-containing aliphatic hydrocarbon group in the structure have.

The above-mentioned n _a2 + 1 is preferably 2 to 4, more preferably 2 or 3.

Specific examples of the structural unit represented by the formula (a1-1) are shown below.

Specific examples of the structural unit represented by the formula (a1-2) are shown below.

The constituent unit (a1) of the component (A1) may be one kind or two or more kinds.

The proportion of the structural unit (a1) in the component (A1) is preferably 20 to 80 mol%, more preferably 20 to 75 mol%, and still more preferably 25 to 70 mol% based on the total structural units constituting the component (A1) Mol% is more preferable. The resist pattern can be easily obtained by setting it to the lower limit value, and lithography characteristics such as sensitivity, resolution and LWR are improved. In addition, by setting it to the upper limit value or less, a balance with other constituent units can be obtained.

(Other constituent units)

The component (A1) may further contain other structural units not corresponding to the structural unit (a1) in addition to the structural unit (a1). The other constituent unit is not particularly limited as long as it is a constituent unit that can not be classified into the above-mentioned constituent unit, and is used for resist resins for ArF excimer laser and KrF excimer laser (preferably for ArF excimer laser) A number of conventionally known ones are usable, and examples thereof include the following constituent units (a2) to (a4).

The structural unit (a2):

The structural unit (a2) is a structural unit containing a lactone-containing cyclic group, -SO ₂ -containing cyclic group or a carbonate-containing cyclic group.

The lactone-containing cyclic group, -SO ₂ -containing cyclic group or carbonate-containing cyclic group of the constituent unit (a2) is effective for improving the adhesion of the resist film to the substrate when the component (A1) is used for forming a resist film.

When the structural unit (a1) includes a lactone-containing cyclic group, -SO ₂ -containing cyclic group or a carbonate-containing cyclic group in its structure, the structural unit also corresponds to the structural unit (a2) Such a constituent unit corresponds to the constituent unit (a1) and does not correspond to the constituent 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. When a lactone ring is counted as a first ring, only a lactone ring is referred to as a monocyclic type, and when a ring structure has another ring structure, it is referred to as a polycyclic type regardless of its structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

The lactone-containing cyclic group in the structural unit (a2) is not particularly limited, and any cyclic group may be used. Specifically, there may be mentioned groups represented by the following general formulas (a2-r-1) to (a2-r-7)

[Wherein, Ra ^'21 each independently represent 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; Is an alkylene group, an oxygen atom or a sulfur atom of 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), and n ' An integer of 0 to 2, and m 'is 0 or 1.]

As the alkylene group having 1 to 5 carbon atoms in A "in the general formulas (a2-r-2), (a2-r-3) and (a2-r-5), linear or branched alkylene groups When the alkylene group includes an oxygen atom or a sulfur atom, specific examples thereof include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and the like. -O- or -S-, for example, -O-CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ -, and the like. As A ", an alkylene group having 1 to 5 carbon atoms or -O- is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is most preferable.

As the alkyl group in the above general formula (a2-r-1) ~ (a2-r-7), Ra '21, an alkyl group having 1 to 6 carbon atoms are preferred. The alkyl group is preferably a straight chain or branched chain. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl and hexyl. Of these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

As the alkoxy group in Ra ^'21, is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably a straight chain or branched chain. Specifically, there may be mentioned as the alkyl group in the Ra ^'21 any alkyl group and an oxygen atom a group (-O-) is connected.

Examples of Ra 'halogen atoms of ^21, and a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom is preferable.

As the Ra 'at a halogenated alkyl group of ^21, there may be mentioned a group in which some or all of the hydrogen atoms of the alkyl group with the halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

Ra 'in -COOR ", -OC (= O) R" at ^21, R "is a hydrogen atom or an alkyl group;

The alkyl group in R "may be any of linear, branched and 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.

When R "is a cyclic alkyl group, the number of carbon atoms is preferably from 3 to 15, more preferably from 4 to 12, and most preferably from 5 to 10. Specific examples thereof include a fluorine atom or a fluorinated alkyl group A monocycloalkane which may or may not be present, a group in which at least one hydrogen atom is removed from a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane, etc. More specifically, A monocycloalkane such as pentane or cyclohexane, or a group in which at least one hydrogen atom is removed from a polycycloalkane such as adamantane, norbornane, isobonane, tricyclodecane or tetracyclododecane.

Ra 'as the hydroxy alkyl group of from ^21, preferably a carbon number of 1-6 and, specifically, with at least one of the hydrogen atoms of any alkyl group as the alkyl group as the above substituent may be a group substituted with a hydroxyl group.

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

The "-SO ₂ -containing cyclic group" refers to a cyclic group containing a ring containing -SO ₂ - in its ring skeleton, and more specifically, the sulfur atom (S) in -SO ₂ - And is a ring-shaped unit forming part of the ring skeleton. A ring containing -SO ₂ - in the ring skeleton is counted as the first ring, and in the case of the ring alone, a monocyclic group or a ring having another ring structure is referred to as a polycyclic group, regardless of its structure. The -SO ₂ -containing cyclic group may be a monocyclic group or a polycyclic group.

The -SO ₂ -containing cyclic group is particularly preferably a cyclic group containing -O-SO ₂ - in its ring skeleton, that is, a sultone ring in which -OS-in the -O-SO ₂ - forms part of a cyclic skeleton Is preferably a cyclic group.

Specific examples of the -SO ₂ -containing cyclic group include the groups represented by the following general formulas (a5-r-1) to (a5-r-4)

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

In the general formulas (a5-r-1) to (a5-r-4), A '' represents a group represented by the general formulas (a2- Quot; A "in FIG.

(A2-r-1) to (a2-r) in the above-mentioned Ra ^{'51 may be the same} as the alkyl group, alkoxy group, halogen atom, halogenated alkyl group, -COOR " -7) it can be given as to any of the Ra ^'21 described.

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

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 and only the carbonate ring is a monocyclic group, the other ring structure is referred to as a polycyclic group regardless of its structure. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group.

The carbonate ring-containing cyclic group is not particularly limited and any arbitrary group can be used. Specifically, groups represented by the following general formulas (ax3-r-1) to (ax3-r-3) may be mentioned.

Wherein each Ra ' ^x31 is independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR ", -OC (= O) R", a hydroxyalkyl group or a cyano group; R "is a hydrogen atom or an alkyl group; A" is an alkylene group, an oxygen atom or a sulfur atom having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom; q 'is 0 or 1;

A "in the formulas (a3-r-1) to (a3-r-3) 5).

Ra 'alkyl group in ^31, an alkoxy group, a halogen atom, a halogenated alkyl group, -COOR ", -OC (= O ) R", as a hydroxyalkyl group, each of the general formulas (a2-r-1) ~ (a2-r -7) it may be mentioned, such as in any of the Ra ^'21 described.

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

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

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. La ²¹ represents -O-, -COO-, -CON (R ') -, -OCO-, -CONHCO- or -CONHCS-, and R' represents a hydrogen atom or a methyl group. Provided that when La ²¹ is -O-, then Ya ²¹ is not -CO-. Ra ²¹ is a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ₂ -containing cyclic group.]

In the formula (a2-1), R is as defined above.

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

(Bivalent hydrocarbon group which may have a substituent)

The hydrocarbon group as a divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually saturated.

Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group containing a ring in the structure.

Examples of the straight chain or branched chain aliphatic hydrocarbon group include the groups exemplified as Va ¹ in the above-mentioned formula (a1-1).

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

As the aliphatic hydrocarbon group having a ring in the structure, a cyclic aliphatic hydrocarbon group (a group in which two hydrogen atoms are removed from an aliphatic hydrocarbon ring) which may contain a substituent group containing a hetero atom in the ring structure, a cyclic aliphatic hydrocarbon group A group bonded to the terminal of the straight chain or branched chain aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed in the straight chain or branched chain aliphatic hydrocarbon group. Examples of the straight chain or branched chain aliphatic hydrocarbon group include those described above.

The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

Specific examples of the cyclic aliphatic hydrocarbon group include the groups exemplified by Va ¹ in the above-mentioned formula (a1-1).

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, 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, more preferably a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group or tert- The ethoxy group is most preferred.

Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

Examples of the halogenated alkyl group as the substituent include groups in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom.

The cyclic aliphatic hydrocarbon group may be substituted with a substituent group in which a part of the carbon atoms constituting the cyclic structure includes a hetero atom. The substituent containing the hetero atom is preferably -O-, -C (= O) -O-, -S-, -S (= O) _2- or -S (= O) ₂ -O-.

Specific examples of the aromatic hydrocarbon group as the divalent hydrocarbon group include the groups exemplified by Va ¹ in the above-mentioned formula (a1-1).

In the aromatic hydrocarbon group, the 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.

(A divalent linking group containing a hetero atom)

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

When Y ^{< a} > is a divalent linking group containing a heteroatom, preferable examples of the linking group include -O-, -C (= O) -O-, -C (= O) -, -C (= O) -NH-, -NH-, -NH-C (= NH) - (H may be substituted with a substituent such as an alkyl group or an acyl group) = O) ₂ -, -S (= O) ₂ -O-, a group represented by the formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C (= O) ^{= O) -OY 21, - [} Y 21 -C (= O) -O] m "-Y 22 -, -Y 21 -OC (= O) -Y 22 - or -Y ²¹ -S (= O) ₂ -OY ²² - [wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom and m "is an integer of 0 to 3], etc. .

When the divalent linking group containing the hetero atom is -C (= O) -NH-, -NH- or -NH-C (= NH) -, the H may be substituted with a substituent such as an alkyl group or acyl . The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.

Formula ^{-Y 21 -OY 22 -, -Y 21} -O-, -Y 21 -C (= O) -O-, -C (= O) -OY 21, - [Y 21 -C (= O) ^{_{-O] m "-Y 22 -,}} -Y 21 -OC (= O) -Y 22 - or _{^{-Y 21 -S (= O) 2}} -OY 22 - of, Y ²¹ and Y ²² are each independently Examples of the divalent hydrocarbon group include the same groups as those described above for the divalent linking group, such as a divalent hydrocarbon group which may have a substituent.

Y ²¹ is preferably a linear aliphatic hydrocarbon group, more preferably a straight chain alkylene group, more preferably a straight chain alkylene group having 1 to 5 carbon atoms, particularly preferably a methylene group or an ethylene group.

Y ²² is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain 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, more preferably 0 or 1 , And 1 is particularly preferable. The group represented by the formula - [Y ²¹ -C (═O) -O] _m "-Y ²² - is particularly preferably a group represented by the formula -Y ²¹ -C (═O) -OY ₂₂ - , A group represented by the formula - (CH ₂ ) _{a '} -C (═O) -O- (CH ₂ ) _b' - is preferable, and a 'is an integer of 1 to 10, B 'is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, More preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1.

Ya ^{21 is preferably a} single bond or 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 a lactone-containing cyclic group, -SO ₂ -containing cyclic group or a carbonate-containing cyclic group.

Examples of the lactone-containing cyclic group, -SO ₂ -containing cyclic group and carbonate-containing cyclic group in Ra ²¹ include groups represented by the general formulas (a2-r-1) to (a2-r-7) groups represented by formulas (a5-r-1) to (a5-r-4) and groups represented by formulas (ax3-r-1) to (ax3-r-3), respectively.

Among them, a lactone-containing cyclic group or -SO ₂ -containing cyclic group is preferable, and groups represented by the above general formulas (a2-r-1), (a2-r-2) or (a5-r-1) (R-lc-1-17), (r-lc-2-1) to (r- 1) and (r-sl-1-18), respectively.

The constituent unit (a2) of the component (A1) may be one kind or two or more kinds.

When the component (A1) has the structural unit (a2), the proportion of the structural unit (a2) is preferably 1 to 80 mol%, more preferably 10 To 70 mol%, more preferably 10 mol% to 65 mol%, and particularly preferably 10 mol% to 60 mol%. By incorporating the constituent unit (a2) in an amount of not less than the lower limit value, the effect can be sufficiently obtained. By making the constitutional unit (a2) be not more than the upper limit value, balance with other constituent units can be obtained, and various lithographic properties such as DOF and CDU and favorable pattern shape do.

Constituent unit (a3):

The structural unit (a3) is a structural unit containing a polar group-containing aliphatic hydrocarbon group (excluding those corresponding to the structural units (a1) and (a2) described above).

The component (A1) has the constituent unit (a3), so that the hydrophilicity of the component (A) is increased, contributing to improvement of the resolution.

Examples of the polar group include a hydroxyl group, a cyano group, a carboxyl group, a hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group is substituted with a fluorine atom, and a hydroxyl group is particularly preferable.

Examples of the aliphatic hydrocarbon group include a straight chain or branched chain hydrocarbon group (preferably an alkylene group) having 1 to 10 carbon atoms, and a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be either a monocyclic group or a polycyclic group, and for example, a resin for a resist composition for an ArF excimer laser may be appropriately selected from among many proposed ones. 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 a hydroxyl group, a cyano group, a carboxyl group, or an aliphatic polycyclic group containing a hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group is substituted with a fluorine atom is more preferable. Examples of the polycyclic group include groups excluding two or more hydrogen atoms in a bicycloalkane, a tricycloalkane, a tetracycloalkane, and the like. Specific examples thereof include groups in which at least two hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobonane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, a group excluding two or more hydrogen atoms in adamantane, a group excluding two or more hydrogen atoms in norbornane, and a group excluding two or more hydrogen atoms in tetracyclododecane are industrially preferable.

The constituent unit (a3) is not particularly limited as long as it contains a polar group-containing aliphatic hydrocarbon group, and any arbitrary structure can be used.

As the constituent unit (a3), a constituent unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at a position may be substituted with a substituent is preferably a constituent unit containing a polar group-containing aliphatic hydrocarbon group.

When the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, the structural unit (a3) is preferably a structural unit derived from a hydroxyethyl ester of acrylic acid, and the hydrocarbon group is preferably In the case of a cyclic structure, preferred examples include the structural unit represented by the following formula (a3-1), the structural unit represented by the formula (a3-2), and the structural unit represented by the formula (a3-3)

Wherein R is as defined 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, 1 is an integer of 1 to 5, s is It is an integer from 1 to 3.]

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

j is preferably 1, and it is particularly preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group.

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

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

The constituent unit (a3) of the component (A1) may be one kind or two or more kinds.

Is preferably from 5 to 50 mol%, more preferably from 5 to 40 mol% based on the total of all the constituent units constituting the component (A1), in the case that the component (A1) And more preferably 5 to 25 mol%. When the ratio of the constituent unit (a3) is at least the lower limit value, the effect can be sufficiently obtained by containing the constituent unit (a3), and when it is not more than the upper limit value, balance with other constituent units becomes easy.

Constituent unit (a4):

The structural unit (a4) is a structural unit containing an acid-labile aliphatic cyclic group.

The dry etching resistance of a resist pattern formed by the component (A1) having the structural unit (a4) improves. In addition, the hydrophobicity of the component (A1) increases. It is considered that the improvement of the hydrophobicity contributes to the improvement of the resolution, the resist pattern shape and the like particularly in the case of organic solvent development.

The "acid-untreated cyclic group" in the constituent unit (a4) is a group having a structure in which when an acid is generated in the resist composition by exposure (for example, when acid is generated from the component (A) Is a cyclic group remaining in the constituent unit without dissociating even if the acid acts.

As the structural unit (a4), for example, a structural unit derived from an acrylate ester containing an acid-labile aliphatic cyclic group is preferable. Examples of the cyclic group include those exemplified above for the structural unit (a1), and examples thereof include a resist for an ArF excimer laser, a KrF excimer laser (preferably for an ArF excimer laser) A number of conventionally known ones can be used as the resin component of the composition.

Particularly, at least one selected from a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group, and a norbornyl group is preferable in view of industrial availability and the like. 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 the following general formulas (a4-1) to (a4-7).

^Wherein R ^? Is as defined above.

The constituent unit (a4) of the component (A1) may be one kind or two or more kinds.

When the component (A1) has the structural unit (a4), the proportion of the structural unit (a4) is preferably from 1 to 30 mol%, more preferably from 3 to 30 mol% based on the total of all the structural units constituting the component (A1) To 20 mol% is more preferable. When the ratio of the constituent unit (a4) is not less than the lower limit value, the effect can be sufficiently obtained by including the constituent unit (a4). When the proportion is less than the upper limit value, balance with other constituent units can be easily obtained.

The component (A1) is preferably a polymer having at least a structural unit (a1), and is preferably a copolymer having at least one structural unit selected from the structural units (a2) to (a4) in addition to the structural unit (a1).

As such a copolymer, a copolymer comprising a repeating structure of the constituent units (a1) and (a2), a repeating structure of the constituent units (a1) and (a3); A copolymer consisting of repeating units of the structural units (a1), (a2) and (a3); And a repeating structure of the structural units (a1), (a2), (a3) and (a4).

The mass average molecular weight (Mw) (based on polystyrene conversion by gel permeation chromatography (GPC)) of the component (A1) is not particularly limited and is preferably from 1,000 to 50,000, more preferably from 1,500 to 30,000, ~ 20000 is most preferred. If it is below the upper limit of the above range, there is a solubility in a resist solvent sufficient for use as a resist. If the lower limit of the above range is exceeded, the dry etching resistance and the cross-sectional shape of the resist pattern are favorable.

The dispersion degree (Mw / Mn) is not particularly limited and is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5. Mn represents the number average molecular weight.

The component (A1) is obtained by polymerizing monomers which derive each constituent unit by known radical polymerization using, for example, a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate Can be obtained.

The chain transfer agent such as HS-CH ₂ -CH ₂ -CH ₂ -C (CF ₃ ) ₂ -OH is used in combination with the component (A1) ₃ ) ₂ -OH group may be introduced. Thus, a copolymer into which a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom is introduced is effective for reduction of development defects and reduction of LER (line edge roughness: uneven irregularity of line side wall).

The monomer for deriving each constituent unit may be a commercially available monomer or a monomer synthesized by a known method.

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, further preferably 75% by mass, and even more preferably 100% by mass with respect to the total mass of the component (A) do. When the above ratio is 25 mass% or more, lithographic properties such as MEF, circularity and roughness reduction are further improved.

The resist composition of the present invention may contain a base component (hereinafter referred to as " component (A2) ") whose polarity is increased by the action of an acid which does not correspond to the component (A1) .

(A2) is not particularly limited, and a large number of conventionally known base components for the chemically amplified resist composition (for example, for ArF excimer laser, KrF excimer laser (preferably for ArF excimer laser) Base resin). The component (A2) may be used alone or in combination of two or more.

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

The content of the component (A) in the resist composition of the present invention may be adjusted depending on the thickness of the resist film to be formed.

<(D0) component>

(D0) is a compound represented by the following general formula (d0-1).

Wherein Y ¹ is a single bond or a divalent linking group. V ¹ is a single bond or a divalent cyclic group which may have a substituent. R ¹ is a monovalent group represented by the formula (r-d0), and * in the formula (r-d0) represents a bond. R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. n is 0 or 1, and when n is 0, V ¹ is not a single bond. m is an integer of 1 or more, and M ^{m +} is an organic cation of m.

· Negative ion part

In the formula (d0-1), Y ¹ is a single bond or a divalent linking group.

As the divalent linking group of Y ¹ , a divalent hydrocarbon group which may have a substituent, a divalent linking group including a hetero atom, and the like are preferable.

The divalent linking group containing a divalent hydrocarbon group or a hetero atom which may have a substituent in Y ¹ includes a divalent linking group such as a divalent hydrocarbon group which may have a substituent and is exemplified by Ya ²¹ in the formula (a2-1) And a divalent linking group containing a hetero atom. In addition to these examples, examples of the substituent which the linear or branched aliphatic hydrocarbon group in the divalent hydrocarbon group which may have a substituent of Y ¹ may have include an alkoxy group, a monovalent group represented by the formula (r-d0) . The alkoxy group as the substituent is preferably an alkoxy group having 1 to 10 carbon atoms.

Y ^{1 represents a} single bond, a straight chain or branched chain aliphatic hydrocarbon group which may have a substituent, a group represented by -Y ²¹ -O-, a group represented by -Y ²¹ -S (═O) ₂ -OY ²² - Y ²¹ and Y ²² are as defined above.

In the formula (d0-1), V ¹ is a single bond or a divalent cyclic group which may have a substituent.

As the divalent cyclic group of V ¹ , a cyclic hydrocarbon group exemplified by Ra ' ³ in the formula (a1-r-1) (a cyclic alicyclic hydrocarbon group, a polycyclic alicyclic hydrocarbon group, an aromatic hydrocarbon group ) Is preferably a group excluding one hydrogen atom. Among them, a group in which a hydrogen atom is further removed from a monocyclic alicyclic hydrocarbon group exemplified by Ra ' ³ or a group in which a hydrogen atom is further removed from a polycyclic alicyclic hydrocarbon group is preferable, and a monocyclic alicyclic A group in which a hydrogen atom is further removed from the hydrocarbon group is more preferable.

Examples of the substituent which the divalent cyclic group in V ¹ may have 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 a substituent in the divalent cyclic group is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

The alkoxy group as a substituent in the divalent cyclic group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group or tert- , Methoxy group and ethoxy group are most preferable.

The halogen atom as a substituent in the bivalent cyclic group includes 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 a substituent represented by a bivalent cyclic group include groups in which a part or all of the hydrogen atoms of the alkyl group as the substituent in the bivalent cyclic group are substituted with the halogen atom.

The divalent cyclic group may be substituted with a substituent group in which a part of carbon atoms constituting the ring structure contains a hetero atom. The substituent containing the hetero atom is preferably -O-, -C (= O) -O-, -S-, -S (= O) _2- or -S (= O) ₂ -O-.

In the formula (d0-1), R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. Examples of the substituent which the alkyl group having 1 to 5 carbon atoms may have include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, a carbonyl group, an alkoxy group having 1 to 5 carbon atoms and a monovalent group represented by the formula (r-d0) .

In the formula (d0-1), n is 0 or 1. However, when n is 0, V ¹ is not a single bond.

Preferred examples of the anion moiety of component (D0) are shown below.

· Cation part

In the formula (d0-1), m is an integer of 1 or more, and M ^{m +} is an organic cation of m valent.

The organic cation of M ^{m +} is not particularly limited, and among them, m is preferably an onium cation, more preferably a sulfonium cation or an iodonium cation, and the following general formula (ca-1) to (ca- 4) are particularly preferable.

^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 bond together to form a ring together with the sulfur atom in the formula. R ²⁰⁸ ~ R ²⁰⁹ each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 5, R ²¹⁰ is an aryl group which may have a substituent, an alkyl group, an alkenyl group, or -SO ₂ - and containing a cyclic group, L ²⁰¹ is -C (= O) - or -C (= O) represents a -O-, Y ²⁰¹ are each independently an arylene group, an alkylene group, or represents an alkenylene group, x is 1 or 2, W ²⁰¹ is (x +1).

The aryl group in R ²⁰¹ ~ R ^207, and R ²¹¹ ~ R ^212, and include an aryl group of non-substituted having from 6 to 20 carbon atoms, preferably a phenyl group, a naphthyl group.

As the alkyl group for R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² , a straight or cyclic alkyl group 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 which 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, to (ca-r-7), respectively.

Wherein R &lt; ²⁰¹ &gt; each independently represents a hydrogen atom, a cyclic group which may have a substituent, a straight chain alkyl group or a straight chain alkenyl group.

The cyclic group which may have a substituent of R ' ²⁰¹ , the chain alkyl which may have a substituent, or the chain alkenyl group which may have a substituent may be the same as R ¹⁰¹ in the following 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 as the acid dissociable group represented by the formula (a1-r-2).

When R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ , and R ²¹¹ to R ²¹² are bonded to each other to form a ring with a sulfur atom in the formula, hetero atoms such as a sulfur atom, an oxygen atom and a nitrogen atom, Or a functional group such as -SO-, -SO ₂ -, -SO ₃ -, -COO-, -CONH- or -N (R _N ) - (wherein R _N is an alkyl group having 1 to 5 carbon atoms) You can. As the ring to be formed, one ring containing the sulfur atom in the formula in the ring skeleton includes a sulfur atom, preferably a 3 to 10 membered ring, and particularly preferably a 5 to 7 membered ring. Specific examples of the ring formed include, for example, thiophene ring, thiazole ring, benzothiophene ring, thiotrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthene ring, A tetrahydrothiophenium ring, a tetrahydrothiopyraninium ring, and the like.

Each of R ²⁰⁸ to R ²⁰⁹ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. When the alkyl group is an alkyl group, they may be bonded to each other to form a ring.

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 a -SO ₂ - containing cyclic group which may have a substituent.

As the aryl group in R ²¹⁰ , an unsubstituted aryl group having 6 to 20 carbon atoms is exemplified, and a phenyl group or a naphthyl group is preferable.

As the alkyl group for R ²¹⁰ , a linear or cyclic alkyl group having 1 to 30 carbon atoms is preferable.

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 at R ²¹⁰ include the same as the "-SO ₂ -containing cyclic group" of Ra ²¹ in the general formula (a2-1) a5-r-1) is preferable.

Y ²⁰¹ each independently represent an arylene group, an alkylene group or an alkenylene group.

The arylene group for Y ²⁰¹ includes a group in which one hydrogen atom is removed from the aryl group exemplified as the aromatic hydrocarbon group in R ¹⁰¹ in the below-mentioned formula (b-1).

The alkylene group and alkenylene group in Y ²⁰¹ may be the same as the aliphatic hydrocarbon group as the divalent hydrocarbon group in Va ¹ in the general formula (a1-1).

In the above formula (ca-4), x is 1 or 2.

W ²⁰¹ is (x + 1), that is, a divalent or trivalent linking group.

As the divalent linking group in W ²⁰¹ , a divalent hydrocarbon group which may have a substituent is preferable, and hydrocarbon groups such as Y a ²¹ in the general formula (a2-1) can be exemplified. The divalent linking group in W ²⁰¹ may be any of linear, branched and cyclic, and is preferably cyclic. Among them, a group in which two carbonyl groups are combined at both terminals of an 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 W at ^201, on the divalent linking group W in the ²⁰¹ group the bivalent connecting the hydrogen atom in the group, the divalent connecting group other than one, and the like group which combines more. As the trivalent linking group in W ²⁰¹ , a group in which two carbonyl groups are bonded to an arylene group is preferable.

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

G1 represents an integer of 1 to 5, g2 represents an integer of 0 to 20, and g3 represents an integer of 0 to 20.] [wherein, g1, g2 and g3 represent repeating numbers,

Wherein R " ²⁰¹ is a hydrogen atom or a substituent, and the substituent is the same as the substituent which R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² may have.]

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

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

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

Among them, the cation moiety (M ^{m +} ) is preferably a cation represented by the formula (ca-1), and more preferably a cation represented by the formula (ca-1-1) to (ca-1-67).

As the component (D0), it is particularly preferable to use a compound represented by the following general formula (d0-1-1) or (d0-1-2).

Wherein R ² , m and M ^{m +} are the same as R ² , m and M ^{m +} in the formula (d0-1). Y ^{1 '} is a straight chain or branched chain aliphatic hydrocarbon group which may have a substituent. V ^{1 '} is a divalent cyclic group which may have a substituent.]

The formula (d0-1-1) of, Y ^{1 'is} an aliphatic hydrocarbon group with straight or branched chain which optionally has a substituent, the substituents exemplified in the description of Y ¹ in the formula (d0-1) of the above-described A straight chain or branched chain aliphatic hydrocarbon group in a divalent hydrocarbon group which may have a substituent.

In the formula (d0-1-2), V ^{1 '} is a divalent cyclic group which may have a substituent, and may be a substituted or unsubstituted divalent cyclic group having 2 to 10 carbon atoms which may have a substituent exemplified in the description of V ¹ in the formula (d0-1) And the like.

(D0) may be used singly or in combination of two or more.

The content of the component (D0) in the resist composition is preferably from 1 to 50 parts by mass, more preferably from 1.5 to 25 parts by mass, and still more preferably from 2 to 15 parts by mass, per 100 parts by mass of the component (A).

When the content of the component (D0) is not less than the preferable lower limit value, particularly good lithography characteristics and resist pattern shape are easily obtained. On the other hand, if the content of the component (D1) is not more than the preferable upper limit value, the sensitivity can be kept good and the throughput is also excellent.

<Other components>

In the resist composition of the present invention, it is preferable that the resist composition further contains an acid generator component (B) (hereinafter referred to as "component (B)") which generates an acid upon exposure in addition to the components (A) It is acceptable.

[Component (B)] [

As the component (B), there is no particular limitation, and any of those proposed so far as acid generators for chemically amplified resists can be used.

Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisaryl sulfonyl diazomethanes, poly (bis-sulfonyl) diazomethane Diazomethane-based acid generators such as diethyleneglycol-based diazomethane-based acid generators, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators. Among them, it is preferable to use an onium salt-based acid generator.

Examples of the onium salt-based acid generator include compounds represented by the following general formula (b-1) (hereinafter also referred to as "component (b-1) (hereinafter also referred to as "component (b-2)") or a compound represented by formula (b-3) (hereinafter also referred to as "component (b-3)").

Wherein R ¹⁰¹ and R ¹⁰⁴ to R ¹⁰⁸ are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a straight chain alkenyl group which may have a substituent. R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. V ¹⁰¹ to V ¹⁰³ each independently represent a single bond, an alkylene group, or a fluorinated alkylene group. L ¹⁰¹ to L ¹⁰² each independently represent a single bond or an oxygen atom. L ¹⁰³ to L ¹⁰⁵ each independently represent a single bond, -CO- or -SO ₂ -. M ' ^{m +} is an ^{m &lt}; 2 ^&gt; onium cation.

{Negative ion part}

The negative ion part of the component (b-1)

In formula (b-1), R ¹⁰¹ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a straight chain alkenyl group which may have a substituent.

(A 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. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually saturated.

The aromatic hydrocarbon group in R &lt; ¹⁰¹ &gt; is a hydrocarbon group having an aromatic ring. The number of carbon atoms of the aromatic hydrocarbon group is preferably from 3 to 30, more preferably from 5 to 30, still more preferably from 5 to 20, still more preferably from 6 to 15, and most preferably from 6 to 10. Provided that the number of carbon atoms does not include the number of carbon atoms in the substituent group.

Specific examples of aromatic rings having aromatic hydrocarbon groups in R ¹⁰¹ include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocyclic rings in which a part of carbon atoms constituting aromatic rings thereof are substituted with a hetero atom And the like. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom and a nitrogen atom.

Specific examples of the aromatic hydrocarbon group represented by R ¹⁰¹ include a group in which one hydrogen atom is ^removed from the aromatic ring (aryl group: e.g., phenyl group, naphthyl group, etc.), one of the hydrogen atoms in the aromatic ring 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 like arylalkyl group). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

The cyclic aliphatic hydrocarbon group for R &lt; ¹⁰¹ &gt; includes an aliphatic hydrocarbon group containing a ring in its structure.

As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group in which one hydrogen atom is removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a straight chain or branched aliphatic hydrocarbon group, And groups in which the hydrocarbon group is interposed in the straight chain or branched chain aliphatic hydrocarbon group.

The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which at least one hydrogen atom is removed from the monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, and the like. The polycyclic alicyclic hydrocarbon group is preferably a group in which at least one hydrogen atom is removed from the polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically includes adamantane, norbornane, isobonane , Tricyclodecane, tetracyclododecane, and the like

Among them, the cyclic aliphatic hydrocarbon group for R &lt; ¹⁰¹ &gt; is preferably a group in which at least one hydrogen atom is removed from the monocycloalkane or polycycloalkane, more preferably a group excluding one hydrogen atom from the polycycloalkane, A t-butyl group and a norbornyl group are particularly preferable, and an adamantyl group is most preferable.

The straight-chain or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3 desirable.

Examples of the aliphatic hydrocarbon group in a straight chain, and an alkylene group of preferably straight chain, 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.

As the aliphatic hydrocarbon group branched-chain, and an alkylene group of preferably branched chain, _{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 ) -, and -C (CH ₂ CH ₃ ) 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 -, -C (CH ₂ CH _{3) 2} -CH ₂ - alkyl group such as ethylene; _{-CH (CH 3) CH 2 CH} 2 -, -CH 2 CH (CH 3) CH 2 - alkyl trimethylene group and the like; And alkyl alkylene groups such as alkyltetramethylene groups such as -CH (CH ₃ ) CH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) CH ₂ CH ₂ - and the like. As the alkyl group in the alkyl alkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

The cyclic hydrocarbon group in R &lt; ¹⁰¹ &gt; may include a hetero atom such as a heterocycle. Specifically, a lactone-containing cyclic group represented by any one of the above-mentioned general formulas (a2-r-1) to (a2-r-7) , An -SO ₂ -containing cyclic group, and other heterocyclic groups described below.

Examples of the substituent in the cyclic hydrocarbon group of R &lt; ¹⁰¹ &gt; 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 and a tert-butyl group.

The alkoxy group as a substituent is preferably an alkoxy group having from 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group or a tert- The ethoxy group is most preferred.

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.

Examples of the halogenated alkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms such as groups in which some or all of hydrogen atoms such as methyl, ethyl, propyl, n-butyl and tert-butyl groups are substituted with the above halogen atoms .

The carbonyl group as a substituent is a group substituted with a methylene group (-CH ₂ -) constituting a cyclic hydrocarbon group.

(A linear alkyl group which may have a substituent)

As the alkyl group on chain represented by R ¹⁰¹ , a straight chain or branched chain may be used.

The straight-chain alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specific examples thereof include a 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, , A tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a heneicosyl group, and a docosyl group.

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. Specific examples thereof include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, -Ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

(A straight chain alkenyl group which may have a substituent)

The chain alkenyl group represented by R ¹⁰¹ may be straight chain or branched chain, preferably has 2 to 10 carbon atoms, more preferably 2 to 5, more preferably 2 to 4, and particularly preferably 3 Do. Examples of the straight chain alkenyl group include a vinyl group, a propenyl group (allyl group), and a butyryl group. Examples of the branched-chain alkenyl group include a 1-methylvinyl group, a 2-methylvinyl group, a 1-methylpropenyl group and a 2-methylpropenyl group.

As the chain alkenyl group, among these groups, a vinyl group and a propenyl group are more preferable, and a vinyl group is particularly preferable.

Examples of the substituent in the alkyl group or the alkenyl group on the chain 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 a cyclic group in the R ¹⁰¹ .

Among them, R ¹⁰¹ is preferably a cyclic group which may have a substituent, more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, a lactone-containing cyclic group represented by each of the above-mentioned formulas (a2-r-1) to (a2-r-7) And -SO ₂ -containing cyclic groups represented by formulas (a5-r-1) to (a5-r-4), respectively.

In the formula (b-1), Y ¹⁰¹ is a divalent linking group containing a single bond or an oxygen atom.

When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, the Y ¹⁰¹ may contain an atom other than an oxygen atom. Examples of the atoms other than the oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, and a nitrogen atom.

Examples of the divalent linking group containing an oxygen atom include an oxygen atom (ether bond: -O-), an ester bond (-C (= O) -O-), an oxycarbonyl group (-OC , A non-hydrocarbon-based oxygen atom-containing linking group such as an amide bond (-C (= O) -NH-), a carbonyl group (-C (= O) -) and a carbonate bond (-OC (= O) -O-); And combinations of the non-hydrocarbon-based oxygen atom-containing linking group and the alkylene group. The combination may further include a sulfonyl group (-SO ₂ -). Examples of the combination include a linking group represented by the following formulas (y-al-1) to (y-al-7).

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 at V ' ¹⁰² is preferably an alkylene group having 1 to 30 carbon atoms.

The alkylene group at V ' ¹⁰¹ and V' ¹⁰² may be a straight chain alkylene group or a branched chain alkylene group, preferably a straight chain alkylene group.

Specific examples of the alkylene group for 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 -; Ethylene group [-CH ₂ CH ₂ -]; _{-CH (CH 3) CH 2 -} , -CH (CH 3) CH (CH 3) -, -C (CH 3) 2 CH 2 -, -CH (CH 2 CH 3) CH 2 - such as the ethylene-alkyl ; A 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 - alkyl trimethylene group and the like; A tetramethylene group [-CH ₂ CH ₂ CH ₂ CH ₂ -]; An alkyltetramethylene group such as -CH (CH ₃ ) CH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) CH ₂ CH ₂ -; A pentamethylene group [-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -] and the like.

In addition, some of the methylene groups in the alkylene group at V ' ¹⁰¹ or V' ¹⁰² may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a divalent group excluding one hydrogen atom from the cyclic aliphatic hydrocarbon group of Ra ' ³ in the formula (a1-r-1), more preferably a cyclohexylene group, More preferably a thienylene group or a 2, 6-adamantylene group.

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

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

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

Specific examples of the anion moiety of the component (b-1) include, for example, a fluorinated alkylsulfonate anion such as a trifluoromethanesulfonate anion or a perfluorobutanesulfonate anion when Y ¹⁰¹ is a single bond ; When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, an anion represented by any one of the following formulas (an-1) to (an-3) may be mentioned.

Wherein R ¹⁰¹ is an aliphatic cyclic group which may have a substituent, a group each represented by the above formulas (r-hr-1) to (r-hr-6), or a chain alkyl group which may have a substituent ; r ^"102 is an aliphatic cyclic group which may have a substituent group, the formula (a2-r-1) ~ (a2-r-7) lactone representing respectively containing a cyclic group, or the formula (a5-r-1 ) ~ (a5-r-4 ) each represent a -SO ₂ - containing cyclic group, and; R " ¹⁰³ is independently 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 of 0 to 3, q " Is independently an integer of 1 to 20, t "is an integer of 1 to 3, and n" is 0 or 1.

R ^"101, R" ¹⁰² and R "aliphatic ring which may have a ¹⁰³ substituents of dishes it is preferable that, due exemplified as the cyclic aliphatic hydrocarbon group in the R ^101. Cyclic in Examples of the substituent, R ¹⁰¹ And a substituent which may be substituted with an aliphatic hydrocarbon group.

R "aromatic ring group which may have a substituent at ¹⁰³ it is desirable, due exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in the R ^101. Examples of the substituent, a substituted group of the aromatic hydrocarbon in R ¹⁰¹ And the like.

R "group of the chain which may have a substituent in the ^101, is due exemplified as the alkyl group of the chain in the R ¹⁰¹ is preferable. R" alkenyl chain which may have a substituent in the ¹⁰³ groups, wherein R ¹⁰¹ Is preferably a group exemplified as a chain alkenyl group in the formula (I).

The negative ion part of component (b-2)

In formula (b-2), R ¹⁰⁴ and R ¹⁰⁵ are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent or a chain alkenyl group which may have a substituent, Include the same ones as R ¹⁰¹ in the formula (b-1). Provided that R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring.

R ¹⁰⁴ and R ¹⁰⁵ are preferably a linear alkyl group which may have a substituent and more preferably a linear or branched alkyl group or a straight chain or branched chain fluorinated alkyl group.

The number of carbon atoms of the above chain alkyl group is preferably from 1 to 10, more preferably from 1 to 7, and still more preferably from 1 to 3. R ^104, in the range of R chain alkyl group of the carbon number, the number of carbon atoms of ^105, solubility is also preferably smaller, by reason of the good, such as for a resist solvent. In addition, R ^104, a group of R ¹⁰⁵ chain The larger the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid is, and the better the transparency to high-energy light of 200 nm or less and the electron beam, which is preferable. The proportion of the fluorine atoms in the alkyl group on the chain, that is, the fluoride group is preferably 70 to 100%, more preferably 90 to 100%, and most preferably, the perfluoroalkyl group in which all the hydrogen atoms are substituted with fluorine atoms .

In the formula (b-2), V ¹⁰² and V ¹⁰³ each independently represent a single bond, an alkylene group or a fluorinated alkylene group, and the same groups as those of V ¹⁰¹ in the formula (b-1)

In the formula (b-2), L ¹⁰¹ to L ¹⁰² each independently represent a single bond or an oxygen atom.

The anion portion of the component (b-3)

In formula (b-3), R ¹⁰⁶ to R ¹⁰⁸ are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and R ¹⁰¹ in the general formula (b-1).

Each of L ¹⁰³ to L ¹⁰⁵ independently represents a single bond, -CO- or -SO ₂ -.

{Cation part}

In the formulas (b-1), (b-2) and (b-3), M'm ⁺ is an m-valent onium cation, and a sulfonium cation or an iodonium cation is preferable. Specifically, organic cations represented by the general formulas (ca-1) to (ca-4) exemplified as M ^{m +} (m organic cations) in the formula (d0-1) are preferable.

As the component (B), the aforementioned acid generators may be used alone, or two or more of them may be used in combination.

When the resist composition of the present invention contains the component (B), the content of the component (B) is preferably from 0.5 to 60 parts by mass, more preferably from 1 to 50 parts by mass, more preferably from 1 to 50 parts by mass, per 100 parts by mass of the component (A) To 40 parts by mass is more preferable. By setting the content of the component (B) in the above range, pattern formation is sufficiently performed. Further, when each component of the resist composition is dissolved in an organic solvent, a homogeneous solution can be obtained and storage stability is favorable, which is preferable

[Component (D1)] [

The resist composition of the present invention may further contain an acid diffusion controller component in addition to the component (A) and the component (D0), or in addition to the component (A), the component (D0) .

The acid diffusion control agent component acts as a catalyst (acid diffusion control agent) for trapping an acid generated by exposure from the above component (B) or the like.

As the acid diffusion control agent component, a photo-degradable base (D1) (hereinafter referred to as "(D1) component") which decomposes by exposure to lose acid diffusion controllability is preferable. Furthermore, the component (D0) also acts as a probe (acid diffusion control agent), but does not correspond to the component (D1)

(D1), the contrast between the exposed portion and the unexposed portion can be improved when the resist pattern is formed.

The component (D1) is not particularly limited as long as it is decomposed by exposure to lose its acid diffusion controllability, and a compound represented by the following general formula (d1-1) (hereinafter referred to as a (d1-1) component) The compound represented by the general formula (d1-2) (hereinafter referred to as the "component (d1-2)") and the compound represented by the following general formula (d1-3) Is preferably at least one compound selected from the group consisting of

The components (d1-1) to (d1-3) in the exposed part decompose and lose acid diffusion controllability (basicity), so they do not act as a catalyst and act as a catalyst in the unexposed area.

[Wherein, Rd Rd ¹ ~ ⁴ is an alkenyl group which may have a branched alkyl group, or a substituent in the chain which may have a ring group, substituents may have a substituent. It is to be noted that the fluorine atom is not bonded to the carbon atom adjacent to the S atom in Rd ² in the formula (d1-2). Yd ¹ is a single bond or a divalent linking group. m is an integer of 1 or more, and M &lt; ^{m +} &^gt;

{(d1-1) component}

‥ Anion part

Formula (d1-1) of, R ^{1 101} of Rd is an alkenyl group which may have a branched alkyl group, or a substituent in the chain which may have a ring group, substituents may have a substituent, the formula (b-1) And the like.

Among them, Rd ¹ is preferably an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkyl group which may have a substituent. The substituent which these groups may have is preferably a hydroxyl group, a fluorine atom or a fluorinated alkyl group.

As the aromatic hydrocarbon group, a phenyl group or a naphthyl group is more preferable.

The alicyclic group is more preferably a group excluding at least one hydrogen atom in a polycycloalkane such as adamantane, norbornane, isobonane, tricyclodecane, and tetracyclododecane.

The above-mentioned straight chain alkyl group preferably has 1 to 10 carbon atoms and specifically includes straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, A straight chain alkyl group; Methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methyl Pentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

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

Rd ¹ is preferably a fluorinated alkyl group in which some or all of the hydrogen atoms constituting the linear alkyl group are substituted by fluorine atoms, and a fluorinated alkyl group in which all the hydrogen atoms constituting the linear alkyl group are substituted with a fluorine atom Chain perfluoroalkyl group).

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

... cationic part

In the formula (d1-1), M ^{m +} is an organic cation of m valent.

Examples of organic cations M ^{m +,} equal to M ^{m +} in the formula (d0-1) of the above-described, inter alia, the general formula (ca-1) ~ be preferably the same and each represents a cation with (ca-4) and , And the cations represented by the above formulas (ca-1-1) to (ca-1-67) are more preferable.

As the component (d1-1), one kind may be used alone, or two or more kinds may be used in combination.

{(d1-2) component}

‥ Anion part

Formula (d1-2) of from, Rd ² is an alkenyl group which may have a branched-chain alkyl group which may have a ring group, substituents may have a substituent, or a substituent group, the formula (b-1) R ¹⁰¹ &lt; / RTI &gt;

Provided that the fluorine atom is not bonded to the carbon atom adjacent to the S atom (it is not fluorine-substituted) in Rd ² . As a result, the anion of the component (d1-2) becomes an appropriate weakly acid anion, and the ability to function as the component (D) improves.

Rd ² is preferably an aliphatic cyclic group which may have a substituent and may be a group excluding at least one hydrogen atom (may have a substituent) in adamantane, norbornane, isobonane, tricyclodecane, tetracyclododecane, etc., ; It is more preferable that the group is a group excluding at least one hydrogen atom in the camphor.

The hydrocarbon group of Rd ² may have a substituent, and examples of the substituent include the same substituent that the hydrocarbon group (aromatic hydrocarbon group, aliphatic hydrocarbon group) in Rd ¹ of the formula (d1-1) may have.

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

... cationic part

In the formula (d1-2), M ^{m +} is an organic cation of ^m and is the same as M ^{m +} in the formula (d1-1).

As the component (d1-2), one kind may be used alone, or two or more kinds may be used in combination.

{(d1-3) component}

‥ Anion part

Formula (d1-3) of, Rd ³ is an alkenyl group which may have a branched alkyl group, or a substituent in the chain which may have a ring group, substituents may have a substituent, R ¹⁰¹ in the formula (b-1) , And is preferably a cyclic group containing fluorine atom, a chain alkyl group, or a straight chain alkenyl group. Among them, a fluorinated alkyl group is preferable, and the same as the fluorinated alkyl group of Rd ¹ is more preferable.

Formula (d1-3) of, Rd is ^4, and alkenyl groups of chain which may have an alkyl group, or a substituent of the chain which may have a ring group, substituents may have a substituent, R in the above formula (b-1) ¹⁰¹ &lt; / RTI &gt;

Among them, an alkyl group, an alkoxy group, an alkenyl group, and a cyclic group which may have a substituent are preferable.

The alkyl group in Rd ⁴ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, A pentyl group, an isopentyl group, and a neopentyl group. Part of the hydrogen atoms of the alkyl group Rd is ⁴ may be substituted by a hydroxyl group, a cyano group or the like.

The alkoxy group in Rd ⁴ is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, , and tert-butoxy group. Among them, a methoxy group and an ethoxy group are preferable.

The alkenyl group in Rd ⁴ is the same as 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 an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms as a substituent.

The cyclic group in Rd ⁴ is the same as R ¹⁰¹ in the above formula (b-1), and examples thereof include cyclopentane, cyclohexane, adamantane, norbornane, isobonane, tricyclodecane, tetracyclododecane An alicyclic group excluding one or more hydrogen atoms in the cycloalkane of the cycloalkane, or an aromatic group such as a phenyl group or a naphthyl group is preferable. When Rd ⁴ is an alicyclic group, the resist composition is well dissolved in an organic solvent, whereby lithography characteristics are improved. When Rd ⁴ is an aromatic group, in the lithography using EUV or the like as an exposure light source, the resist composition exhibits excellent light absorption efficiency and good sensitivity and lithography characteristics.

Formula (d1-3) of, Yd ¹ is a single bond or a divalent connecting group.

The divalent linking group in Yd ¹ is not particularly limited, and examples thereof include a divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent, and a divalent linking group containing a hetero atom. These are the same as those described for the divalent linking group of Ya ²¹ in the formula (a2-1).

Yd ¹ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, more preferably a methylene group or an ethylene group.

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

... cationic part

In the formula (d1-3), M ^{m +} is an organic cation of ^m and is the same as M ^{m +} in the formula (d1-1).

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

As the component (D1), any one of the above components (d1-1) to (d1-3) may be used, or two or more of them may be used in combination.

The content of the component (D1) is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and further preferably 1 to 8 parts by mass, per 100 parts by mass of the component (A).

When the content of the component (D1) is a preferable lower limit value or more, particularly good lithography characteristics and resist pattern shapes are obtained. On the other hand, if it is below the upper limit value, the sensitivity can be kept good and the throughput is also excellent.

(Production method of component (D1)) [

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

The method for producing the component (d1-3) is not particularly limited, and is manufactured in the same manner as the method described in, for example, US2012-0149916.

[Component (D2)] [

The acid diffusion control agent component may contain a nitrogen-containing organic compound component (hereinafter referred to as "component (D2)") which does not correspond to the components (D0) and (D1).

The component (D2) is not particularly limited as long as it functions as an acid diffusion control agent and does not correspond to the components (D0) and (D1), and may be arbitrarily used from known ones. Of these, aliphatic amines, especially secondary aliphatic amines and tertiary aliphatic amines, are preferred.

The aliphatic amine is an amine having at least one aliphatic group, and the aliphatic group preferably has 1 to 12 carbon atoms.

Examples of the aliphatic amines include amines (alkylamines or alkylalcoholamines) substituted by at least one hydrogen atom of ammonia NH ₃ with an alkyl or hydroxyalkyl group having 12 or less carbon atoms, or cyclic amines.

Specific examples of alkylamines and alkylalcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine; Dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine and dicyclohexylamine; N-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-octylamine, trialkylamines such as n-nonylamine, tri-n-decylamine and tri-n-dodecylamine; And alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine and tri-n-octanolamine. Of these, trialkylamines having 5 to 10 carbon atoms are more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

The cyclic amine includes, for example, a heterocyclic compound 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 amines include piperidine and piperadine.

As the aliphatic polycyclic amine, the number of carbon atoms is preferably from 6 to 10. Specific examples thereof include 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] Undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane, and the like.

Examples of other aliphatic amines include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} Amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, triethanolamine triacetate and the like, and triethanolamine triacetate is preferable.

As the component (D2), an aromatic amine may also be used.

Examples of the aromatic amine include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, .

(D2) may be used alone or in combination of two or more.

(D2) is usually used in a range of 0.01 to 5 parts by mass based on 100 parts by mass of the component (A). By setting the concentration in the above range, the resist pattern shape, stability at the time of standing, and the like are improved.

[Component (E)] [

The resist composition of the present invention may contain, as optional components, at least one member selected from the group consisting of an organic carboxylic acid and an oxo acid of phosphorus and derivatives thereof for the purpose of preventing deterioration of sensitivity and improving the resist pattern shape, (E) (hereinafter referred to as &quot; component (E) &quot;).

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 preferable.

Examples of the phosphorous acid include phosphoric acid, phosphonic acid and phosphinic acid, and among these, phosphonic acid is particularly preferable.

Examples of the derivative of the oxo acid of phosphorus include an ester in which the hydrogen atom of the oxo acid is substituted with a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, .

Examples of phosphoric acid derivatives include phosphate esters such as phosphoric acid-di-n-butyl ester and phosphoric acid diphenyl ester.

Examples of the 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 derivatives of phosphinic acid include phosphinic acid esters and phenylphosphinic acid.

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

The component (E) is usually used in a range of 0.01 to 5 parts by mass based on 100 parts by mass of the component (A).

[Component (F)] [

The resist composition of the present invention may contain a fluorine additive (hereinafter referred to as "component (F)") for imparting water repellency to the resist film.

Examples of the component (F) include fluorine-containing polymer compounds described in JP-A Nos. 2010-002870, 2010-032994, 2010-277043, 2011-13569, and 2011-128226 Can be used.

More specifically, as the component (F), a polymer having a structural unit (f1) represented by the following formula (f1-1) may be mentioned. As the polymer, a polymer (homopolymer) composed solely of the constituent unit (f1) represented by the following formula (f1-1); A copolymer of the structural unit (f1) and the structural unit (a1); The structural unit (f1) is preferably a copolymer of the structural unit derived from acrylic acid or methacrylic acid and the structural unit (a1). Here, as the structural unit (a1) copolymerized with the structural unit (f1), a structural unit derived from 1-ethyl-1-cyclooctyl (meth) acrylate is preferable.

[Wherein, R is the same as above, Rf ¹⁰² and Rf ¹⁰³ each independently represents a hydrogen atom, a halogen atom, a 1 to 5 carbon atoms, or represents a halogenated alkyl group of 1 to 5 carbon atoms, Rf ¹⁰² and Rf ¹⁰³ is the same It may be either different or different. nf ¹ is an integer of 1 to 5, and Rf ¹⁰¹ is an organic group containing a fluorine atom.]

In formula (f1-1), R bonded to the carbon atom at the? -Position is the same as described above. As R, a hydrogen atom or a methyl group is preferable.

Examples of the halogen atom of Rf ¹⁰² and Rf ^{103 in} the formula (f1-1) 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 represented by Rf ¹⁰² and Rf ¹⁰³ include the same alkyl groups having 1 to 5 carbon atoms as R described above, and a methyl group or an ethyl group is preferable. Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms for Rf ¹⁰² and Rf ¹⁰³ include groups in which a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms is substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable. Among them, Rf ¹⁰² and Rf ¹⁰³ are preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, and are preferably a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group.

Formula (f1-1) of, ¹ nf is an integer from 1 to 5. The integer of 1-3, and more preferably 1 or 2.

Formula (f1-1) of, Rf ¹⁰¹ is preferably a hydrocarbon group containing a fluorine atom as the organic group containing fluorine atom.

The hydrocarbon group containing a fluorine atom may be any of linear, branched or cyclic, and preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and particularly preferably 1 to 10 carbon atoms .

In the hydrocarbon group containing a fluorine atom, it is preferable that at least 25% of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably at least 50% of the hydrogen atoms are fluorinated, and more preferably at least 60% Is particularly preferable in that the hydrophobicity of the resist film upon immersion exposure is high.

Among them, a fluorinated hydrocarbon group having 1 to 5 carbon atoms is particularly preferable as Rf ¹⁰¹ , and a trifluoromethyl group, -CH ₂ -CF ₃ , -CH ₂ -CF ₂ -CF ₃ , -CH (CF ₃ ) ₂ , - CH ₂ -CH ₂ -CF ₃ , -CH ₂ -CH ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₃ is most preferred.

The mass average molecular weight (Mw) (based on polystyrene conversion by gel permeation chromatography) of the component (F) is preferably from 1,000 to 50,000, more preferably from 5,000 to 40,000, and most preferably from 10,000 to 30,000. When the upper limit of the above range is exceeded, solubility in a resist solvent sufficient for use as a resist is high. If the lower limit of the above range is exceeded, the dry etching resistance and the cross-sectional shape of the resist pattern are favorable.

The dispersion degree (Mw / Mn) of the component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5.

As the component (F), one kind may be used alone, or two or more kinds may be used in combination.

The component (F) is used in a proportion of 0.5 to 10 parts by mass based on 100 parts by mass of the component (A).

The resist composition of the present invention may further contain additionally miscible additives as desired, such as an additional resin for improving the performance of a resist film, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, a halation inhibitor, .

[Component (S)] [

The resist composition of the present invention can be produced by dissolving the resist material in an organic solvent (hereinafter, also referred to as "(S) component")).

As the component (S), any one that can dissolve each component to be used and make it a homogeneous solution can be used. Conventionally, any one of known solvents as chemically amplified resists can be appropriately selected and used .

Lactones such as? -Butyrolactone; Ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone and 2-peptanone; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; A compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, a monomethyl ether, monoethyl ether, Monoalkyl ethers such as monopropyl ether and monobutyl ether, and compounds having an ether bond such as monophenyl ether [among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred; Cyclic ethers such as dioxane, esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate; An ether such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene Aromatic organic solvent, dimethylsulfoxide (DMSO), and the like.

These organic solvents may be used alone or in combination of two or more.

Among them, PGMEA, PGME,? -Butyrolactone, EL, and cyclohexanone are preferable.

A mixed solvent in which PGMEA and a polar solvent are mixed is also preferable. The compounding ratio (mass ratio) may be suitably determined in consideration of the compatibility of the PGMEA and the polar solvent, and is preferably within the range of 1: 9 to 9: 1, more preferably 2: 8 to 8: 2 desirable.

More specifically, when EL or cyclohexanone is blended as a polar solvent, the mass ratio of PGMEA: EL or cyclohexanone is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8 : 2. When PGME is blended as a polar solvent, the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, more preferably 3: 7: 3. Mixed solvents of PGMEA, PGME and cyclohexanone are also preferable.

In addition, as the component (S), a mixed solvent of γ-butyrolactone and at least one member selected from PGMEA and EL is also preferable. In this case, as the mixing ratio, the mass ratio of the former to the latter is preferably 70:30 to 95: 5.

The amount of the component (S) to be used is not particularly limited and is appropriately set in accordance with the thickness of the coating film at a concentration applicable to a substrate or the like. Generally, it is used so that the solid concentration of the resist composition is in the range of 1 to 20 mass%, preferably 2 to 15 mass%.

According to the resist composition of the present invention, when forming a resist pattern, it is possible to form a resist pattern with high sensitivity, excellent lithography characteristics, and good shape.

The resist composition of the present invention contains the compound (D0) represented by the general formula (d0-1). (D0) is a kind of photodegradable base which acts as a catalyst (acid diffusion control agent) for trapping an acid generated by exposure. (D0) has a structure of a camphanic acid skeleton (R ¹ ), and a linking group "-V ¹ -Y ¹ - (CHR ² ) _n -" between R ¹ and SO ₃ - . By having such a high-polarity bulky structure, the diffusion of the negative ion part in the resist film exposure part is suppressed. By using the resist composition of the present invention containing the component (D0), it is considered that various lithographic properties such as roughness reduction, mask reproducibility, and process margin are improved.

&Quot; Method of forming resist pattern &quot;

The method for forming a resist pattern of the present invention includes a step of forming a resist film on a support by using the resist composition of the present invention, a step of exposing the resist film, and a step of developing the resist film to form a resist pattern.

The resist pattern forming method of the present invention can be carried out, for example, as follows.

First, the resist composition according to the present invention is coated on a support by a spinner or the like and baked (post-apply baking (PAB)) treatment is performed at a temperature of 80 to 150 캜 for 40 to 120 seconds, For 60 to 90 seconds to form a resist film.

Next, an exposure apparatus such as an ArF exposure apparatus, an electron beam lithography apparatus, an EUV exposure apparatus, or the like is used for the resist film, and an exposure or mask pattern interposed between a mask (mask pattern) (Post exposure bake (PEB)) treatment is carried out at a temperature of 80 to 150 ° C for 40 to 120 seconds, preferably 60 to 90 seconds, for example, after performing selective exposure by direct irradiation of electron beams Second.

Next, the resist film is developed. The developing treatment is carried out using an alkaline developing solution in the case of the alkali developing process and a developing solution (organic developing solution) containing an organic solvent in the case of the solvent developing process.

After the developing treatment, rinsing treatment is preferably carried out. The rinse treatment is preferably a water treatment using pure water in the case of an alkali developing process and a rinsing solution containing an organic solvent in the case of a solvent developing process.

In the case of the solvent developing process, after the developing treatment or the rinsing treatment, a treatment for removing the developing solution or the rinsing liquid adhering to the pattern by the supercritical fluid may be performed.

After the development treatment or the rinsing treatment, drying is performed. In some cases, a baking process (post-baking) may be performed after the above development process. In this manner, a resist pattern can be obtained.

The support is not particularly limited and conventionally known ones can be used, and examples thereof include a substrate for electronic components and a substrate having a predetermined wiring pattern formed thereon. More specifically, examples thereof include substrates made of metal such as silicon wafers, copper, chromium, iron and aluminum, and glass substrates. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold and the like can be used.

As the support, an inorganic and / or organic film may be provided on the substrate as described above. The inorganic film may be an inorganic anti-reflection film (inorganic BARC). Examples of the organic film include an organic antireflection film (organic BARC) and an organic film such as a lower organic film in a multilayer resist method.

Here, the 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 a resist pattern formed on the upper resist film is used as a mask, Patterning of the film is performed, and a high aspect ratio pattern can be formed. That is, according to the multi-layer resist method, since the necessary thickness can be secured by the lower organic film, the resist film can be made thin and a fine pattern with a high aspect ratio can be formed.

In the multilayer resist method, basically, a method of forming a two-layer structure of an upper resist film and a lower layer organic film (two-layer resist method), and a method of forming an intermediate layer (metal thin film or the like) Layer structure (a three-layer resist method).

The wavelength to be used for exposure is not particularly limited and the radiation such as ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X- And the like. The resist composition has high usability 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 ordinary exposure (dry exposure) performed in an inert gas such as air or nitrogen, or may be liquid immersion lithography.

The liquid immersion exposure is an exposure method in which a space between a resist film and a lens in the lowermost position of the exposure apparatus is filled with a solvent (immersion medium) having a refractive index larger than that of air and exposure (immersion exposure) is performed in this state.

As the immersion medium, a solvent having a refractive index that is larger than the refractive index of air and smaller than the refractive index of the exposed resist film 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 that is 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 silicone-based solvent, and a hydrocarbon-based solvent.

Specific examples of the fluorine-based inert liquid include liquids containing 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 , The boiling point is preferably 70 to 180 ° C, and more preferably 80 to 160 ° C. If the fluorine-based inert liquid has a boiling point in the above range, the removal of the medium used for immersion after the end of exposure can be carried out with a simple method.

As the fluorine-based inert liquid, a perfluoroalkyl compound in which the hydrogen atoms of the alkyl group are all substituted with fluorine atoms is particularly preferable. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.

More specifically, as the perfluoroalkyl ether compound, perfluoro (2-butyl-tetrahydrofuran) (boiling point: 102 ° C) may be mentioned. As the perfluoroalkylamine compound, perfluorotributylamine (Boiling point 174 DEG C).

As the immersion medium, water is preferably used from the viewpoints of cost, safety, environmental problems, versatility and the like.

Examples of the alkali developing solution used in the developing treatment in the alkali development process include an aqueous solution of 0.1 to 10 mass% tetramethylammonium hydroxide (TMAH).

The organic solvent contained in the organic developing solution used in the developing treatment in the solvent developing process may be any solvent that can dissolve the component (A) (component (A) before exposure) and may be appropriately selected from known organic solvents. Specific examples thereof include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents and ether solvents, hydrocarbon solvents and the like.

The ketone-based 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-based solvent is an organic solvent containing an alcoholic hydroxyl group in its structure, and the "alcoholic hydroxyl group" means a hydroxyl group bonded to the carbon atom of the aliphatic hydrocarbon group. The nitrile-based solvent is an organic solvent containing a nitrile group in its structure. The amide-based solvent is an organic solvent containing an amide group in its structure. The ether solvent is an organic solvent containing C-O-C in the structure.

In the organic solvent, an organic solvent containing a plurality of functional groups characterizing each of the solvents is also present in the structure. In this case, it is assumed that the solvent corresponds to any solvent species including the functional group possessed by the organic solvent. For example, diethylene glycol monomethyl ether corresponds to any one of alcohol-based solvents and ether-based solvents in the above-mentioned classification.

The hydrocarbon solvent is a hydrocarbon solvent which is composed of hydrocarbons which may be halogenated and has no substituent other than 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 preferable.

Among the organic solvents contained in the organic developing solution, polar solvents are preferable among them, and ketone solvents, ester solvents, nitrile solvents and the like are preferable.

Specific examples of the solvents include ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1- But are not limited to, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, Methyl naphthyl ketone, isophorone, propylene carbonate,? -Butyrolactone, and methyl amyl ketone (2-heptanone).

As the ketone solvent, methylamyl ketone (2-heptanone) is preferable.

Examples of the ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, isoamylether, ethyl methoxyacetate, ethyl ethoxyacetate, propyleneglycol monomethylether acetate, Ethyl ether acetate, ethylene glycol monopropyl 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, di Ethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3- Methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4- Methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3- Methoxypentyl acetate, propyleneglycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, ethyl lactate, Propyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, Ethyl propionate, ethyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl -3-ethoxypropionate, and propyl-3-methoxypropionate.

As the ester-based solvent, butyl acetate is preferable.

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

A known additive may be added to the organic developer, if necessary. As the additive, for example, a surfactant can be mentioned. The surfactant is not particularly limited, and 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 fluorinated surfactant or a silicon surfactant is more preferable.

When the surfactant is blended, the blending amount thereof is usually 0.001 to 5 mass%, preferably 0.005 to 2 mass%, more preferably 0.01 to 0.5 mass%, based on the total amount of the organic developer.

The developing treatment can be carried out by a known developing method. For example, a developing solution is dipped into a developing solution for a predetermined time (dipping method), a developing solution is formed on the surface of the developing solution by surface tension, A method of spraying the developer onto the surface of the support (spraying method), a method of extracting the developer while scanning the developer introducing nozzle at a constant speed (dynamic dispensing method) on a support rotating at a constant speed, etc. .

As the organic solvent contained in the rinsing liquid used for the rinsing treatment after the developing treatment in the solvent developing process, those which are difficult to dissolve the resist pattern can be appropriately selected and used in the organic solvent as the organic solvent used for the organic developing solution. Usually, at least one solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent is used. Of these, at least one selected from a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent and an amide-based solvent is preferable, and at least one selected from an alcoholic solvent and an ester- , And alcohol solvents are particularly preferable.

The alcoholic solvent used in the rinsing liquid is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be any of linear, branched and cyclic. Specific examples thereof include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, - octanol, benzyl alcohol, and the like. Among them, 1-hexanol, 2-heptanol and 2-hexanol are preferable, and 1-hexanol or 2-hexanol is more preferable.

These organic solvents may be used singly or in a mixture of two or more kinds. It may be mixed with an organic solvent or water other than the above. The amount of water in the rinsing liquid is preferably 30 mass% or less, more preferably 10 mass% or less, more preferably 5 mass% or less, and most preferably 3 mass% % Or less is particularly preferable.

A known additive may be added to the rinse liquid, if necessary. As the additive, for example, a surfactant can be mentioned. Examples of the surfactant include those described above. Nonionic surfactants are preferred, and fluorinated surfactants or silicone surfactants are more preferred.

When the surfactant is blended, the blending amount thereof is usually 0.001 to 5 mass%, preferably 0.005 to 2 mass%, more preferably 0.01 to 0.5 mass%, based on the total amount of the rinse liquid.

The rinsing treatment (rinsing treatment) using the rinsing liquid can be carried out by a known rinsing method. Examples of the method include a method of drawing a rinsing liquid onto a support rotating at a constant speed (spin coating method), a method of dipping a support in a rinsing solution for a predetermined time (dipping method), a method of spraying a rinsing solution onto the surface of a support (Spray method).

"compound"

The compound of the present invention is represented by the following general formula (d0) (hereinafter also referred to as "compound (d0)").

Wherein Y ¹ is a single bond or a divalent linking group. V ¹ is a single bond or a divalent cyclic group which may have a substituent. R ¹ is a monovalent group represented by the formula (r-d0), and * in the formula (r-d0) represents a bond. R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. n is 0 or 1, and when n is 0, V ¹ is not a single bond. m is an integer of 1 or more, and M " ^{m +} is a cation of m valency.

In the formula ^{(d0), Y 1, V} 1, R 1, R 2, n and m are the same as the formula (d0-1) of the ^{Y 1, V 1, R 1} , R 2, n and m.

M ^{"m +} is an m-valent cation, and the like alkali metal cation, an organic cation. Examples of the alkali metal ions, and include sodium ion, lithium ion, potassium ion and the like, a sodium ion or lithium ion is preferable Examples of the organic cation include a nitrogen-containing cation such as an ammonium ion and a pyridinium ion, and an organic cation of M ^{m +} in the formula (d0-1).

(Production method of compound (d0)) [

As the compound (d0), for example, the compound (d01) in which the cationic addition is an alkali metal cation or an organic cation (nitrogen cation) can be produced by reacting a compound (d01-1) represented by the following general formula (d01-2) shown by the following formula (d01-2).

Also, for example, the compound (d02) (which is the same as the compound (D0)) which is a cationic moiety (this is the same as the organic cation of Mm ⁺ in the formula (d0-1) Is obtained by salt exchange of organic cations.

Wherein Y ¹ , V ¹ , R ² , n and m are the same as Y ¹ , V ¹ , R ² , n and m in the formula (d0). M ₁ " ^{m +} is an alkali metal cation or an organic cation (nitrogen cation) of m valence M ₂ " ^{m +} is an organic cation of m valence (the same as the organic cation of M ^{m +} in the formula (d0-1)) . X _ha is a halogen atom, and Z ^- is an unconjugated ion.]

In the formula, M ₁ ^{"m +} is an alkali metal cation or an organic cation valence m (nitrogen-containing cation), with a, M _2" ^{m +} is an organic cation of M ^{m +} in the m-valent organic cation (the formula (d0-1) and And the like, and examples thereof include the alkali metal cations and organic cations exemplified as the m-valent cation of M " ^{m +} , respectively.

X _ha is a halogen atom, and examples thereof include a bromine atom, a chlorine atom, an iodine atom and a fluorine atom. From the viewpoint of excellent reactivity, a bromine atom or a chlorine atom is preferable, and a chlorine atom is particularly preferable.

Z ^- is an unconjugated ion, for example, a halogen ion such as a bromide ion or a chloride ion; BF ₄ ^- , AsF ₆ ^- , SbF ₆ ^- , PF ₆ ^- or ClO ₄ ^-, etc. in which an acid having a lower acidity than that of the compound (d01) can be obtained.

The reaction of the compound (d01-1) and the compound (d01-2) is carried out, for example, in the presence of a base.

Examples of the base include organic bases such as triethylamine, 4-dimethylaminopyridine (DMAP) and pyridine; And inorganic bases such as sodium hydride, K ₂ CO ₃ and Cs ₂ CO ₃ .

Specific examples of the reaction solvent include tetrahydrofuran (THF), dichloromethane, dichloroethane, acetone, dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide (DMSO), acetonitrile .

The amount of the compound (d01-2) to be used is preferably approximately 1 to 3 equivalents, more preferably 1 to 2 equivalents relative to the compound (d01-1).

The reaction temperature is preferably -20 to 50 占 폚, more preferably 0 to 40 占 폚.

The reaction time varies depending on the reactivity of the compound (d01-1) and the compound (d01-2), the reaction temperature, and the like, but is usually preferably 1 to 12 hours, more preferably 1 to 6 hours.

The salt exchange between the compound (d01) and the organic cations can be carried out in the same manner as the conventional salt substitution method. For example, the compound (d01) and the salt exchange compound (d02-1) can be reacted by stirring in a solvent such as water, dichloromethane, acetonitrile or chloroform.

The reaction temperature is preferably about 0 to 100 占 폚, and more preferably about 0 to 50 占 폚.

The reaction time varies depending on the reactivity of the compound (d01) and the salt exchange compound (d02-1), the reaction temperature, etc., but is usually preferably from 10 minutes to 24 hours, more preferably from 10 minutes to 12 hours .

After completion of the reaction, conventionally known methods can be used for the isolation and purification of the compound (d01) or the compound (d02). For example, any one of concentration, solvent extraction, distillation, crystallization, recrystallization, , Or a combination of two or more.

[Example]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

In this embodiment, the compound represented by the formula (1) is referred to as "compound (1)" and the compound represented by the other formula is described as such.

Furthermore, in the analysis by NMR, the internal standard of ¹ H-NMR and the internal standard of ¹³ C-NMR are tetramethylsilane (TMS).

&Lt; Preparation of resist composition >

(Examples 1 to 5 and Comparative Examples 1 to 5)

Each component shown in the following Table 1 was mixed and dissolved to prepare a resist composition.

(A) Component Component (B) (D0) component (D1) Component (E) Component (F) Component (S) component Example 1 (A) -1
[100] (B) -1
[10.2] (D0) -1
[6.9] - (E) -1
[2.0] (F) -1
[2.0] (S) -1
[4485] Example 2 (A) -1
[100] (B) -1
[10.2] (D0) -2
[9.9] - (E) -1
[2.0] (F) -1
[2.0] (S) -1
[4485] Example 3 (A) -1
[100] (B) -1
[10.2] (D0) -3
[9.3] - (E) -1
[2.0] (F) -1
[2.0] (S) -1
[4485] Example 4 (A) -1
[100] (B) -1
[10.2] (D0) -4
[9.4] - (E) -1
[2.0] (F) -1
[2.0] (S) -1
[4485] Example 5 (A) -2
[100] (B) -1
[10.2] (D0) -1
[6.9] - (E) -1
[2.0] (F) -1
[2.0] (S) -1
[4485] Comparative Example 1 (A) -1
[100] (B) -1
[10.2] - (D1) -1
[6.7] (E) -1
[2.0] (F) -1
[2.0] (S) -1
[4485] Comparative Example 2 (A) -1
[100] (B) -1
[10.2] - (D1) -2
[6.0] (E) -1
[2.0] (F) -1
[2.0] (S) -1
[4485] Comparative Example 3 (A) -1
[100] (B) -1
[10.2] - (D1) -3
[6.7] (E) -1
[2.0] (F) -1
[2.0] (S) -1
[4485] Comparative Example 4 (A) -1
[100] (B) -1
[10.2] - (D1) -4
[6.0] (E) -1
[2.0] (F) -1
[2.0] (S) -1
[4485] Comparative Example 5 (A) -2
[100] (B) -1
[10.2] (D1) -4
[6.0] (E) -1
[2.0] (F) -1
[2.0] (S) -1
[4485]

In Table 1, the numerical value in [] is the compounding amount (parts by mass). Each of the abbreviations has the following meanings.

(A) -1: a polymer compound represented by the following formula (A1-1); The copolymerization composition ratio l / m obtained by GPC measurement in terms of mass average molecular weight (Mw), molecular weight dispersion (Mw / Mn) in terms of standard polystyrene and carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) The ratio (molar ratio) of each constituent unit) is shown below.

Mw 6900, Mw / Mn 1.61, 1 / m = 50/50.

(A) -2: a polymer compound represented by the following formula (A1-2); Mw 7900, Mw / Mn 1.56, l / m / n / o / p = 35/24/16/13/12.

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

(D0) -1 to (D0) -4: compounds represented by the following formulas (D0-1), (D0-4), (D0-5) and (D0-26); &Lt; Production example of compound >

(D1) -1 to (D1) -4: The compounds represented by the following formulas (D1) -1 to (D1) -4, respectively.

(E) -1: Salicylic acid.

(F) -1: a polymer compound (homopolymer) represented by the following formula (F) -1; Mw 24000, Mw / Mn 1.38.

(S) -1: mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether / cyclohexanone = 45/30/25 (mass ratio).

&Lt; Formation of resist pattern &

Resist patterns were formed by the following resist pattern forming method using each example resist composition.

An organic anti-reflective coating composition "ARC95" (trade name, manufactured by Brewer Science) was applied onto a 12-inch silicon wafer using a spinner and baked on a hot plate at 205 ° C. for 60 seconds and dried, An antireflection film was formed.

Next, each of the resist compositions was coated on the organic antireflection film using a spinner, subjected to a prebake (PAB) treatment at 90 DEG C for 60 seconds on a hot plate, and dried to form a resist film having a thickness of 80 nm Film.

Next, a coating liquid for forming a protective film &quot; TILC-323 &quot; (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was coated on the resist film using a spinner and heated at 90 DEG C for 60 seconds to obtain a top coat .

Next, a mask (6% halftone) was interposed using an ArF liquid immersion exposure apparatus NSR-S609B (Nikon Corporation; NA (numerical aperture) = 1.07, Dipole-X (0.78 / 0.97) w / POLANO) An ArF excimer laser (193 nm) was selectively irradiated onto the resist film on which the coat was formed.

Then, a post-exposure baking (PEB) treatment was performed at 80 占 폚 for 60 seconds, and a solution of 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) Alkali development for 10 seconds was carried out, and then pure rinsing was carried out for 30 seconds, followed by shaking and drying.

As a result, in both examples, a resist pattern of line and space (hereinafter referred to as "LS pattern") in which line patterns with a width of 50 nm were arranged at equal intervals (pitch of 100 nm) was formed in the resist film.

[Optimum exposure dose Eop]

The optimum exposure amount Eop (mJ / cm ² ) at the time when the LS pattern of the target size was formed was obtained by the above-mentioned resist pattern forming method. The results are shown in Table 2.

[Evaluation of exposure margin (EL margin)] [

In forming the LS pattern, the exposure amount when the line of the LS pattern was formed within the range of ± 5% of the target dimension was obtained, and the EL margin (unit:%) was obtained by the following formula. The results are shown in Table 2.

EL margin (%) = (E1-E2 / Eop) 100

E1: exposure dose (mJ / cm ² ) when an LS pattern with a line width of 47.5 nm was formed;

E2: exposure dose (mJ / cm &lt; ² &gt;) when an LS pattern with a line width of 52.5 nm was formed

Further, the EL margin indicates that the amount of change in the pattern size accompanying the fluctuation of the exposure amount is small as the value is large.

[Evaluation of Line Wise Roughness (LWR)]

The LS pattern formed by the resist pattern forming method described above was subjected to measurement of the space width by a SEM (scanning electron microscope, acceleration voltage 300V, trade name: S-9380, Hitachi High Technologies) (3s) of the standard deviation (s) were obtained from the results, and averaged over 3s of 400 points was calculated as a measure indicating the LWR. The results are shown in Table 2.

The smaller the value of 3s, the smaller the roughness of the line width and the more uniform LS pattern was obtained.

[Evaluation of mask error factor (MEEF)] [

A LS pattern having a pitch of 100 nm is formed by using the same mask pattern as that for forming the LS pattern at the same exposure amount and using a mask pattern having a target size of the line pattern of 45 to 54 nm (1 nm unit, 10 points in total) Respectively. At this time, the slope of the straight line when the size (nm) of the line pattern formed on the resist film was plotted on the ordinate axis using the mask pattern on the abscissa of the target size (nm) was calculated as MEEF. The results are shown in Table 2.

MEEF (straight line slope) means that the closer the value is to 1, the better the mask reproducibility.

Eop
(mJ / cm ² ) 5% EL
margin
(%) LWR
(nm) MEEF Example 1 18.5 12.22 3.20 2.05 Example 2 18.5 12.2 3.16 1.97 Example 3 18.9 12.48 3.15 1.96 Example 4 18.7 12.32 3.16 1.94 Example 5 26.4 14.32 4.67 1.96 Comparative Example 1 19.3 11.56 3.49 2.09 Comparative Example 2 19.0 11.27 3.63 2.14 Comparative Example 3 18.7 10.58 3.59 2.38 Comparative Example 4 22.7 11.91 3.35 2.23 Comparative Example 5 32.7 14.11 4.79 1.98

The results shown in the Tables show that the resist compositions of Examples 1 to 4 are superior to the resist compositions of Comparative Examples 1 to 4 and the resist compositions of Example 5 and ELWR , MEEF was good and lithography characteristics were excellent.

&Lt; Preparation examples of compounds: Examples 6 to 62 >

(Example 6)

To a mixture of isethionic acid (7.69 g) and pyridine (92.4 g), campacic chloride (13.5 g) was added. After heating at 40 占 폚 for 3 hours, triphenylsulfonium bromide (17.8 g), pure water (200 g) and dichloromethane (200 g) were added and stirred at room temperature for 12 hours. After stirring, the organic phase was collected, washed with water, and the organic phase solvent was distilled off under reduced pressure to obtain the target compound (D0-1) (25 g). This synthesis route is shown below.

The obtained compound (D0-1) was subjected to NMR measurement, and the structure was classified from the following results.

^{1 H-NMR (400 MHz,} dmso-d6): δ (ppm) = 7.89 (m, 15H, ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m , 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(Examples 7 to 60)

Synthesis was carried out in the same manner as in Example 6 except that triphenylsulfonium bromide was changed to a compound comprising a predetermined cation and bromine ion (Br &lt; ^- & gt ^; ) to obtain the target compounds (D0-2) to (D0-55 Respectively.

(Examples 61 and 62)

Synthesis was conducted in the same manner as in Example 6 except that triphenylsulfonium bromide was changed to a compound comprising a triphenylsulfonium cation and a predetermined anion to obtain the target compounds (D0-56), (D0-57) Respectively.

The obtained compounds (D0-2) to (D0-57) were subjected to NMR measurement, and the respective structures were classified from the following results.

(D0-2)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.72-7.84 (m, 12H, ArH), 7.56 (d, 2H, ArH), 4.43 (t, 2H, COOCH 2), 3.35 (s _{, 3H, CH 3), 2.81} (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 0.79 -1.10 (m, 9H, Campanoic acid)

(D0-3)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.50 (d, 2H, ArH), 8.37 (d, 2H, ArH), 7.93 (t, 2H, ArH), 7.55-7.75 (m, 7H, ArH), 4.43 (t , 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m , &Lt; / RTI &gt; 1 H, campaic acid), 0.79-1.10 (m, 9H,

(D0-4)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.75-7.86 (m, 10H, ArH), 7.61 (s, 2H, ArH), 4.62 (s, 2H, CH 2), 4.43 (t _{, 2H, COOCH 2), 2.81} (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.31 (s, 6H, CH 3), 1.49-1.98 (m, 20H, CCH 2 SO 3 + 0.0 &gt; (m, 9H, &lt; / RTI &gt;

(D0-5)

(M, 10H, ArH), 7.59 (s, 2H, ArH), 4.55 (s, 2H, CH2), 4.43 (t, 2H , COOCH2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.29 (m, 6H, CH3), 1.98 (t, 2H, CCH2 S O3), 1.90-1.93 (m, 4H, CH2, cyclopentyl), 1.48-1.75 (m, 7H, cyclopentyl + camphoric acid), 0.77-1.10 (m, 12H,

(D0-6)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.76-7.82 (m, 10H, ArH), 7.59 (s, 2H, ArH), 4.55 (s, 2H, CH 2), 4.43 (t _{, 2H, COOCH 2), 2.81} (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.29 (m, 6H, CH 3), 1.90-2.08 (m, 4H, cyclopentyl + CCH ₂ SO ₃ ), 1.48-1.75 (m, 10H, CH ₃ + cyclopentyl + campaic acid), 0.79-1.10 (m, 9H,

(D0-7)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 10.05 (s, 1H, OH), 7.64.-7.87 (m, 10H, ArH), 7.56 (s, 2H, ArH), 4.43 (t _{, 2H, COOCH 2), 2.81} (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.22 (m, 6H, CH 3), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, Campanoic acid), 0.79-1.10 (m, 9H, Campanoic acid)

(D0-8)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.71-7.89 (m, 10H, ArH), 7.59 (s, 2H, ArH), 4.53 (s, 2H, CH 2), 4.43 (t _{, 2H, COOCH 2), 2.81} (m, 2H, camphorsulfonic acid), 2.30 (s, 6H, ArCH 3), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, Campanoic acid), 0.79-1.10 (m, 9H, Campanoic acid)

(D0-9)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.75-7.86 (m, 10H, ArH), 7.63 (s, 2H, ArH), 4.55 (s, 2H, CH 2), 4.43 (t _{, 2H, COOCH 2), 2.81} (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.30 (s, 6H, ArCH 3), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, Campanoic acid), 1.43 (s, 9H, t-butyl), 0.79-1.10

(D0-10)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.75-7.87 (m, 10H, ArH), 7.63 (s, 2H, ArH), 4.94 (t, 2H, OCH 2 CF 2), 4.84 _{(s, 2H, OCH 2)} , 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.37 (s, 6H, CH 3), 1.98 _{(t, 2H, CCH 2 SO} 3), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

¹⁹ F-NMR (376 MHz, dmso-d6):? (Ppm) = - 80.4, -119.7

 (D0-11)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.72-7.83 (m, 10H, ArH), 7.59 (s, 2H, ArH), 4.90 (m, 1H, sultone), 4.62 to 4.68 ( m, 3H, CH ₂ O + sultone), 4.43 (t, 2H, COOCH 2), 3.83-3.89 (m, 1H, sultone), 3.43 (m, 1H, sultone), 2.81 (m, 2H, camphorsulfonic acid), 1.75-2.49 (m, 14H, camphorsulfonic acid + CCH ₂ SO ₃ + sultone _{+ Ar-CH 3), 1.56} (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-12)

(Ppm) = 7.74-7.84 (m, 10H, ArH), 7.61 (s, 2H, ArH), 5.42 (t, 1H, oxo-norbornane), 4.97 s, 1H, oxo-norbornane), 4.67-4.71 (m, 4H, CH 2 + oxo-norbornane), 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.69 to 2.73 (m, 1H, oxo-norbornane), 2.41 (m, 1H, camphorsulfonic acid), 2.32 (s, 6H, Ar-CH 3), 2.06-2.16 (m, 2H, oxo-norbornane), 1.98 (t _{, 2H, CCH 2 SO 3)} , 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-13)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.73-7.85 (m, 10H, ArH), 7.59 (s, 2H, ArH), 4.43 (t, 2H, COOCH 2), 3.83 (t _{, 2H, OCH 2), 2.81} (m, 2H, camphorsulfonic acid), 2.33 (s, 6H, CH 3), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 1.45 (m, 4H, CH 2), 1.29 (m, 4H, CH 2), 0.79-1.10 (m, 12H, camphorsulfonic acid + CH ₃₎

(D0-14)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.53 (d, 2H, ArH), 8.27 (d, 2H, ArH), 7.95 (t, 2H, ArH), 7.74 (t, 2H, ArH), 7.20 (s, 1H , ArH), 6.38 (s, 1H, ArH), 4.43 (t, 2H, COOCH 2), 4.05 (t, 2H, cationic _{-OCH 2), 2.86 (s,} 3H, ArCH _{3), 2.81 (m, 2H} , camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.84 (s, 3H, ArCH 3), 1.69 (quin, 2H _{, CH 2), 1.56 (m} , 1H, camphorsulfonic acid), 1.37 (quin, 2H, CH 2), 1.24-1.26 (m, 4H, CH 2), 0.79-1.10 (m, 12H, camphorsulfonic acid + CH ₃ )

(D0-15)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.99-8.01 (d, 2H, Ar), 7.73-7.76 (t, 1H, Ar), 7.58-7.61 (t, 2H, Ar), _{5.31 (s, 2H, SCH 2} C = O), 4.43 (t, 2H, COOCH 2), 3.49-3.62 (m, 4H, CH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.18-2.49 (m , 5H, CH ₂ S + camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-16)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.02-8.05 (m, 2H, phenyl), 7.61-7.73 (m, 3H, phenyl), 4.43 (t, 2H, COOCH 2), 3.76 _{-3.86 (m, 4H, SCH 2} ), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.09-2.12 (m, 2H, CH 2), 1.98 (t, 2H, CCH _{2 SO 3), 1.84-1.93 (m} , 2H, CH 2), 1.61-1.70 (m, 2H, CH 2), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-17)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.04-8.09 (m, 2H, phenyl), 7.69-7.79 (m, 3H, phenyl), 4.43 (t, 2H, COOCH 2), 3.29 _{(s, 6H, CH 3)} , 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid) , 0.79-1.10 (m, 9H, Campanoic acid)

(D0-18)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.07 (d, 2H, phenyl), 7.81 (d, 2H, phenyl), 4.43 (t, 2H, COOCH 2), 4.10 (t, 2H _{, CH 2), 3.59 (d} , 2H, CH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.20 (d, 2H, CH 2), 1.71-2.19 (m _{, 6H, CH 2 + CCH 2} SO 3), 1.56 (m, 1H, camphorsulfonic acid), 1.23 (s, 9H, t-Bu), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-19)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.77-7.89 (m, 10H, ArH), 7.70 (s, 2H, ArH), 5.10 (s, 2H, OCOCH 2 O), 4.43 ( _{t, 2H, COOCH 2),} 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.07-2.19 (m, 9H, CH 3), 1.98 (t, 2H, CCH 2 SO 3 ), 1.56 (m, 1H, Campanoic acid), 0.79-1.10 (m, 9H,

(D0-20)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.84 (d, 6H, ArH), 7.78 (d, 6H, ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H , camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 1.33 (s, 27H, tBu-CH 3), 0.79 -1.10 (m, 9H, Campanoic acid)

(D0-21)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.73-7.89 (m, 12H, ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 ( m, 1H, camphorsulfonic acid), 2.38 (s, 6H, CH 3), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid )

¹⁹ F-NMR (376 MHz, dmso-d6):? (Ppm) = - 70.2

(D0-22)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.69-7.85 (m, 10H, ArH), 7.56 (s, 2H, ArH), 4.75 (s, 4H, CH 2), 4.43 (t _{, 2H, COOCH 2), 2.81} (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.31 (s, 6H, ArCH 3), 2.19 (m, 2H, adamantane), 1.47- 1.98 (m, 18H, adamantane + CCH ₂ SO ₃ + camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-23)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.72-7.84 (m, 10H, ArH), 7.59 (s, 2H, ArH), 4.56 (s, 2H, CH 2), 4.43 (t _{, 2H, COOCH 2), 2.81} (m, 2H, camphorsulfonic acid), 2.49 (m, 2H, adamantane), 2.41 (m, 1H, camphorsulfonic acid), 2.27-2.34 (m, 13H, CH 3 + O (M, 4H, CCH ₂ SO ₃ + adamantane), 1.72-1.79 (m, 2H, adamantane), 1.56 , 9H, &lt; / RTI &gt;

(D0-24)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.72-7.84 (m, 10H, ArH), 7.59 (s, 2H, ArH), 4.64 (s, 2H, CH 2), 4.43 (t _{, 2H, COOCH 2), 3.70} (s, 3H, OCH 3), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.29 (s, 6H, CH 3), 1.98 (t _{, 2H, CCH 2 SO 3)} , 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-25)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.78-7.89 (m, 10H, ArH), 7.64 (s, 2H, ArH), 4.43 (t, 2H, COOCH 2), 3.79 (s _{, 3H, OCH 3), 2.81} (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.32 (s, 6H, CH 3), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, Campanoic acid), 0.79-1.10 (m, 9H, Campanoic acid)

(D0-26)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.76-7.87 (m, 10H, ArH), 7.69 (s, 2H, ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m , 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.13 (s, 6H, CH 3), 1.66-2.03 (m, 17H, adamantane _{+ CCH 2 SO 3), 1.56} (m, 1H , &Lt; / RTI &gt; acid), 0.79-1. 10 (m, 9H,

(D0-27)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.79-7.93 (m, 12H, ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.73 ( 2H, CO-CH ₂ ), 2.41 (m, 1H, Campanoic acid), 2.19 (s, 6H, ArCH ₃ ), 1.98 (t, 2H, CCH ₂ SO ₃ ), 1.65-1.72 _{CH 2), 1.56 (m,} 1H, camphorsulfonic acid), 1.25-1.38 (m, 14H, CH 2), 0.79-1.10 (m, 12H, camphorsulfonic acid + CH ₃₎

(D0-28)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.76 (s, 1H, ArH), 8.59-8.64 (m, 1H, ArH), 8.42 (t, 2H, ArH), 8.03-8.19 ( m, 5H, ArH), 7.81 (t, 1H, ArH), 7.69 (t, 2H, ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H , camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

¹⁹ F-NMR (376 MHz, dmso-d6):? (Ppm) = - 62.1

(D0-29)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 4.43 (t, 2H, COOCH 2), 3.36 (t, 6H, CH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m , 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.68 (quintet, 6H, CH 2), 1.56 (m, 1H, camphorsulfonic acid), 1.35-1.44 (m, 6H, CH 2) , 0.79-1.10 (m, 18H, camphorsulfonic acid + CH ₃₎

(D0-30)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.29 (d, 4H, ArH), 7.93-8.09 (m, 6H, ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m , 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

¹⁹ F-NMR (376 MHz, dmso-d6):? (Ppm) = - 47.9

(D0-31)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.90-8.24 (m, 7H, ArH), 4.43 (t, 2H, COOCH 2), 3.85 (s, 3H, OCH 3), 2.81 ( m, 2H, camphorsulfonic acid), 2.41 (m, 7H, ArCH 3 + camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H , &Lt; / RTI &gt;

¹⁹ F-NMR (376 MHz, dmso-d6):? (Ppm) = - 48.8

(D0-32)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.49 (d, 2H, ArH), 8.30 (d, 2H, ArH), 7.93 (t, 2H, ArH), 7.73 (t, 2H, ArH), 7.30 (s, 2H , ArH), 4.52 (s, 2H, OCH 2), 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid ), 2.16-2.24 (m, 8H, Ar-CH 3 + adamantane), 1.98 (t, 2H, CCH 2 SO 3), 1.44-1.92 (m, 16H, adamantane CH + ₃ + camphorsulfonic acid) , 0.79-1.10 (m, 9H, Campanoic acid)

(D0-33)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 9.73 (br s, 1H, OH), 8.47 (d, 2H, ArH), 8.24 (d, 2H, ArH), 7.91 (t, 2H , ArH), 7.71 (t, 2H, ArH), 7.18 (s, 2H, ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid ), 2.10 (s, 6H, ArCH 3), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-34)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.75-7.87 (m, 10H, ArH), 7.62 (s, 2H, ArH), 4.43 (t, 2H, COOCH 2), 3.97 (t _{, 2H, CH 2), 2.81} (m, 2H, camphorsulfonic acid), 2.03-2.56 (m, 11H, CH 2 + CH 3 + camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m , &Lt; / RTI &gt; 1 H, campaic acid), 0.79-1.10 (m, 9H,

¹⁹ F-NMR (376 MHz, dmso-d6):? (Ppm) = - 123.5, -121.8, -111.6, -78.3

(D0-35)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.75-7.86 (m, 10H, ArH), 7.60 (s, 2H, ArH), 4.43 (t, 2H, COOCH 2), 3.87 (t _{, 2H, CH 2), 2.81} (m, 2H, camphorsulfonic acid), 2.41 (m, 3H, camphorsulfonic acid _{+ CH 2), 2.24-2.35 (m} , 6H, CH 2), 2.12 (m, 6H, N- _{CH 3), 1.98 (t,} 2H, CCH 2 SO 3), 1.86 (t, 2H, CH 2), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-36)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.77-7.89 (m, 10H, ArH), 7.71 (s, 2H, ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m , 2H, camphorsulfonic acid), 2.51 (s, 2H, CH 2), 2.41 (m, 1H, camphorsulfonic acid), 2.20 (s, 6H, CH 3), 1.98 (m, 5H, CCH 2 SO 3 + Ada only 1H), 1.62-1.73 (m, 12H, adamantane), 1.56 (m, 1H,

(D0-37)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.74-7.84 (m, 10H, ArH), 7.61 (s, 2H, ArH), 4.49-4.66 (m, 4H, norbornane + OCH ₂ ), 4.43 (t, 2H, COOCH 2), 3.24 (m, 1H, norbornane), 2.81 (m, 2H, camphorsulfonic acid), 2.44-2.54 (m, 2H, norbornane), 2.41 (m, 1H, camphorsulfonic acid), 2.37 (s, 6H, ArCH _3), 1.91-2.06 (m, 4H, norbornane _{+ CCH 2 SO 3), 1.57-1.67} (m, 3H, norbornane + camphorsulfonic acid), 0.79 to 1.10 ( m, 9H, &lt; / RTI &gt;

(D0-38)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.80-7.92 (m, 10H, ArH), 7.67 (s, 2H, ArH), 4.66 (s, 2H, CH 2), 4.43 (t _{, 2H, COOCH 2), 2.81} (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 2.37 (s, 6H, ArCH 3), 1.98 (t, 2H, CCH 2 SO 3), 1.93 _{(q, 2H, CH 2)} , 1.14-1.57 (m, 9H, cyclohexyl + camphorsulfonic acid), 0.79-1.10 (m, 12H, camphorsulfonic acid + CH ₃₎

(D0-39)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.44 (d, 1H, ArH), 8.22 (m, 2H, ArH), 7.73-7.89 (m, 13H, ArH), 7.50 (d, 1H, ArH), 4.43 (t , 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m , &Lt; / RTI &gt; 1 H, campaic acid), 0.79-1.10 (m, 9H,

(D0-40)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.24 (d, 4H, ArH), 7.59 (t, 2H, ArH), 7.47 (t, 4H, ArH), 4.43 (t, 2H, _{COOCH 2), 2.81 (m,} 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 0.79 to 1.10 ( m, 9H, &lt; / RTI &gt;

(D0-41)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.55 (d, 2H, ArH), 8.38 (d, 2H, ArH), 8.32 (d, 2H, ArH), 8.03 (d, 2H, ArH), 7.93-7.97 (m, 1H , ArH), 7.82-7.88 (m, 8H, ArH), 7.55 (d, 2H, ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-42)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 4.46 (m, 4H, CH 2 (C = O) + COOCH 2), 3.38-3.58 (m, 4H, CH 2 SCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.56-2.33 (m, 24H, Ad + CH 2 CH 2 + CCH 2 SO 3 + camphorsulfonic acid), 0.79-1.10 (m, 9H , &Lt; / RTI &gt;

(D0-43)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.75 (s, 2H, Ar), 4.43 (t, 2H, COOCH 2), 3.91-3.96 (m, 2H, CH 2), 3.72- _{3.79 (m, 2H, CH 2} ), 2.81 (m, 2H, camphorsulfonic acid), 2.29-2.41 (m, 5H, CH 2 + camphorsulfonic acid), 1.75-2.19 (m, 23H, Ar-CH 3 + Ada only Tan _{+ CCH 2 SO 3), 1.56} (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-44)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.82 (m, 2H, Ar), 4.43 (t, 2H, COOCH 2), 3.73-3.91 (m, 4H, CH 2), 2.81 ( m, 2H, camphorsulfonic acid), 1.56-2.43 (m, 31H, Ar-CH 3 + CH 2 + adamantane camphorsulfonic acid + SO ₃ + ₂ + CCH camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid )

(D0-45)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.23 (d, 4H, ArH), 7.98 (d, 4H, ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H , camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 1.37 (s, 18H, CH 3 of tert-butyl), 0.79-1.10 (m, 9H, Campanoic acid)

¹⁹ F-NMR (376 MHz, dmso-d6):? (Ppm) = - 48.5

 (D0-46)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.77-7.98 (m, 10H, ArH), 7.64 (s, 2H, ArH), 4.57 (s, 2H, CH 2 O), 4.43 ( _{t, 2H, COOCH 2),} 2.81 (m, 2H, camphorsulfonic acid), 2.40 (m, 7H, camphorsulfonic acid _{+ CH 3), 2.02-2.26 (m} , 9H, adamantane), 1.98 (t, 2H, _{CCH 2 SO 3), 1.76 (} br s, 6H, adamantane), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-47)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.77-7.89 (m, 10H, ArH), 7.64 (s, 2H, ArH), 5.70 (t, 1H, OCHC = O), 4.82 ( _{s, 2H, ArOCH 2),} 4.46-4.30 (m, 4H, OCOCH 2 + COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.71-2.64 (m, 1H, OCH 2 CH 2), 2.41 (m , 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 2.33-2.24 (m, 7H, CH 3 + OCH 2 CH 2), 1.56 (m, 1H, camphorsulfonic acid), 0.79 to 1.10 ( m, 9H, &lt; / RTI &gt;

(D0-48)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.28 (d, 2H, ArH), 8.11 (d, 1H, ArH), 7.86 (t, 1H, ArH), 7.63-7.81 (m, 7H, ArH), 4.43 (t , 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m , &Lt; / RTI &gt; 1 H, campaic acid), 0.79-1.10 (m, 9H,

(D0-49)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.05 (d, 2H, ArH), 7.74 (d, 2H, ArH), 4.43 (t, 2H, COOCH 2), 3.85 (s, 3H _{, S-CH 3), 2.81} (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 1.30 (s, 18H, t-Bu), 0.79-1. 10 (m, 9H,

(D0-50)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.41 (m, 2H, ArH), 8.12 (d, 1H, ArH), 7.73-7.93 (m, 2H, ArH), 7.19 (d, 1H, ArH), 5.23 (s , 2H, CH 2), 4.95 (m, 1H, adamantane), 4.43 (t, 2H, COOCH 2), 4.03 (m, 2H, CH 2 s), 3.75 (m _{, 2H, CH 2 S),} 2.81 (m, 2H, camphorsulfonic acid), 2.27-2.43 (m, 5H, SCH 2 CH 2 + camphorsulfonic acid), 1.42-1.99 (m, 17H, adamantane + CCH ₂ SO ₃ + &lt; / RTI &gt; cupric acid), 0.79-1.10 (m, 9H,

(D0-51)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.42 (m, 2H, ArH), 8.17 (d, 1H, ArH), 7.78-7.91 (m, 2H, ArH), 7.23 (d, 1H, ArH), 5.26 (s , 2H, CH 2), 4.43 (t, 2H, COOCH 2), 3.75-4.19 (m, 7H, SCH 2 + CH 3), 2.81 (m, 2H, camphorsulfonic acid), _{2.29-2.60 (m, 5H, SCH 2} CH 2 + camphorsulfonic acid), 1.98 (t, 2H, CCH 2 SO 3), 1.56 (m, 1H, camphorsulfonic acid), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-52)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 8.28 (d, 2H, ArH), 8.12 (d, 1H, ArH), 7.88 (t, 1H, ArH), 7.80 (d, 1H, ArH), 7.62-7.74 (m, 5H , ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid), 1.98 (t, 2H, _{CCH 2 SO 3), 1.56 (} m, 1H, camphorsulfonic acid), 1.27 (s, 9H, CH 3), 0.79-1.10 (m, 9H, camphorsulfonic acid)

(D0-53)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.76-7.90 (m, 12H, ArH), 4.43 (t, 2H, COOCH 2), 2.81 (m, 2H, camphorsulfonic acid), 2.62- 2.69 (m, 1H, kampan), 2.41 (m, 1H, camphorsulfonic acid), 2.08-2.26 (m, 8H, Ar-CH 3 + kampan), 1.98 (t, 2H, CCH 2 SO 3), 1.65-1.72 (m, 1H, kampan), 1.56 (m, 1H, camphorsulfonic acid), 1.19 (s, 3H, CH 3), 0.79-1.10 (m, 15H, camphorsulfonic acid + CH ₃ + CH ₃₎

(D0-54)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.76-7.90 (m, 12H, ArH), 5.00 (s, 1H, hyper-lactone), 4.77 (s, 2H, hyper-lactone), _{4.43 (t, 2H, COOCH 2} ), 4.27 (s, 1H, hyper-lactone), 2.94 (s, 1H, hyper-lactone), 2.81 (m, 2H, camphorsulfonic acid), 2.41 (m, 1H, camphorsulfonic acid ), 2.13 (d, 6H, CH 3), 2.11-1.73 (m, 11H, hyper-lactone _{+ CCH 2 SO 3), 1.56} (m, 2H, camphorsulfonic acid + hyper-lactone), 0.79-1.10 (m, 9H, &lt; / RTI &gt;

(D0-55)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.72-7.83 (m, 10H, ArH), 7.59 (s, 2H, ArH), 5.90 (d, 1H, CH), 4.87-5.05 ( (m, 2H, CH ₂ ), 4.43 (t, 2H, COOCH ₂ ), 4.23 (M, 11H, CH ₃ + oxo-sultone + camphor acid + CCH ₂ SO ₃ ), 1.56

(D0-56)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.89 (m, 15H, ArH), 5.04 (m, 1H, decahydro-naphthyl), 3.15 (q, 1H, decahydro-naphthyl), 2H), 2.41 (m, 2H, Campanoic acid), 2.74 (m, 1H, decahydronaphthyl), 2.45 (m, 2H, decahydronaphthyl) Decahydronaphthyl), 1.94 (m, 2H, decahydronaphthyl), 1.50-1.69 (m, 7H, decahydronaphthyl + campaic acid), 0.79-1.10 (m, 10H, )

(D0-57)

^{1 H-NMR (400MHz, dmso} -d6): δ (ppm) = 7.89 (m, 15H, ArH), 4.43 (t, 4H, COOCH 2), 3.40 (t, 2H, C (C) CHSO 3), 2.81 (m, 2H, campaic acid), 1.56 (m, 2H, campaic acid), 0.79-1.10 (m, 18H,

Claims (5)

1. A resist composition which generates an acid upon exposure to light and changes its solubility in a developer by the action of an acid, wherein the resist composition comprises a base component (A) in which the solubility in a developer is changed by the action of an acid, ) Represented by the following formula (D0).

Wherein Y ¹ is a single bond or a divalent linking group. V ¹ is a single bond or a divalent cyclic group which may have a substituent. R ¹ is a monovalent group represented by the formula (r-d0), and * in the formula (r-d0) represents the number of bonds (bonds). R ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent. n is 0 or 1, and when n is 0, V ¹ is not a single bond. m is an integer of 1 or more, and M ^{m +} is a cation of m valency. The method according to claim 1,
And an acid generator component (B) which generates an acid upon exposure. The method according to claim 1 or 2,
(A1) having a constituent unit (a1) containing an acid-decomposable group whose polarity is increased by the action of an acid in the base component (A). A process for producing a resist pattern, comprising the steps of: forming a resist film on a support using the resist composition of any one of claims 1 to 3;
A step of exposing the resist film, and
And developing the resist film to form a resist pattern. A compound represented by the following general formula (d0).

Wherein Y ¹ is a single bond or a divalent linking group. V ¹ is a single bond or a divalent cyclic group which may have a substituent. R ¹ is a monovalent group represented by the formula (r-d0), and * in the formula (r-d0) represents the number of bonds. R ² may be a hydrogen atom or a substituent
Is an alkyl group having 1 to 5 carbon atoms. n is 0 or 1, and when n is 0, V ¹ is not a single bond. m is an integer of 1 or more, and M " ^{m +} is a cation of m valency.