KR20170064477A - Resist composition, method of forming resist pattern and compound - Google Patents

Abstract

Provided are a resist composition, a resist pattern forming method, and a compound.
A resist composition which generates an acid upon exposure to light and changes the solubility in a developing solution by the action of an acid, which comprises an acid generator component which generates an acid upon exposure and a compound represented by the general formula (d0) Wherein the resist composition comprises a photo-acid generator. A step of forming a resist film on the support using the resist composition; a step of exposing the resist film; and a step of developing the resist film after exposure to form a resist pattern. [In the formula (d0), R ¹ and R ² each independently represent a C1-20 branched, branched or cyclic hydrocarbon group which may have a substituent. The substituent bonded to the carbon atom adjacent to the carbonyl group or the sulfonyl group does not have a halogen atom-bearing group, an aromatic group or a proton acceptor functional group. M ^{m +} is an organic cation of m. m is an integer greater than or equal to 1.]
[Chemical Formula 1]

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 resist composition, a resist pattern forming method and a compound.

In the lithography technique, for example, a resist film made of a resist material is formed on a substrate, and the resist film is subjected to selective exposure with radiation such as light, electron beam or the like through a mask having a predetermined pattern formed thereon, A step of forming a resist pattern of a predetermined shape on the resist film is carried out.

A resist material in which the exposed portion changes to a property of dissolving in the developing solution is referred to as a positive type and a resist material in which the exposed portion is changed to a property of not dissolving in the developing solution is referred to as a negative type.

BACKGROUND ART [0002] In recent years, in the production of semiconductor devices and liquid crystal display devices, pattern miniaturization has progressed rapidly by the progress of lithography technology.

In general, the exposure light source is shortened (made into a high energy) by the technique of micronization. Specifically, conventionally, ultraviolet rays represented by g-line and i-line have been used, but now mass production of semiconductor devices using KrF excimer laser or ArF excimer laser has been started. Electron beams, EUV (Extreme Ultraviolet) and X-rays of a shorter wavelength (high energy) than these excimer lasers have also been studied.

Resist materials are required to have lithography properties such as sensitivity to resolution of these exposure light sources and resolving ability to reproduce patterns of fine dimensions.

As a resist material satisfying such a demand, a chemically amplified resist composition containing a base component whose solubility in a developing solution changes 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), the 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, It is generally used to contain ingredients. 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, and the polarity of the base resin is increased by the action of the acid, The exposed portion becomes soluble in the 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 a solvent developing process using a developing solution (organic developing solution) containing an organic solvent is applied, the solubility in the organic developing solution relatively decreases when the polarity of the base resin is increased. Dissolved and removed to form a negative resist pattern in which the exposed portion remains as a pattern. The solvent developing process for forming a negative resist pattern is sometimes referred to as a negative developing process (for example, Patent Document 1).

In general, a quencher component such as an amine component is suitably added to the resist composition in addition to the base component and the acid generator component in order to control the diffusion of acid generated from the acid generator, for example, by exposure For example, Patent Document 2). In such a resist composition, there is a problem that the dimension of the resist pattern formed before and after the storage varies due to the fact that the amine component and the other components are interacted with each other when the resist composition is prepared and stored for a certain period of time.

On the other hand, for example, in Patent Document 2, decomposition (time-dependent deterioration) of other component components during the storage period is suppressed by combining two specific components as a quencher component.

Japanese Laid-Open Patent Publication No. 2009-025723 Japanese Laid-Open Patent Publication No. 2013-3512

While the progress of the fine patterning of the resist pattern progresses, a satisfactory lithography characteristic is further required for the resist material. There has been a room for improvement in the resist material in order to suppress the dimensional fluctuation due to the temporal influence of the resist material and to achieve good lithography characteristics.

However, a compound with a high quenching efficiency has a large time-dependent risk. On the contrary, a compound with a small time-lapse risk has a low quenching efficiency. Therefore, it is possible to suppress the dimensional fluctuation due to time- The improvement of the lithography characteristics is difficult to achieve at the same time.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a resist composition which suppresses dimensional fluctuation due to temporal influence and is excellent in lithography characteristics and a method of forming a resist pattern using the resist composition.

A first aspect of the present invention is a resist composition which generates an acid upon exposure and changes solubility in a developer by the action of an acid, wherein the acid generator component (B) for generating an acid upon exposure and (D0) containing a compound represented by the formula (d0).

A second aspect of the present invention is a resist pattern forming method comprising the steps of: forming a resist film using the resist composition of the first aspect; exposing the resist film; and developing the resist film after exposure to form a resist pattern Lt; / RTI >

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

[Chemical Formula 1]

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, which is a chain, branched chain or cyclic hydrocarbon group. When a substituent is bonded to the carbon atom of R ¹ adjacent to the carbonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . R ² is a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, and is a chain, branched chain or cyclic hydrocarbon group. When a substituent is bonded to the carbon atom of R ² adjacent to the sulfonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . M ^< ^{m + >} is ^{m &lt}; ² > m is an integer of 1 or more.]

According to the present invention, it is possible to provide a resist composition which suppresses dimensional fluctuations due to time-course effects and has good lithography properties, and a method of forming a resist pattern using the resist composition.

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" is intended to include linear, branched, and cyclic monovalent saturated hydrocarbon groups, unless otherwise specified. The alkyl group in the alkoxy group is also the same.

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 the hydrogen atoms of the alkyl group or alkylene group are substituted with fluorine atoms.

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

Includes the case of substituting a hydrogen atom (-H) with a monovalent group and the case of substituting a methylene group (-CH ₂ -) with a divalent 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 terminal of a carboxyl group 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 a substituent (R ^{? 0} ) is substituted with a substituent containing an ester bond, or an ^? -Hydroxyacrylic ester in which a substituent (R ^{? 0} ) is substituted with a hydroxyalkyl group or a group in which the hydroxyl group is substituted do. The carbon atom at the? -Position of the acrylic ester refers to 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 sometimes referred to as an? -Substituted acrylate ester. In some cases, an acrylic acid ester and an alpha-substituted acrylic acid ester are collectively referred to as " (alpha-substituted) acrylic ester ".

The term " structural unit derived from acrylamide " means a structural unit comprising an ethylene double bond of acrylamide cleaved.

The acrylamide may have a hydrogen atom bonded to the carbon atom at the? -Position thereof substituted with a substituent, and one or both of the hydrogen atoms of the amino group of the acrylamide may be substituted with a substituent. 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 substituting the hydrogen atom bonded to the carbon atom at the? -Position of the acrylamide include those exemplified 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 comprising 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 but also other substituents such as alkyl groups and halogenated alkyl groups, and derivatives thereof. Examples of the derivatives thereof include those obtained by substituting the hydrogen atom of the hydroxyl group of the hydroxystyrene which may be substituted with a hydrogen atom at the α-position with an organic group, a benzen ring of hydroxystyrene where the hydrogen atom at the α- And those having a substituent other than a hydroxyl group bonded thereto. The? Position (carbon atom at?) Refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.

Examples of the substituent substituting the hydrogen atom at the? -Position of hydroxystyrene include the same ones exemplified as the substituent at the? -Position in the? -Substituted acrylate ester.

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

The term " vinylbenzoic acid derivative " means a vinylbenzoic acid in which hydrogen atoms at the alpha -position of vinylbenzoic acid are substituted with other substituents such as an alkyl group and a halogenated alkyl group, and derivatives thereof. Examples of the derivatives thereof include those obtained by substituting hydrogen atoms of the carboxyl groups of vinylbenzoic acid in which the hydrogen atom at the α-position may be substituted with organic groups, benzene rings of vinylbenzoic acid in which the hydrogen atom at the α-position may be substituted with substituents, And those having a substituent other than a carboxyl group bonded thereto. The? Position (carbon atom at?) Refers to a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The term " styrene derivative " includes the concept that the hydrogen atom at the? -Position of styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group.

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

The alkyl group as the substituent at the? -Position is preferably a linear or branched alkyl group, and more specifically, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group, tert-butyl group, pentyl group, isopentyl group, 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. The halogen atom includes 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 a group 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 present invention relates to a resist composition which generates an acid upon exposure and changes solubility in a developing solution by the action of an acid, which comprises an acid generator component (B) which generates an acid upon exposure and an acid generator component (D0) containing a compound represented by the following general formula (I).

In the present invention, the resist composition contains a base component (A) (hereinafter also referred to as "component (A)") whose solubility in a developing solution changes by the action of an acid and an acid generator (B) (hereinafter also referred to as " component (B) ").

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, Since the solubility of the component (A) in the developing solution does not change in the light portion, a difference in solubility in the developing solution occurs between the exposed portion and the unexposed portion. Therefore, when the resist film is developed, if the resist composition is a positive type, the exposed portion is dissolved and removed to form a positive resist pattern. When the resist composition is negative, the unexposed portion is dissolved and removed to form a negative resist pattern do.

In the present specification, a resist composition for forming a positive resist pattern by dissolving and removing the exposed portion is referred to as a positive resist composition, and a negative resist composition for forming a negative resist pattern through dissolution and removal of the unexposed portion is referred to as a negative resist composition.

In the present invention, the resist composition may be a positive resist composition or a negative resist composition.

 In the present invention, the resist composition may be used for an alkali development process using an alkali developer for development processing at the time of forming a resist pattern. In the development process, a solvent development using an organic solvent (organic developer) Process.

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

Specifically, in the present invention, the resist composition may contain,

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

(2) The component (A) is a component that generates an acid upon exposure, and may further contain a component (B).

That is, in the case of (2), the component (A) becomes a base component which generates an acid by exposure and has a solubility in the developer changed by the action of an acid. When the component (A) generates an acid upon exposure and the solubility of the component in the developer changes due to the action of an acid, the component (A1) described later generates an acid by exposure, And is preferably a polymer compound whose solubility in a developer varies depending on the action of an acid. 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.

In the present invention, the resist composition is particularly preferably the case of the above (1).

<Photobase Reactive Component>

The resist composition of the present invention contains a photobase deflocculating component (D0) (hereinafter sometimes referred to as "component (D0)") containing a compound represented by the following general formula (d0).

The component (D0) acts as a quencher (acid diffusion control agent) for trapping an acid generated from, for example, a later-described component (B) or the like by exposure and contributes to improvement in lithography characteristics.

Heretofore, it has been known that a compound acting as a quencher has a low quench efficiency and a high pKa of a conjugate acid, which has a low quenching efficiency.

On the other hand, a compound having a high pKa of a conjugated acid is apt to react with other polymers in the resist composition and interacts with other components to cause decomposition (time-course deterioration) of the other components to be mixed (in other words, ) Was thought to be.

Thus, the present inventors have intensively studied and, as a result, have found that by employing a photobase deflocculating component (D0) containing a compound represented by the general formula (d0), a resist composition excellent in storage stability It came to the following.

(2)

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, which is a chain, branched chain or cyclic hydrocarbon group. When a substituent is bonded to the carbon atom of R ¹ adjacent to the carbonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . R ² is a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, and is a chain, branched chain or cyclic hydrocarbon group. When a substituent is bonded to the carbon atom of R ² adjacent to the sulfonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . M ^&lt; ^{m + &gt;} is ^{m &lt}; ² &gt; m is an integer of 1 or more.]

In the formula (d0), R ¹ and R ² are each independently a chain, branched chain or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

As the chain or branched chain hydrocarbon group having 1 to 20 carbon atoms in R ¹ and R ² , an alkyl group having 1 to 10 carbon atoms is more preferable, and as the linear or branched alkyl group, specifically, , Methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, A propyl group, a 2,2-dimethylpropyl group, a 2,2-dimethylbutyl group, a hexyl group, an octyl group, a nonyl group and a decyl group.

Among them, a methyl group, a t-butyl group and a decyl group are more preferable.

When the hydrocarbon group having 1 to 20 carbon atoms in R ¹ and R ² is a cyclic hydrocarbon group, it may be aliphatic, polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. The monocycloalkane preferably has 3 to 8 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, and cyclooctane. The polycyclic alicyclic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from the polycycloalkane. The polycycloalkane preferably has 7 to 12 carbon atoms, and specifically includes adamantane, norbornane, cyclo Heptane, isoborane, tricyclodecane, tetracyclododecane and the like.

When the hydrocarbon group having 1 to 20 carbon atoms in R ¹ and R ² is a cyclic hydrocarbon group, it is more preferably cyclohexane or adamantane among the above.

Examples of the substituent that the hydrocarbon group having 1 to 20 carbon atoms in R ¹ and R ² may have include an alkyl group, an oxygen atom (= O), -COOR ", -OC (= O) R" And the like.

The alkyl group as the substituent is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably a linear or branched chain. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl and hexyl. Among them, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

R "in the above -COOR" and -OC (═O) R "is a hydrogen atom or a linear, branched or cyclic alkyl group of 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, particularly preferably a methyl group or an ethyl group.

When R "is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, monocycloalkane, a group in which at least one hydrogen atom is removed from a polycycloalkane such as a bicycloalkane, a tricycloalkane, or a tetracycloalkane can be exemplified. More specifically, it is preferable that at least one hydrogen atom is removed from a monocycloalkane such as cyclopentane or cyclohexane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane And the like.

As the hydroxyalkyl group as the substituent, the number of carbon atoms is preferably from 1 to 6, and specific examples include groups in which at least one hydrogen atom of the alkyl group exemplified as the alkyl group as the substituent is substituted with a hydroxyl group.

In the present invention, when a substituent is bonded to the carbon atom of R ¹ adjacent to the carbonyl group in the formula (d0), the substituent is selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group And does not have at least one kind selected.

When a substituent is bonded to the carbon atom of R ² adjacent to the sulfonyl group in the formula (d0), the substituent is selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group It shall not have more than one species.

Examples of the group having a halogen atom include a halogen atom, a halogenated alkyl group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and the substituent preferably has no fluorine atom.

Examples of the halogenated alkyl group include halogenated alkyl groups in which some or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms (in particular, fluorine atoms). Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, Etc.), branched chain alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl and the like) and cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl).

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

Specific examples of the aromatic hydrocarbon group include groups obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group), groups in which one of the hydrogen atoms of the aryl group is substituted with an alkylene group (e.g., a benzyl group, Butyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl and 2-naphthylethyl), and the like.

The proton acceptor functional group is a functional group having a group capable of electrostatically interacting with the proton or a lone pair of electrons, and includes, for example, a functional group having a macrocyclic structure such as a cyclic polyether, And a functional group having a nitrogen atom having an electron pair.

Examples of preferred partial structures of the proton acceptor functional groups include crown ethers, azacrown ethers, tertiary amines, secondary amines, primary amines, pyridine, imidazole, pyrazine and aniline structures.

In the present invention, examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R ¹ and R ² include the groups represented by the general formulas (a2-r-1) to (a2-r -7), groups represented by any of the general formulas (a5-r-1) to (a5-r-4), groups represented by any of the general formulas (ax3-r-1) Which may be a contribution.

In the present invention, among the above, a group represented by the general formula (a2-r-2) is preferable.

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

Examples of the organic cation of m-valence of M ^{m +} include the same organic cation as the m-valent organic cation in general formulas (b-1) to (b-3) described later.

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

(3)

Wherein one of R ¹¹ and R ¹² is a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent and the other is a chain, branched chain or ring having 1 to 20 carbon atoms which may have a substituent Lt; / RTI &gt; hydrocarbon group. When a substituent is bonded to the carbon atom of R ¹¹ adjacent to the carbonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . When a substituent is bonded to the carbon atom of R ¹² adjacent to the sulfonyl group in the formula, the substituent has at least one group selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . M ^&lt; ^{m + &gt;} is ^{m &lt}; ² &gt; m is an integer of 1 or more.]

In formula (d0-1), either one of R &lt; ¹¹ &gt; and R &lt; ¹² &gt; is a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent, and the other is a chain- Chain or cyclic hydrocarbon group.

The description of the cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent for R ¹¹ and R ¹² and the chain, branched chain or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent .

The compound represented by the general formula (d0-1) is preferably a compound represented by any of the following general formulas (d0-1a), (d0-1b), or (d0-1c).

[Chemical Formula 4]

^Wherein R ^11a is a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent and R ^12a is a chain or branched hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. When a substituent is bonded to the carbon atom of R ^11a adjacent to the carbonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . When a substituent is bonded to the carbon atom of R ^12a adjacent to the sulfonyl group in the formula, the substituent has at least one group selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . M ^&lt; ^{m + &gt;} is ^{m &lt}; ² &gt; m is an integer of 1 or more.]

In the general formula (d0-1a), the cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent in R ^11a includes a cyclic hydrocarbon group having 3 to 20 carbon atoms, which may have a substituent described in the above R ¹ or R ² A cyclic hydrocarbon group and the same hydrocarbon group.

In the general formula (d0-1a), the chain or branched chain hydrocarbon group having 1 to 20 carbon atoms which may have a substituent in R ^12a includes a hydrocarbon group which may have a substituent described in the above R ¹ or R ² Chain hydrocarbon group having 1 to 20 carbon atoms and the same hydrocarbon group.

[Chemical Formula 5]

^Wherein R ^11b is a chain or branched hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and R ^12b is a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent. When a substituent is bonded to the carbon atom of R ^11b adjacent to the carbonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . When a substituent is bonded to the carbon atom of R ^12b adjacent to the sulfonyl group in the formula, the substituent has at least one group selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . M ^&lt; ^{m + &gt;} is ^{m &lt}; ² &gt; m is an integer of 1 or more.]

Formula (d0-1b) of, R ^11b substituent a hydrocarbon group of chain-like or branched having 1 to 20 carbon atoms which may have in the carbon atoms which may have a substituent described in the above R ¹ or R ² Chain hydrocarbon group having 1 to 20 carbon atoms and the same hydrocarbon group.

In the general formula (d0-1b), the cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent in R ^12b includes a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent described in the above R ¹ or R ² A cyclic hydrocarbon group and the same hydrocarbon group.

[Chemical Formula 6]

[ ^Wherein R ^11c and R ^12c are a chain or branched chain hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. R ^11c and R ^12c may be the same or different. When a substituent is bonded to the carbon atom of R ^11c adjacent to the carbonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . When a substituent is bonded to the carbon atom of R ^12c adjacent to the sulfonyl group in the formula, the substituent has at least one group selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . M ^&lt; ^{m + &gt;} is ^{m &lt}; ² &gt; m is an integer of 1 or more.]

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

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

(7)

[Chemical Formula 8]

[Chemical Formula 9]

The compound represented by the general formula (d0) is a compound wherein a substituent group bonded to the carbon atom of R ¹ adjacent to the carbonyl group in formula (d0) or to the carbon atom of R ² adjacent to the sulfonyl group in formula (d0) , The aromatic group, and the proton acceptor functional group, the pKa of the conjugated acid can be maintained at a relatively high level.

In the present invention, the acid dissociation constant (pKa) of the conjugate acid of the compound represented by the general formula (d0) is preferably larger than 2.5. In the present invention, the pKa of the conjugate acid of the compound represented by the general formula (d0) is more preferably 3.0 or more, and particularly preferably 4.0 or more.

In the present invention, the term &quot; acid dissociation constant (pKa) &quot; refers to an acid which is generally used as an index showing the acid strength of a target substance. The pKa value of the conjugated acid of the compound represented by the general formula (d0) can be determined by measurement by a conventional method. Calculated values using known software such as &quot; ACD / Labs &quot; (trade name, manufactured by Advanced Chemistry Development Co.) may also be used.

When the pKa of the conjugate acid is equal to or more than the lower limit value, the quenching efficiency of the acid increases, and the diffusion of the acid generated from the component (B) described later can be appropriately controlled.

As the component (D0), the above-described compounds may be used singly or in combination of two or more.

In the resist composition of the present invention, the content of the component (D0) is preferably from 0.5 to 20 parts by mass, more preferably from 1 to 10 parts by mass, further preferably from 1 to 8 parts by mass, per 100 parts by mass of the component (A) . When the content of the component (D0) is within the above range, a homogeneous solution can be obtained when each component of the resist composition is dissolved in an organic solvent while sufficiently exhibiting the quenching effect of an acid generated from an acid generator or the like described later, It is preferable because storage stability is improved.

Since the resist composition of the present invention contains the compound (D0) represented by the general formula (d0), the quenching effect of the acid can be enhanced, so that the diffusion length of the acid can be controlled and the storage stability will be.

The compound represented by the general formula (d0) is a compound wherein a substituent group bonded to the carbon atom of R ¹ adjacent to the carbonyl group in formula (d0) or to the carbon atom of R ² adjacent to the sulfonyl group in formula (d0) , The pKa of the conjugated acid can be kept high and the diffusion length of the acid can be appropriately controlled since it does not have at least one kind selected from the group consisting of a group having an amino group, an aromatic group, and a proton acceptor functional group, The efficiency can be made high.

In the conventional quencher component, when the pKa of the conjugated acid is increased, it is likely to react with other polymers in the resist composition. That is, by interacting with ester bonds and the like of other compounding components, decomposition (time-dependent deterioration) of the other compounding components proceeds, in other words, storage stability is poor.

On the other hand, in the present invention, it is considered that the compound represented by the general formula (d0) can inhibit the contact with other compounding components due to the steric hindrance because the anion skeleton is large in volume. As a result, it is possible to prevent the deterioration of the resist composition with time, and it is considered that a resist composition excellent in storage stability can be obtained.

In other words, the present invention is capable of both improving the quench efficiency and alleviating the temporal risk, and is a very useful resist composition.

&Lt; Acid Generator Component: Component (B) &gt;

The resist composition of the present invention contains an acid generator component (B) (hereinafter, referred to as component (B)) which generates an acid upon exposure. As the component (B), there is no particular limitation, and those which have been 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 generators 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 general formula (b-3)

[Chemical formula 10]

Wherein R ¹⁰¹ and R ¹⁰⁴ to R ¹⁰⁸ each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring. Any two of R ¹⁰⁶ to R ¹⁰⁷ may be bonded to each other to form a ring. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. V ¹⁰¹ to V ¹⁰³ are each independently 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 organic cation of m.

{NO ONE}

The anion of component (b-1)

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

(A cyclic group which may have a substituent in R ¹⁰¹ )

The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

The aromatic hydrocarbon group in R &lt; ¹⁰¹ &gt; is preferably an aromatic hydrocarbon ring represented by a bivalent aromatic hydrocarbon group in Va ¹ of the formula (a1-1) described later, or an aromatic compound containing two or more aromatic rings, An aryl group removed from the phenyl group, and a phenyl group and a naphthyl group are preferable.

The cyclic aliphatic hydrocarbon group in R ¹⁰¹ is a group in which one hydrogen atom is removed from the monocycloalkane or polycycloalkane exemplified in the divalent aliphatic hydrocarbon group in Va ¹ of the formula (a1-1) And an adamantyl group and a norbornyl group are preferable.

The cyclic hydrocarbon group for R ¹⁰¹ may include a hetero atom such as a heterocyclic ring and specifically includes a lactone group represented by the general formulas (a2-r-1) to (a2-r-7) containing the formula (a5-r-1) a cyclic group, below ~ (a5-r-4) each represent a -SO ₂ - containing cyclic group, other than the (r-hr-1) ~ (r-hr -16). &Lt; / RTI &gt;

(11)

Examples of the substituent in the cyclic hydrocarbon group represented by R ¹⁰¹ include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group and a nitro group.

The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, , Ethoxy group is most preferable.

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 an alkyl group having 1 to 5 carbon atoms such as a group in which a part or all of hydrogen atoms such as methyl, ethyl, propyl, n-butyl and tert- have.

(Chain alkyl group which may have a substituent in R ¹⁰¹ )

The chain alkyl group represented by R &lt; ¹⁰¹ &gt; may be either linear or branched.

The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, , 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 chain type alkenyl group which may have a substituent in R ¹⁰¹ )

The chain-like alkenyl group of R &lt; ¹⁰¹ &gt; may be either linear or branched, preferably has 2 to 10 carbon atoms, more preferably 2 to 5, still more preferably 2 to 4, 3 is particularly preferable. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butyryl group. Examples of the branched-chain alkenyl group include 1-methylpropenyl group, 2-methylpropenyl group and the like.

As the chain-like alkenyl group, the above-mentioned propenyl group is particularly preferable.

Examples of the substituent in the chain type alkyl group or alkenyl group of R ¹⁰¹ include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, 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 the following formulas (a2-r-1) to (a2-r-7), a group obtained by removing at least one hydrogen atom from a phenyl group, a naphthyl group or a polycycloalkane, -SO ₂ -containing cyclic groups represented by the general formulas (a5-r-1) to (a5-r-4)

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

If the Y ¹⁰¹ 2-valent connecting group containing an oxygen atom, and Y is ^101, it may contain an atom other than an oxygen atom. Examples of the atom 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 Hydrocarbon group-containing oxygen atom-containing linking groups such as an amide bond (-C (= O) -NH-), a carbonyl group (-C (= O) -) ; A combination of a non-hydrocarbon-based oxygen atom-containing linking group and an alkylene group; and the like. The combination may further include a sulfonyl group (-SO ₂ -). Examples of such a combination include linking groups represented by the following formulas (y-al-1) to (y-al-7).

[Chemical Formula 12]

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

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

V as an alkylene group in the ^"101 and V" ^102, specifically, 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 ) -, and -C (CH ₂ CH ₃ ) ₂ -; an 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 - alkyl group such as ethylene; 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 -]; - CH (CH 3) CH 2 CH 2 CH 2 -, -CH 2 CH (CH 3) An alkyltetramethylene group such as CH ₂ CH ₂ -, a pentamethylene group [-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -] and the like.

A part of the methylene groups in the alkylene group in V ' ¹⁰¹ or V' ¹⁰² may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from a cyclic aliphatic hydrocarbon group of Ra ' ³ in the formula (a1-r-1) to be described later, and a cyclohexylene group, -Adamantylene group or a 2,6-adamantylene group is more preferable.

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. A fluorinated alkylene group in the V ¹⁰¹ is, a part or all of the hydrogen atoms of the alkylene group of the ¹⁰¹ V may be substituted with a fluorine atom. Among them, V ¹⁰¹ is preferably a single bond or a fluorinated alkylene group having 1 to 4 carbon atoms.

In 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 portion of the component (b-1) include, for example,

When Y &lt; ¹⁰¹ &gt; is a single bond, fluorinated alkylsulfonate anion such as trifluoromethanesulfonate anion or perfluorobutanesulfonate anion can be exemplified, and Y &lt; ¹⁰¹ &gt; is a divalent link An anion represented by any one of the following formulas (an-1) to (an-3) may be mentioned.

[Chemical Formula 13]

Wherein R " ¹⁰¹ represents an aliphatic cyclic group which may have a substituent, a group respectively represented by the above formulas (r-hr-1) to (r-hr-6), or a chain alkyl group and; r ^"102 is an aliphatic cyclic group which may have a substituent, described later expression (a2-r-1) ~ lactone-containing cyclic group represents respectively (a2-r-7), or the general formula described below (a5- r-1) ~ (a5- r-4) -SO 2 represent respectively-containing cyclic group and; R ^"103 is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a substituent V " ¹⁰¹ is a fluorinated alkylene group; L" ¹⁰¹ is -C (═O) - or -SO ₂ -; and v "is independently an integer of 0 to 3 And q "are each independently an integer of 1 to 20, and n" is 0 or 1. &quot;

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

The aromatic cyclic group which may have a substituent in R " ¹⁰³ is preferably a group exemplified as an aromatic hydrocarbon group in the cyclic hydrocarbon group for R &lt; ^{101 &} gt ;. Examples of the substituent include the same substituent as the substituent that the aromatic hydrocarbon group in R ¹⁰¹ may be substituted.

The chain alkyl group which may have a substituent in R " ¹⁰¹ is preferably a group exemplified as a chain alkyl group in R &lt; ^{101 &} gt ;. The chain type alkenyl group which may have a substituent in R " ¹⁰³ is preferably a group exemplified as a chain type alkenyl group in R &lt; ^{101 &} gt ;. V " ¹⁰¹ is preferably a fluorinated alkylene group having 1 to 3 carbon atoms, particularly preferably -CF ₂ -, -CF ₂ CF ₂ -, -CHFCF ₂ -, -CF (CF ₃ ) CF ₂ - -CH (CF ₃₎ CF ₂ - a.

The anion 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-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, Include the same ones as R ¹⁰¹ in the formula (b-1), respectively. However, R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring.

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

The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and still more preferably 1 to 3 carbon atoms. The number of carbon atoms of the chain-like alkyl group represented by R ¹⁰⁴ and R ¹⁰⁵ is preferably as small as possible within the above range of the number of carbon atoms and solubility in a resist solvent. In the chain alkyl group represented by R ¹⁰⁴ and R ^105, the more the number of hydrogen atoms substituted with fluorine atoms is, the stronger the strength of the acid is, and since the transparency to the high energy light of 200 nm or less and the electron beam is improved, Do. The ratio of the fluorine atoms in the chain alkyl group, that is, the fluoride group is preferably 70 to 100%, more preferably 90 to 100%, and most preferably, the perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms to be.

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 of component (b-3)

In the formula (b-3), R ¹⁰⁶ to R ¹⁰⁸ are each independently a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, Include the same ones as R ¹⁰¹ in the formula (b-1), respectively.

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

{Kationbu}

In the formulas (b-1), (b-2) and (b-3), M'm ⁺ is an organic cation other than the cation in the compound of the formula (b1-1) Sulfonium cation or iodonium cation, and a cation represented by the following general formulas (ca-1) to (ca-4) is particularly preferable.

[Chemical Formula 14]

[Wherein, R ²⁰¹ ~ R ²⁰⁷ and R ²¹¹ ~ R ²¹² each independently represents an aryl group, an alkyl group or an alkenyl group which may have a ^{substituent, R 201 ~ R 203, R} 206 ~ R 207, R 211 ~ R ²¹² may bond together to form a ring 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, an alkyl group, an alkenyl group, or -SO ₂ which may contain a substituent group-containing a cyclic group, L ²⁰¹ is Y ²⁰¹ represents, independently of each other, an arylene group, an alkylene group or an alkenylene group, x is 1 or 2, and W ²⁰¹ represents ((O) - or - x + 1).

The aryl group for R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² includes an unsubstituted aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group.

The alkyl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² is a chain or cyclic alkyl group and preferably has 1 to 30 carbon atoms.

The alkenyl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² preferably has 2 to 10 carbon atoms.

Examples of the substituent 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, r-1) to (ca-r-7).

The aryl group in the arylthio group as a substituent is the same as exemplified for R ¹⁰¹ , and specifically includes a phenylthio group or a biphenylthio group.

[Chemical Formula 15]

: Wherein each R ' ²⁰¹ independently represents a hydrogen atom, a cyclic group which may have a substituent, a chain-like alkyl group or a chain-like alkenyl group.

The cyclic group which may have a substituent of R ' ²⁰¹ , the chain type alkyl group which may have a substituent, or the chain type alkenyl group which may have a substituent is the same as R ¹⁰¹ in the above formula (b-1) , A cyclic group which may have a substituent or a chain-like alkyl group which may have a substituent may be the same as the acid dissociable group represented by the formula (a1-r-2) described later.

R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ , and R ²¹¹ to R ²¹² , when mutually bonded to form a ring together with the sulfur atom in the formula, may be a hetero atom such as a sulfur atom, an oxygen atom or a nitrogen atom, May be bonded through a functional group such as -SO-, -SO ₂ -, -SO ₃ -, -COO-, -CONH- or -N (R _N ) - (R _N is an alkyl group having 1 to 5 carbon atoms) do. As the ring to be formed, one ring containing a sulfur atom in the formula in its ring skeleton is preferably 3 to 10 atomic rings including a sulfur atom, and it is particularly preferable that it is a 5 to 7-membered ring. Specific examples of the ring to be formed include, for example, thiophene ring, thiazole ring, benzothiophene ring, thianthrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thiosanthene ring, A thianthrene ring, a phenoxathiine ring, a tetrahydrothiophenium ring, a tetrahydrothiopyranium 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 bond to each other to form a ring.

R ²¹⁰ is an optionally substituted aryl group, optionally substituted alkyl, optionally substituted alkenyl, or optionally substituted -SO ₂ - containing cyclic group.

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

The alkyl group in R ²¹⁰ is a chain or cyclic alkyl group, preferably having 1 to 30 carbon atoms.

The alkenyl group in R ²¹⁰ preferably has 2 to 10 carbon atoms.

Examples of the -SO ₂ -containing cyclic group which may have a substituent in R ²¹⁰ include the same ones as the "-SO ₂ -containing cyclic group" of Ra ²¹ in the general formula (a2-1) described later, A group represented by the following general formula (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 obtained by removing one hydrogen atom from the aryl group exemplified as the aromatic hydrocarbon group for R ¹⁰¹ in the above 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) to be described later.

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 for W ²⁰¹ , a divalent hydrocarbon group which may have a substituent is preferable, and the same hydrocarbon group as Ya ²¹ in the general formula (a2-1) described later can be exemplified. The bivalent 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 ends 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.

Connection of the trivalent group is ²⁰¹ W, and ²⁰¹ W the group 1 to remove the hydrogen atom from the divalent linking group in, in addition to the divalent linking group, and the like which combines the divalent connecting group.

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 the suitable cation represented by the formula (ca-1) include cation represented by the following formulas (ca-1-1) to (ca-1-63)

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

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,

[Chemical Formula 19]

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

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

[Chemical Formula 20]

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

[Chemical Formula 21]

As the component (B), the above-mentioned acid generators may be used singly or in combination of two or more.

The content of the component (B) in the resist composition of the present invention is preferably 0.5 to 60 parts by mass, more preferably 1 to 50 parts by mass, further preferably 1 to 40 parts by mass, per 100 parts by mass of the component (A). By setting the content of the component (B) within 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 is obtained, and storage stability is improved, which is preferable.

&Lt; Component (A) &gt;

In the present invention, the &quot; base component &quot; 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 is improved, and furthermore, a nano-level photosensitive resin pattern is easily formed.

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

As the non-polymeric polymer, those having a molecular weight of 500 or more and less than 4000 are usually used. Hereinafter, the term &quot; low molecular weight compound &quot; refers to a non-polymeric substance having a molecular weight of 500 or more and less than 4000.

As the polymer, usually those having a molecular weight of 1000 or more are used. Hereinafter, "resin" refers to a polymer having a molecular weight of 1000 or more.

As the molecular weight of the polymer, a weight 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 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 upon exposure.

In the present invention, the component (A) is a structural unit containing an acid-decomposable group whose polarity is increased by the action of an acid (hereinafter sometimes referred to as "structural unit (a1)"), -SO ₂ - (Hereinafter sometimes referred to as a &quot; constituent unit (a2) &quot;) and a constituent unit containing a polar group-containing aliphatic hydrocarbon group (hereinafter referred to as & (Hereinafter, may be referred to as "structural unit (a4)"), a structural unit containing a lactone-containing cyclic group or a carbonate-containing cyclic group ( (Hereinafter sometimes referred to as &quot; structural unit (a5) &quot;).

(Constituent unit (a1))

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

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

Examples of the acid decomposable group whose polarity is increased by the action of an acid include groups which are decomposed by the action of an acid to generate a polar group.

Examples of the polar group include a carboxyl 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 sometimes referred to as "OH-containing polar group") is preferable, a carboxyl group or a hydroxyl group is 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).

Here, &quot; acid dissociable genitalia &

(i) a group having an acid dissociable property by which the bond between the acid dissociable group and an atom adjacent to the acid dissociable group can be cleaved by the action of an acid, or

(ii) a group in which a bond between the acid dissociable group and an atom adjacent to the acid dissociable group is cleaved by the occurrence of a decarboxylation reaction after cleavage of a part of the bond by the action of an acid

.

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

The acid dissociable group is not particularly limited and those proposed so far as acid dissociable groups of base resins for chemically amplified resists can be used.

Among the polar groups, examples of the acid dissociable group for protecting the carboxyl group or the hydroxyl group include an acid dissociable group represented by the following general formula (a1-r-1) (hereinafter referred to as "acetal type acid dissociable group" ).

[Chemical Formula 22]

Wherein Ra ' ¹ and Ra' ² are each a hydrogen atom or an alkyl group, Ra ' ³ is a hydrocarbon group, and Ra' ³ is any of Ra ' ¹ and Ra' ² .

Examples of the alkyl group represented by Ra ' ¹ and Ra' ^{2 in} the formula (a1-r-1) include the same alkyl groups exemplified as substituent groups which may be bonded to the carbon atom at the α- And a methyl group or an ethyl group is preferable, and a methyl group is most preferable.

The hydrocarbon group of Ra ' ³ is preferably an alkyl group of 1 to 20 carbon atoms, more preferably an alkyl group of 1 to 10 carbon atoms, and is preferably a linear or branched alkyl group. Specific examples thereof include a methyl group, Propyl group, isopropyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, Dimethylpropyl group, 2,2-dimethylbutyl group and the like.

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

In the case where the aromatic hydrocarbon group is an aromatic ring, specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene, etc. Part of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms Aromatic heterocyclic rings, and the like. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom and a nitrogen atom.

Specific examples of the aromatic hydrocarbon group include groups obtained by removing one hydrogen atom from the aromatic hydrocarbon ring (aryl group), groups in which one of the hydrogen atoms of the aryl group is substituted with an alkylene group (e.g., a benzyl group, Butyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl and the like). 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 of Ra' ¹ and Ra ' ² to form a ring, the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group, a tetrahydrofuranyl group, and the like.

Examples of the acid dissociable group for protecting the carboxyl group among the polar groups include an acid dissociable group represented by the following general formula (a1-r-2) (an acid represented by the following formula (a1-r-2) In the dissociable group, what is constituted by an alkyl group is hereinafter referred to as &quot; tertiary alkyl ester-type acid-dissociable group &quot; for convenience).

(23)

[In the formula, Ra ' ⁴ to Ra' ⁶ are hydrocarbon groups, and Ra ' ⁵ and Ra' ⁶ may combine with each other to form a ring.]

Examples of the hydrocarbon group of Ra ' ⁴ to Ra' ⁶ include the same groups as those of Ra ' ³ above. 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 groups represented by the following general formula (a1-r2-1).

On the other hand, when Ra ' ⁴ to Ra' ⁶ do not bond to each other and are independent hydrocarbon groups, there may be mentioned groups represented by the following general formula (a1-r2-2).

&Lt; EMI ID =

[Wherein, Ra, a group forming 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 the, exemplified as the "Ra in the alkyl group is formulas (a1-r-1) of the alkyl group having 1 to ¹⁰ 10 ^'3 linear or branched alkyl group of Ra One period is preferable. Equation (a1-r2-1) of, Ra is preferably an alkyl group exemplified as the ring type of "aliphatic cyclic group which ¹¹ this configuration, Ra in the formula (a1-r-1) ' 3.

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

Equation (a1-r2-2) of, Ra is preferably a linear, branched or cyclic alkyl group exemplified as the hydrocarbon groups of ^{3, 13,} formula (a1-r-1) Ra of the ' Do. Among them, it is more preferable that R &lt; ³ &gt; is a group exemplified as a cyclic alkyl group.

Specific examples of the formula (a1-r2-1) are shown below. In the following formulas, &quot; * &quot;

(25)

Specific examples of the formula (a1-r2-2) are shown below.

(26)

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 referred to as a "tertiary alkyloxycarbonyl acid dissociable group" ).

(27)

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

In the formula (a1-r-3), Ra ' ⁷ to Ra' ⁹ are 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? -Position may be substituted with a substituent, an acid-decomposable group whose polarity is increased by the action of an acid; Structural units derived from a vinylbenzoic acid or a vinylbenzoic acid derivative wherein at least a part of the hydrogen atoms in the hydroxyl group of the structural unit derived from styrene or a hydroxystyrene derivative is protected by a substituent containing an acid-decomposable group, -C (═O) -OH in which at least a part of the hydrogen atoms are protected by a substituent containing an 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.

As the structural unit (a1), a structural unit represented by the following general formula (a1-1) or (a1-2) is preferable.

(28)

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, a urethane bond or an amide bond, n _a1 is 0 to 2,

Ra ¹ is an acid dissociable group represented by the above formulas (a1-r-1) to (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 general formula (a1-1), the alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group , n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group and 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. The halogen atom includes 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 in Va ¹ may be saturated or unsaturated, and is preferably saturated.

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

As Va ^1, the bivalent hydrocarbon group may be bonded through an ether bond, a urethane bond or an amide bond.

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

As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specific examples thereof include a methylene group [-CH ₂ -], an ethylene group [- (CH ₂ ) ₂ -] and a trimethylene group [- CH ₂ ) ₃ -], tetramethylene group [- (CH ₂ ) ₄ -], pentamethylene group [- (CH ₂ ) ₅ -] and the like.

Aliphatic hydrocarbon group of the branched, with preferably an alkylene group of branched, and _{specifically, -CH (CH 3) -,} -CH (CH 2 CH 3) -, -C (CH 3) 2 -, _{-C (CH 3) (CH 2} CH 3) -, -C (CH 3) (CH 2 CH 2 H 3) -, -C (CH 2 CH 3) 2 - a methylene group, such as alkyl; -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 -; alkyltrimethylene groups such as -CH (CH ₃ ) CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) CH ₂ -, and the like; -CH (CH ₃ ) CH ₂ CH _And alkyltetramethylene groups such as ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) CH ₂ CH ₂ -, and the like. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Examples of the aliphatic hydrocarbon group containing a ring in the structure include alicyclic hydrocarbon groups (groups in which two hydrogen atoms have been removed from the aliphatic hydrocarbon ring), groups in which alicyclic hydrocarbon groups are bonded to the ends of a linear or branched aliphatic hydrocarbon group , And groups in which an alicyclic hydrocarbon group is introduced in the midst of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same ones 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 polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane, cyclohexane, and the like. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from the polycycloalkane. The polycycloalkane preferably has 7 to 12 carbon atoms, and specifically includes adamantane, norbornane, iso Borane, tricyclodecane, tetracyclododecane and the like.

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

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

Specific examples of the aromatic ring of the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene and phenanthrene; aromatic heterocyclic rings in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom ; And the like. Examples of the heteroatom in the aromatic heterocyclic ring 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 have been removed from the aromatic hydrocarbon ring (arylene group), one of the hydrogen atoms of the group (aryl group) in which one hydrogen atom has been removed from the aromatic hydrocarbon ring, An aryl group in the aryl group of an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, (1), and the like. 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 valency in Wa ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated, and is usually saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or a combination of a linear or branched aliphatic hydrocarbon group and a ring-containing aliphatic hydrocarbon group And specifically a group the same as Va ¹ of the above-mentioned formula (a1-1) can be mentioned.

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

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

[Chemical Formula 29]

In the formulas (a1-2-01), Ra ² is an acid-dissociable group represented by the formula (a1-r-1) or (a1-r-3). n _a2 is an integer of 1 to 3, preferably 1 or 2, and more preferably 1. c is an integer of 0 to 3, preferably 0 or 1, and more preferably 1. R is the same as above.

Specific examples of the formulas (a1-1) and (a1-2) are shown below. In the following formulas, R ^{? Represents} a hydrogen atom, a methyl group or a trifluoromethyl group.

(30)

(31)

(32)

(33)

(34)

The proportion of the structural unit (a1) in the component (A) 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 (A) % Is more preferable. By setting it to the lower limit value or more, lithography characteristics such as sensitivity, resolution, and LWR are improved. In addition, by setting the value below the upper limit value, balance with other constituent units can be obtained.

(The constituent unit (a2))

A structural unit (a2) is, -SO ₂ - is a structural unit containing a cyclic group containing.

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

In the present invention, the component (A1) preferably contains the structural unit (a2).

When the structural unit (a1) contains a -SO ₂ -containing cyclic group in its structure, the structural unit also corresponds to the structural unit (a2) , And does not correspond to the structural unit (a2).

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

(35)

(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 is -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 -SO ₂ -containing cyclic group.]

The bivalent linking group of Ya ²¹ is not particularly limited, but may be a bivalent hydrocarbon group which may have a substituent or a divalent linking group containing a heteroatom.

(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 preferably 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. Specifically, Va in the formula (a1-1) ¹ &lt; / RTI &gt;

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

Examples of the aliphatic hydrocarbon group having a ring in the structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that may contain a substituent group containing a hetero atom in the ring structure, A group in which a hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is introduced in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same ones as 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 for 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, an ethoxy group, an n-propoxy group, an isopropoxy group, a n-butoxy group or a tert- , Ethoxy group is most preferable.

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 carbon atoms constituting the cyclic structure includes a hetero atom. The substituent containing the heteroatom 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 in Va ¹ in the above-mentioned formula (a1-1).

In the aromatic hydrocarbon group, the hydrogen atom contained in 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 ^{&lt; a} &gt; is a divalent linking group containing a heteroatom, preferable examples of the linking group include -O-, -C (= O) -O-, -C (= O) -, -OC -, -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 - or ^{-Y 21 -OC (= O) -Y} 22 - of the group represented by the formula, Y ²¹ and Y ²² each independently represent a divalent hydrocarbon group which may have a substituent, O represents an oxygen atom, and m 'represents an integer of 0 to 3).

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 - or ^{-Y 21 -OC (= O) -Y} 22 - of, Y ²¹ and Y ²² are, each independently, a divalent hydrocarbon group which may have a substituent group. As the bivalent hydrocarbon group, the same groups as the "bivalent hydrocarbon group which may have a substituent" exemplified in the description of the bivalent linking group are mentioned.

As Y ²¹ , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group or an ethylene group is particularly preferable.

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 linear alkyl group having 1 to 5 carbon atoms, preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

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. That is, 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 -. Among them, a group represented by the formula - (CH ₂ ) _{a '} -C (═O) -O- (CH ₂ ) _b' - is preferable. In the formula, a 'is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1. b 'is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1.

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

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

The "-SO ₂ -containing cyclic group" refers to a cyclic group containing a ring containing -SO ₂ - in the cyclic skeleton, and specifically, the sulfur atom (S) in -SO ₂ - Is a cyclic group that forms part of the ring skeleton of &lt; RTI ID = 0.0 &gt; A ring containing -SO ₂ - in the ring skeleton is counted as the first ring, and when the ring is only a ring, it is called a monocyclic ring, and when it has another ring structure, it is called a ring ring regardless of its structure. The -SO ₂ -containing cyclic group may be monocyclic or polycyclic.

The -SO ₂ -containing cyclic group as the cyclic hydrocarbon group in R ¹ is preferably a cyclic group containing -O-SO ₂ - in the cyclic skeleton thereof, that is, -OS- in -O-SO ₂ - It is preferably a cyclic group containing a sultone ring which forms part of the ring skeleton. 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).

(36)

R &lt; ⁵¹ &gt; each independently represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR &quot;, -OC (= O) R &quot;, a hydroxyalkyl group or a cyano group; 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 "is the same as A" in the general formulas (a2-r-1) to (a2-r-7) described later. Ra ^'51 alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, -COOR in ", -OC (= O) R ", a hydroxyl group, the formula (a2-r-1) ~ (a2- is the same as r-7) of the Ra ^'21.

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.

(37)

(38)

[Chemical Formula 39]

As the -SO ₂ -containing cyclic group, the group represented by the general formula (a5-r-1) is preferable, and the groups represented by the general formulas (r-sl-1-1) at least one member selected from the group consisting of (r-sl-3-1) and (r-sl-4-1) 1) is most preferable.

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 from 1 to 80 mol%, more preferably from 5 to 5 mol% based on the total of all structural units constituting the component (A1) To 70 mol%, more preferably 10 mol% to 65 mol%, and particularly preferably 10 mol% to 60 mol%. The effect of incorporating the structural unit (a2) can be sufficiently obtained by setting the amount to not less than the lower limit value, and when it is not more than the upper limit value, balance with other constituent units can be obtained, and various lithography characteristics and pattern shapes are improved.

(The 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 structural 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 linear or branched hydrocarbon group having 1 to 10 carbon atoms (preferably an alkylene group) or a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be monocyclic or polycyclic. For example, the 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 in which two or more hydrogen atoms have been removed from a bicycloalkane, a tricycloalkane, a tetracycloalkane or the like. Specific examples thereof include groups obtained by removing two or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isoborane, tricyclodecane and tetracyclododecane. Among these polycyclic groups, groups in which two or more hydrogen atoms have been removed from adamantane, groups in which two or more hydrogen atoms have been removed from norbornane, and groups in which two or more hydrogen atoms have been removed from tetracyclododecane are industrially preferable.

The constituent unit (a3) is not particularly limited as long as it contains a polar group-containing aliphatic hydrocarbon group.

The constituent unit (a3) is preferably a constituent 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, and 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, When the hydrocarbon group is a polycyclic group, preferred examples include a constituent unit represented by the following formula (a3-1), a constituent unit represented by the formula (a3-2), and a constituent unit represented by the formula (a3-3)

(40)

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. These are preferably those in which a 2-norbornyl group or a 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) contained in the component (A1) may be one kind or two or more kinds.

The proportion of the structural unit (a3) in the component (A1) is preferably 5 to 50 mol%, more preferably 5 to 40 mol% based on the total of all the structural units constituting the resin component (A1) , More preferably from 5 to 25 mol%.

When the ratio of the constituent unit (a3) is set to be a lower limit value or more, the effect of containing the constituent unit (a3) is sufficiently obtained, 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 acidic cyclic group. When the component (A1) has the structural unit (a4), dry etching resistance of the formed resist pattern is improved. 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 and the shape of the resist pattern, especially in the case of organic solvent development.

The "acid-labile cyclic group" in the structural unit (a4) is a cyclic group remaining in the structural unit as it is when the acid is generated from the later-described component (B) by exposure and does not dissociate even if the acid acts.

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

Particularly, at least one member selected from a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group and a norbornyl group is preferable from the viewpoint 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).

(41)

[Wherein R ^{? Represents} a hydrogen atom, a methyl group or a trifluoromethyl group]

The constituent unit (a4) contained in the component (A1) may be one type or two or more types.

When the constituent unit (a4) is contained in the component (A1), the proportion of the constituent unit (a4) is preferably from 1 to 30 mol%, more preferably from 10 to 10 mol% based on the total constituent units constituting the component By mole to 20% by mole.

(The constituent unit (a5))

The structural unit (a5) is a structural unit containing a lactone-containing cyclic group or a carbonate-containing cyclic group.

The lactone-containing cyclic group or the carbonate-containing cyclic group of the constituent unit (a5) is effective for enhancing 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 or a carbonate-containing cyclic group in its structure, the structural unit also corresponds to the structural unit (a5) ), And does not correspond to the structural unit (a5).

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

The "lactone-containing cyclic group" refers to a cyclic group containing a ring (lactone ring) containing -O-C (═O) - in the cyclic backbone. When a lactone ring is counted as a first ring, only a lactone ring is referred to as a monocyclic ring, and when it has another ring structure, it is referred to as a polycyclic ring regardless of its structure. The lactone-containing cyclic group may be monocyclic or polycyclic.

The lactone-containing cyclic group as the cyclic hydrocarbon group in R ¹ is not particularly limited, and any cyclic group can be used. Specific examples thereof include groups represented by the following general formulas (a2-r-1) to (a2-r-7). Hereinafter, &quot; * &quot;

(42)

[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", hydroxy group or cyano group; R " Is an alkylene, oxygen or sulfur atom of 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, n 'is an integer of 0 to 2, m' is 0 or 1, 1.]

In the general formulas (a2-r-1) to (a2-r-7), A "represents an alkyl group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) An oxygen atom, or a sulfur atom. The alkylene group having 1 to 5 carbon atoms in A "is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group and an isopropylene group. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include a group in which -O- or -S- is interposed between the terminal or carbon atom of the alkylene group, and examples thereof include -O -CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ - and the like. A "is preferably an alkylene group of 1 to 5 carbon atoms or -O-, more preferably an alkylene group of 1 to 5 carbon atoms, and most preferably a methylene group. Ra ^'21 are each independently, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, -COOR ", -OC (= O ) R", hydroxy group or cyano group.

With Ra 'group in ²¹ is an alkyl group of 1 to 5 carbon atoms are preferred. Ra 'The alkoxy group in ²¹ is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably a linear or branched chain. Specifically, there may be mentioned a group which is an alkyl group and an oxygen atom (-O-) exemplified as the alkyl group in the above-mentioned Ra ^'21 connection.

Ra 'is a halogen atom in the ^21, and a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a fluorine atom is preferable.

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

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

(43)

The "carbonate-containing cyclic group" means a cyclic group containing a ring (carbonate ring) containing -O-C (═O) -O- in the cyclic backbone. When the carbonate ring is counted as the first ring, only the carbon ring is monocyclic, and when it has another ring structure, it is called the polycyclic ring regardless of its structure. The carbonate-containing cyclic group may be monocyclic or polycyclic.

The cyclic hydrocarbon group-containing cyclic group as the cyclic hydrocarbon group in R ¹ is not particularly limited, and any cyclic group can be used. Specific examples thereof include groups represented by the following formulas (ax3-r-1) to (ax3-r-3).

(44)

[Wherein, Ra ^'x31 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", hydroxy group or cyano group; R " Is an alkylene group, an oxygen atom or a sulfur atom of 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, and q 'is 0 or 1.]

A "in the general formulas (ax3-r-1) to (ax3-r-3) is the same as A" in the general formula (a2-r-1).

(A2-r-1) to (a2-r-1) in the above Ra ^'31 are each an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, -COOR " -r-7) it can be given in the same as those exemplified in the explanation of Ra ^'21.

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

[Chemical Formula 45]

Among them, the lactone-containing cyclic group is preferably a group represented by the general formula (a2-r-1) or (a2-r-2), more preferably a group represented by the formula (r-lc-1-1) .

The constituent unit (a5) of the component (A1) may be one kind or two or more kinds.

When the component (A1) has the structural unit (a5), the proportion of the structural unit (a5) is preferably from 1 to 80 mol%, more preferably from 5 to 5 mol% based on the total of all structural units constituting the component (A1) To 70 mol%, more preferably 10 mol% to 65 mol%, and particularly preferably 10 mol% to 60 mol%. The effect of containing the structural unit (a5) can be sufficiently obtained by setting the amount to be not lower than the lower limit value, and when it is not more than the upper limit value, balance with other structural units can be obtained and various lithographic characteristics and pattern shapes such as DOF and CDU are improved.

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

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) CF ₃ ) ₂ -OH group may be introduced. As described above, 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).

In the present invention, the weight average molecular weight (Mw) of the component (A1) (based on polystyrene conversion by gel permeation chromatography) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 1,500 to 30,000 , And most preferably from 2,000 to 20,000. When the upper limit of the range is less than the upper limit, there is a sufficient solubility in a resist solvent for use as a resist. When the lower limit of the above range is exceeded, the dry etching resistance and the resist pattern cross-sectional shape are favorable.

The component (A1) may be used singly or in combination of two or more.

The proportion of the component (A1) in the base component (A) is preferably 25% by mass or more, more preferably 50% by mass, further preferably 75% by mass, and most preferably 100% by mass based on the total mass of the base component Mass%. When the ratio is 25 mass% or more, the lithography characteristics are further improved.

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.

&Lt; Basic compound component: (D) component &gt;

The resist composition of the present invention may further contain, in addition to the component (D0), an acid diffusion control agent component (hereinafter, also referred to as "component (D)").

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

The component (D) in the present invention may be a photodegradable base (D1) which is decomposed by exposure and loses acid diffusion controllability (hereinafter referred to as "component (D1)") (Hereinafter referred to as &quot; component (D2) &quot;) which does not correspond to the nitrogen-containing organic compound (D2).

[Component (D1)] [

(D1), it is possible to improve the contrast between the exposed portion and the non-exposed portion when forming a resist pattern.

The component (D1) is not particularly limited as long as it is decomposed by exposure to lose acid diffusion controllability, and the compound represented by the following general formula (d1-1) (hereinafter referred to as the "component (d1-1) , A compound represented by the following general formula (d1-2) (hereinafter referred to as a "component (d1-2)") and a compound represented by the following general formula (d1-3) Quot;) is preferable.

The components (d1-1) to (d1-3) do not act as a quencher because they dissolve in the exposed portion and lose acid diffusion controllability (basicity), and act as a quencher in the unexposed portion.

(46)

[Wherein, Rd Rd ¹ ~ ⁴ is cyclic group which may have a substituent, an alkenyl group which may contain a chain-like alkyl group, or a substituent of the type chain which 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 ^&lt; ^{m + &gt;} are each independently an m-valent organic cation.

{(d1-1) component}

· Anonymous

Formula (d1-1) of, Rd ¹ is an alkenyl group of chain which may contain a cyclic group, an alkyl group of chain which may have a substituent, or a substituent which may have a substituent, it is the same as R ¹⁰¹ .

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-like hydrocarbon 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.

The aromatic hydrocarbon group is more preferably a phenyl group or a naphthyl group.

The aliphatic cyclic group is more preferably a group obtained by removing at least one hydrogen atom from a polycycloalkane such as adamantane, norbornane, isoborane, tricyclodecane, or tetracyclododecane.

The chain type hydrocarbon group is preferably a chain type alkyl group. As the chain type alkyl group, the number of carbon atoms is preferably from 1 to 10, and specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, A straight chain alkyl group, a straight chain alkyl group having 1 to 4 carbon atoms, such as a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, Butyl group, 1-methylpentyl 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 atom other than the fluorine atom include an oxygen atom, a carbon atom, a hydrogen atom, a sulfur atom, and a nitrogen atom.

As Rd ¹ , it is preferable that some or all of hydrogen atoms constituting the linear alkyl group are fluorinated alkyl groups substituted by fluorine atoms, and fluorinated alkyl groups in which all the hydrogen atoms constituting the linear alkyl group are substituted with fluorine atoms A linear perfluoroalkyl group).

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

(47)

· Kattenbu

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

The organic cation of M ^{m +} is not particularly limited, and examples thereof include the same cations represented by the above general formulas (ca-1) to (ca-4) -1) to (ca-1-63), respectively.

The component (d1-1) may be used singly or in combination of two or more.

{(d1-2) component}

· Anonymous

Formula (d1-2) of, Rd ^2, the cyclic group which may have a substituent, an alkyl chain which may have a substituent, or an alkenyl group of chain which may have a substituent, the same groups as R ¹⁰¹ have.

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

Rd ² is preferably an aliphatic cyclic group which may have a substituent, and a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. More preferably a group obtained by removing one or more hydrogen atoms from a camphor or the like.

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

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

(48)

· Kattenbu

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).

The component (d1-2) may be used singly or in combination of two or more.

{(d1-3) component}

· Anonymous

In the formula (d1-3), Rd ³ is a cyclic group which may have a substituent, an alkenyl group which may contain a chain-like alkyl group, or a substituent of the chain which may have a substituent, the same groups as R ^101, and , A cyclic group containing a fluorine atom, a chain-like alkyl group, or a chain-like alkenyl group. Among them, a fluorinated alkyl group is preferable, and the same as the fluorinated alkyl group of Rd ¹ is more preferable.

In the formula (d1-3), Rd ⁴ is cyclic group which may have a substituent, an alkyl chain which may have a substituent, or an alkenyl group of chain which may have a substituent, the same groups as R ¹⁰¹ have.

Among them, an alkyl group, alkoxy group, alkenyl group and 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 tert-butyl 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, iso- Butoxy group, and tert-butoxy group. Among them, a methoxy group and an ethoxy group are preferable.

The alkenyl group in Rd ⁴ includes the same groups as those described above for R ^101, and a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group and a 2-methylpropenyl group are preferable. These groups may also have, as a substituent, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

The cyclic group in Rd ⁴ may be the same as those described above for R ^101, and may be a cyclic group derived from a cycloalkane such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane An alicyclic group obtained by removing at least one hydrogen atom, 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 case of lithography using EUV as an exposure light source, the resist composition is excellent in light absorption efficiency, and has good sensitivity and lithography characteristics.

In the formula (d1-3), Yd ¹ is a single bond, or a divalent connecting group.

The divalent linking group in Yd ¹ includes, but is not limited to, a divalent hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group) which may have a substituent, and a divalent linking group containing a hetero atom. These are the same as those exemplified in the explanation of 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.

(49)

(50)

· Kattenbu

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).

The component (d1-3) may be used singly or in combination of two or more.

As the component (D1), any one of the components (d1-1) to (d1-3) may be used, or two or more components 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, 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 less than the upper limit value, the sensitivity can be kept good and the throughput is also excellent.

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 content of the component (D1) is preferably 0.5 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and further preferably 1.0 to 8.0 parts by mass with respect to 100 parts by mass of the component (A). When the lower limit of the above range is exceeded, particularly good lithography properties and resist pattern shapes are obtained. If the upper limit of the above range is not exceeded, the sensitivity can be kept good and the throughput is also excellent.

(Component (D2))

The component (D) may contain a nitrogen-containing organic compound component (hereinafter referred to as a component (D2)) which does not correspond to the component (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 component (D1), and any known component may be used. 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 amine include an amine (alkylamine or alkyl alcohol amine) or a cyclic amine in which at least one hydrogen atom of ammonia NH ₃ is substituted with an alkyl group or a hydroxyalkyl group having 12 or less carbon atoms.

Specific examples of alkylamines and alkylalcoholamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine; Dialkylamines such as propylamine, di-n-heptylamine, di-n-octylamine and dicyclohexylamine; aliphatic amines such as trimethylamine, triethylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, Alkylamine, alkyl alcohol amine such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine and the like. Of these, trialkylamines having 5 to 10 carbon atoms are more preferred, and tri-n-pentylamine or tri-n-octylamine is particularly preferred.

The cyclic amine includes, for example, a heterocyclic compound containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic (aliphatic monocyclic) amine or a polycyclic (aliphatic polycyclic) amine.

Specific examples of the aliphatic monocyclic amine include piperidine, piperazine and the like.

As the aliphatic polycyclic amines, 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] -7-undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane, and the like.

Other aliphatic amines include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl } Amine, tris {2- (1-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 be used.

Examples of the aromatic amine include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or a derivative thereof, diphenylamine, triphenylamine, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, and the like.

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

The component (D2) is usually used in a range of 0.01 to 5.0 parts by mass based on 100 parts by mass of the component (A). By setting the resistivity to the above range, the resist pattern shape, time-course stability after exposure, and the like are improved.

The component (D) may be used singly or in combination of two or more kinds. When the resist composition of the present invention contains the component (D), the component (D) is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 12 parts by mass, per 100 parts by mass of the component (A) More preferably 0.5 to 12 parts by mass. When the lower limit of the above-mentioned range is exceeded, lithographic characteristics such as LWR are further improved when the resist composition is used. In addition, a better resist pattern shape can be obtained. If the upper limit of the above range is not exceeded, the sensitivity can be kept good and the throughput is also excellent.

<Optional ingredients>

[Component (E)] [

In the present invention, the resist composition may contain, as optional components, an organic carboxylic acid and an oxo acid of phosphorus and a derivative thereof, for the purpose of preventing deterioration in sensitivity, and improving the resist pattern shape and time- (Hereinafter referred to as a component (E)) selected from the group consisting of a compound represented by the following general formula (1).

As the organic carboxylic acid, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.

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

Examples of the derivative of the phosphorous oxo acid 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 phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.

Examples of phosphonic acid derivatives include phosphonic acid esters such as dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonic acid ester and dibenzyl phosphonic acid.

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

The component (E) may be used alone or in combination of two or more.

The component (E) is usually used in a range of 0.01 to 5.0 parts by mass based on 100 parts by mass of the component (A).

[Component (F)] [

In the present invention, the resist composition 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, for example, those described in JP-A No. 2010-002870, JP-A No. 2010-032994, JP-A No. 2010-277043, JP-A No. 2011-13569, The fluorinated polymer compound described in the publication No. 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. Examples of the polymer include a polymer (homopolymer) comprising only a constituent unit (f1) represented by the following formula (f1-1), a constituent unit (f1) represented by the following formula (f1-1) (F1) represented by the following formula (f1-1), a structural unit derived from acrylic acid or methacrylic acid, and a copolymer of the aforementioned structural unit (a1). Ethyl-1-cyclooctyl (meth) acrylate or the formula (a1-2-01) shown above as the constituent unit (a1) copolymerized with the constituent unit (f1) Is preferable.

(51)

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

In the formula (f1-1), R is the same as the above. As R, a hydrogen atom or a methyl group is preferable.

In the formula (f1-1), examples of the halogen atom of Rf ¹⁰² and Rf ¹⁰³ include a fluorine atom, a chlorine atom, a bromine atom 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 represented by 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. The halogen atom includes 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 1-5, an integer of 1-3, and more preferably 1 or 2.

In the formula (f1-1), Rf ¹⁰¹ is an organic group containing fluorine atom, is preferably a hydrocarbon group containing a 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, more preferably 1 to 10 carbon atoms. Particularly preferred.

The hydrocarbon group containing a fluorine atom preferably has at least 25% of the hydrogen atoms in the hydrocarbon group fluorinated, more preferably at least 50% fluorinated, and more preferably at least 60% The hydrophobicity of the resist film at the time of immersion exposure becomes high.

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

The weight 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 not exceeded, the solubility in a resist solvent is 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) 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.

The component (F) may be used alone or in combination of two or more.

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

In the present invention, the resist composition may be appropriately added with a miscible additive, for example, an additive resin for improving the performance of the resist film, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, a halation inhibitor, Can be added and contained.

[Component (S)] [

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

The component (S) may be any one capable of dissolving each component to be used and forming a homogeneous solution. Conventionally, any one or two or more kinds of solvents known as solvents for chemically amplified resists Can be used.

Lactones such as? -Butyrolactone, ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, methyl-n-pentyl ketone (2-heptanone) and methyl isopentyl ketone; ketones such as ethylene glycol , Polyhydric alcohols such as diethylene glycol, propylene glycol and dipropylene glycol; compounds having ester linkages such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate and dipropylene glycol monoacetate; Derivatives of polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monoalkyl ether such as monobutyl ether, or compounds having an ether bond such as monophenyl ether of a compound having an ester bond, 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, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate And examples thereof include aromatic hydrocarbon solvents such as anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, Aromatic organic solvents such as mesitylene, dimethylsulfoxide (DMSO), and the like.

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

Among them, PGMEA, PGME,? -Butyrolactone and EL 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, still more preferably 3: 7: 3.

Further, as the component (S), a mixed solvent of at least one selected from PGMEA and EL and? -Butyrolactone 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. In general, the solid content concentration of the resist composition is in the range of 1 to 20% by mass, preferably 2 to 15% by mass.

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

&Lt; Method of forming resist pattern &

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 present invention, exposing the resist film, and developing the resist film after exposure to form a resist pattern .

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

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

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

Next, the exposed resist film is developed.

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

After the developing treatment, rinsing treatment is preferably carried out. In the case of the alkaline development process, rinsing is preferably performed using purified water, and in the case of the solvent development process, a rinsing solution containing an organic solvent is preferably used.

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

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 developing 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 an electronic component and a substrate having a predetermined wiring pattern formed thereon. More specifically, a metal substrate such as a silicon wafer, copper, chromium, iron or aluminum, or a glass substrate can be given. 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 formed on the above-described substrate. As the inorganic film, an inorganic anti-reflection film (inorganic BARC) can be mentioned. Examples of the organic film include an organic antireflection film (organic BARC) and an organic film such as a lower organic film in the multilayer resist method.

Here, 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 formed on a substrate, and a resist pattern formed on the upper resist film is used as a mask And patterning the underlying organic film to form a pattern with a high aspect ratio. That is, according to the multilayer resist method, since the required thickness can be secured by the lower organic film, the resist film can be 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) And a method of forming a multilayer structure of three or more layers (three-layer resist method).

The wavelength to be used for exposure is not particularly limited and may be selected from the group consisting of ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam) It can be carried out using radiation. The resist composition is highly useful as KrF excimer laser, ArF excimer laser, EB or EUV.

The exposure method of the resist film may be a conventional exposure (dry exposure) or an immersion exposure (liquid immersion lithography) in an inert gas such as air or nitrogen.

The liquid immersion exposure is an exposure method in which the space between the resist film and the lens in the lowermost position of the exposure apparatus is previously filled with a solvent (immersion medium) having a refractive index larger than that of air and exposure (immersion exposure) is performed in 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 fluorine-based compounds such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , C ₅ H ₃ F ₇ , And preferably has a boiling point of 70 to 180 ° C, more preferably 80 to 160 ° C. If the fluorine-based inert liquid has a boiling point in the above-mentioned range, it is preferable that the medium used for liquid immersion can be removed by a simple method after the end of exposure.

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.

Specific examples of the perfluoroalkyl ether compound include perfluoro (2-butyl-tetrahydrofuran) (boiling point: 102 ° C), and perfluoroalkylamine compounds include perfluoro (Boiling point 174 占 폚).

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. Specifically, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent or an ether solvent and a hydrocarbon solvent may be used.

If necessary, known additives may be added to the organic developer. Examples of the additive include a surfactant. The surfactant is not particularly limited and, for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.

When a 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 in a developing solution for a predetermined time (dip method), a developing solution is mounted on the surface of the support by surface tension, A method of spraying a developer onto the surface of a support (spraying method), a method of continuously drawing a developer while scanning a developer-dispensing nozzle at a constant speed on a support rotating at a constant speed (a method of dynamic dispensing Law).

The rinsing treatment (rinsing treatment) using the rinsing liquid can be carried out by a known rinsing method. The method includes, for example, a method (rotation coating method) of continuously extracting the rinsing liquid on a support rotating at a constant speed, a method (dip method) of immersing the support in a rinsing liquid for a certain period of time, And spraying method (spraying method).

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

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[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, which is a chain, branched chain or cyclic hydrocarbon group. When a substituent is bonded to the carbon atom of R ¹ adjacent to the carbonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . R ² is a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, and is a chain, branched chain or cyclic hydrocarbon group. When a substituent is bonded to the carbon atom of R ² adjacent to the sulfonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . M ^&lt; ^{m + &gt;} is ^{m &lt}; ² &gt; m is an integer of 1 or more.]

In the above formula, R ¹ and R ² and M ^{m +} are the same as described above.

The compound represented by the third embodiment of the present invention is preferably a compound represented by the above general formula (d0-1), more preferably a compound represented by the general formula (d0-1a), (d0-1b) or (d0-1c) And more preferably a compound represented by any of the above.

Example

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

[Compound Synthesis Example]

5.23 g (55.0 mmol) of methanesulfonamide was dissolved in 52.3 g of tetrahydrofuran (THF) and ice-cooled with stirring. After 6.07 g (60.0 mmol) of triethylamine was added dropwise thereto, a solution of 6.03 g (50.0 mmol) of pivaloyl chloride in 30.2 g of THF was added dropwise over 1 hour, and further stirred for 3 hours Respectively.

A 5% hydrochloric acid aqueous solution and t-butyl methyl ether were added dropwise to the reaction solution, and the temperature was raised to room temperature, followed by separating operation to extract an organic phase. After repeating the step of washing the obtained organic phase with 52.3 g of pure water, the organic phase was concentrated to obtain 7.17 g of Intermediate D0-1-1.

To 7.17 g of the intermediate D0-1-1, 71.7 g of pure water and 1.76 g of sodium hydroxide were added and dissolved. 15.10 g of triphenylsulfonium bromide and 71.7 g of dichloromethane were added to the mixture, and the mixture was stirred, and the organic phase was extracted by separating. After the step of washing the obtained organic phase with 71.7 g of pure water was repeated, and then the organic phase was concentrated to obtain 14.66 g of a photoacid generator (D0) -1.

The obtained compound was subjected to NMR measurement, and the structure was identified from the following results.

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

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&Lt; Preparation of resist composition &gt;

(Examples 1 to 23 and Comparative Examples 1 to 16)

The components shown in Tables 1 to 3 were mixed and dissolved to prepare a resist composition.

The abbreviations in the above table have the following meanings. The numerical value in [] is the compounding amount (parts by mass).

 (A) -1 to (A) -3: The following polymer compounds (A) -1 to (A) -3.

 (B) -1: The following compound (B) -1.

 (D0) -1 to (D0) -19: The above compounds (D0) -1 to (D0) -19.

 (F) -1: The following polymer compound (F) -1.

 (S) -1: mixed solvent of PGMEA / PGME / cyclohexanone (weight ratio 45/30/25).

 (S) -2:? -Butyrolactone.

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<Formation of Resist Pattern 1: Alkali Development Positive Type>

(Examples 1 to 9 and Comparative Examples 1 to 7)

ARC29 &quot; (trade name, manufactured by Brewer Science) was applied on an 8-inch silicon wafer using a spinner and baked on a hot plate at 205 DEG C for 60 seconds and dried to obtain an organic An antireflection film was formed.

Next, the resist composition was applied on the film using a spinner, pre-baked (PAB) treatment was performed on a hot plate at a temperature of 110 캜 for 60 seconds, and then dried to obtain a resist film having a film thickness of 90 nm Thereby forming a resist film.

Subsequently, an ArF excimer laser (193 nm) was selectively formed on the resist film by using an exposure apparatus NSR-S609B (NA = 1.07 Dipole 0.97 / 0.78 with polystyrene manufactured by Nikon Corporation) through a mask pattern (6% halftone) Respectively.

Next, an alkali development was carried out at 23 占 폚 for 10 seconds using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.).

As a result, a line and space pattern (hereinafter also referred to as &quot; LS pattern &quot;) was formed in any of the examples.

In either example, a line-and-space pattern with a line width of 50 nm / pitch of 100 nm was formed.

&Lt; Formation of resist pattern 2: Solvent development Negative type &gt;

(Examples 10 to 23 and Comparative Examples 8 to 16)

ARC29 &quot; (trade name, manufactured by Brewer Science) was applied on an 8-inch silicon wafer using a spinner and baked on a hot plate at 205 DEG C for 60 seconds and dried to obtain an organic An antireflection film was formed.

Subsequently, the resist composition was applied on the film using a spinner, pre-baked (PAB) treatment was performed on a hot plate at a temperature of 90 DEG C for 60 seconds, and then dried to form a resist film having a thickness of 100 nm Film.

Subsequently, an ArF excimer laser (193 nm) was selectively formed on the resist film by using an exposure apparatus NSR-S609B (NA = 1.07 Dipole 0.97 / 0.78 with polystyrene manufactured by Nikon Corporation) through a mask pattern (6% halftone) Respectively.

Subsequently, solvent development was carried out at 23 占 폚 with butyl acetate for 16 seconds, followed by shaking and drying.

As a result, a line and space pattern was formed in any of the examples. In either example, a line-and-space pattern with a line width of 50 nm / pitch of 100 nm was formed.

[Evaluation of optimum exposure dose (Eop)] [

The optimum exposure amount Eop (mJ / cm 2) at which the LS pattern of the target size is formed was determined by the above-described method of forming a resist pattern. The results are shown in the following Tables 4 to 6 as "sensitivity (mJ / cm 2)".

[Evaluation of exposure margin (EL margin)] [

The exposure amount at which the LS pattern line was formed within the range of ± 5% of the target dimension was obtained, and the EL margin (unit:%) was obtained from the following formula. The results are shown in the following Tables 4 to 6 as &quot; 5% EL (%) &quot;.

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

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

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

The larger the value of the EL margin, the smaller the amount of change in the pattern size accompanying the fluctuation of the exposure amount.

 In the formula for calculating the EL margin, &quot; Eop &quot; means the optimum exposure amount (mJ / cm 2). The Eop was obtained by a conventional method.

[Evaluation of mask error factor (MEEF)] [

Mask patterns having a target size (line width) of 45 to 55 nm (intervals of 1 nm, 11 points in total) were used in the same procedure as the formation of the resist pattern, and each line and space pattern having a pitch of 100 nm Was formed at the same exposure amount.

At that time, the slope (MEEF) of the straight line when plotting the line width (nm) of the pattern formed on the resist film on the ordinate axis was calculated using the target size (nm) on the abscissa and each mask pattern. The results are shown in Tables 4 to 6 below as &quot; MEEF &quot;.

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

[Evaluation of LWR (line with roughness)] [

The hole width was measured by a line-of-sight SEM (scanning electron microscope, acceleration voltage 300 V, trade name: S-9380, manufactured by Hitachi High-Technologies Corporation) in the LS pattern formed by the above <formation of resist pattern> (3s) of the standard deviation (s) was obtained from the results, and a value averaged over 3s of 400 points was calculated as a scale representing the LWR. The results are shown in Table 4 to 6 as &quot; LWR (nm) &quot;.

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

[Evaluation of shape]

The LS pattern was observed by a measurement SEM (scanning electron microscope, accelerating voltage 800 V, trade name: S-9220, manufactured by Hitachi, Ltd.). The results are shown in Tables 4 to 6 as &quot; rectangularity &quot;.

[Storage stability]

1) For each of the resist compositions before and after being stored at room temperature for one month, a contact hole pattern was formed by the resist pattern forming method at the optimum exposure dose Eop and the hole diameter (CD) was measured.

2) The difference (before and after storage) of the resist composition of each Example stored at room temperature for one month (CD variation value) was calculated. The results are shown in Tables 4 to 6 as &quot; storage stability &quot;.

The case where ΔCD was less than 1 nm was evaluated as "good" because the storage stability of the resist composition was excellent, and the other samples were evaluated as "poor".

As shown in the above results, the resist composition of the present invention was excellent in storage stability and in lithography properties.

Among them, in Example 5 using the compound (D0) -4 in which at least one of the terminal groups is a cyclic hydrocarbon group and the compound (D0) -5 as the component (D0), the MEEF, the EL margin , And LWR were particularly excellent.

Claims (5)

As a resist composition which generates an acid upon exposure and changes solubility in a developer by the action of an acid,
An acid generator component (B) for generating an acid upon exposure,
A resist composition comprising a photobase deflocculating component (D0) comprising a compound represented by the following general formula (d0).
[Chemical Formula 1]

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, which is a chain, branched chain or cyclic hydrocarbon group. When a substituent is bonded to the carbon atom of R ¹ adjacent to the carbonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . R ² is a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, and is a chain, branched chain or cyclic hydrocarbon group. When a substituent is bonded to the carbon atom of R ² adjacent to the sulfonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . M ^&lt; ^{m + &gt;} is ^{m &lt}; ² &gt; m is an integer of 1 or more.] The method according to claim 1,
Wherein the compound represented by the general formula (d0) is a compound represented by the following general formula (d0-1).
(2)

Wherein one of R ¹¹ and R ¹² is a cyclic hydrocarbon group having 3 to 20 carbon atoms which may have a substituent and the other is a chain, branched chain or ring having 1 to 20 carbon atoms which may have a substituent Lt; / RTI &gt; hydrocarbon group. When a substituent is bonded to the carbon atom of R ¹¹ adjacent to the carbonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . When a substituent is bonded to the carbon atom of R ¹² adjacent to the sulfonyl group in the formula, the substituent has at least one group selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . M ^&lt; ^{m + &gt;} is ^{m &lt}; ² &gt; m is an integer of 1 or more.] The method according to claim 1,
Wherein the conjugate acid of the compound represented by the general formula (d0) has a pKa of greater than 2.5. A step of forming a resist film by using the resist composition according to any one of claims 1 to 3 on the support, a step of exposing the resist film, and a step of developing the resist film after the exposure to form a resist pattern Wherein the resist pattern forming step comprises the steps of: A compound represented by the following general formula (d0).
(3)

[In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, which is a chain, branched chain or cyclic hydrocarbon group. When a substituent is bonded to the carbon atom of R ¹ adjacent to the carbonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . R ² is a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, and is a chain, branched chain or cyclic hydrocarbon group. When a substituent is bonded to the carbon atom of R ² adjacent to the sulfonyl group in the formula, the substituent may be at least one selected from the group consisting of a group having a halogen atom, an aromatic group, and a proton acceptor functional group . M ^&lt; ^{m + &gt;} is ^{m &lt}; ² &gt; m is an integer of 1 or more.]