KR20210077614A - Resist composition and method of forming resist pattern - Google Patents

Abstract

A negative resist composition comprises: a polymer compound (A1) having a structural unit (a10) containing a phenolic hydroxyl group; an acid generator (B0) represented by general formula (b0-1); a crosslinking agent (C); and aromatic compound (Z) having 1 or 2 phenolic hydroxyl groups in a molecule and having no carboxyl group, wherein, Rb1 is an organic group, and Rb2 is a group represented by following general formula (b0-r-1) or (b0-r-2). Accordingly, the present invention provides a resist composition capable of forming a resist pattern with good etching resistance, and a method of forming a resist pattern.

Description

RESIST COMPOSITION AND METHOD OF FORMING RESIST PATTERN

The present invention relates to a resist composition and a method for forming a resist pattern.

This application claims priority based on Japanese Patent Application No. 2019-227234 for which it applied to Japan on December 17, 2019, and uses the content here.

In recent years, in manufacture of a semiconductor element and a liquid crystal display element, pattern refinement|miniaturization is advancing rapidly with the progress of lithography technology. As a method of miniaturization, the wavelength reduction (higher energy) of an exposure light source is generally implemented.

The resist material is required to have lithographic properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.

As a resist material that satisfies these requirements, conventionally, a chemically amplified resist composition containing a base component whose solubility in a developer changes due to the action of an acid and an acid generator component that generates an acid upon exposure has been used. .

The resist material is required to have lithographic properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.

As a resist material that satisfies these requirements, conventionally, a chemically amplified resist composition containing a base component whose solubility in a developer changes due to the action of an acid and an acid generator component that generates an acid upon exposure has been used. .

For example, when the developer is an alkali developer (alkali developing process), the positive chemically amplified resist composition includes a resin component (base resin) that increases solubility in an alkali developer by the action of an acid (base resin) and an acid generator Those containing ingredients are generally used. When a resist film formed using such a resist composition is selectively exposed during resist pattern formation, an 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 of the resist film becomes soluble to the alkali developer. Therefore, by alkali development, a positive pattern in which the unexposed portion of the resist film remains as a pattern is formed.

As a resist material, conventionally, a chemically amplified resist composition containing a base component soluble in an alkali developer (alkali-soluble base component), an acid generator component that generates an acid upon exposure, and a crosslinking agent component have also been used. In such a chemically amplified resist composition, for example, when an acid is generated from an acid generator component by exposure, the acid acts to crosslink between the alkali-soluble base component and the crosslinking agent component, and as a result, solubility in an alkali developer solution this decreases Therefore, when a resist film obtained by applying such a chemically amplified resist composition on a support is selectively exposed in the formation of a resist pattern, the exposed portion of the resist film changes to be poorly soluble in an alkali developer, while the unexposed portion of the resist film is Since it remains soluble and does not change with respect to an alkali developing solution, a negative resist pattern is formed by developing with an alkali developing solution.

For example, Patent Document 1 describes a negative chemically amplified resist composition containing an alkali-soluble polyhydroxystyrene-based resin, an acid crosslinking substance, a specific photoacid generator, and a dissolution accelerator.

Japanese Patent No. 3655030

As a result of the studies of the present invention, when a resist pattern is formed using a negative resist composition employing an alkali-soluble polyhydroxystyrene-based resin as a base component, a micron-order thick resist film is formed using wet etching resistance, When etching was performed by forming a resist pattern, the etching resistance was insufficient in some cases.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resist composition capable of forming a resist pattern with good etching resistance, and a method for forming a resist pattern using the resist composition.

In order to solve the said subject, this invention employ|adopted the following structures.

That is, the first aspect of the present invention provides a polymer compound (A1) having a structural unit (a10) represented by the following general formula (a10-1) and an acid generator (B0) represented by the following general formula (b0-1) A negative resist composition comprising: a crosslinking agent (C); and an aromatic compound (Z) having one or two phenolic hydroxyl groups in the molecule and not having a carboxyl group.

[Formula 1]

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ya ^x1 is a single bond or a divalent linking group. Wa ^x1 is an aromatic hydrocarbon group which may have a substituent. n _ax1 is an integer greater than or equal to 1.]

[Formula 2]

[Wherein, Rb ¹ is an organic group. Rb ² is a group represented by the following general formula (b0-r-1) or the following general formula (b0-r-2).]

[Formula 3]

[In formula (b0-r-1), Rb ²⁰¹ and Rb ²⁰² are each independently an organic group. * indicates a bond. In the formula (b0-r-2), Xb is a group that together with -(O=)CNC(=O)- forms a cyclic group having a cyclic imide structure. * indicates a bond hand.]

A second aspect of the present invention provides a step of forming a resist film on a support using the resist composition according to the first aspect, exposing the resist film, and developing the resist film after exposure to form a resist pattern. A method of forming a resist pattern having

ADVANTAGE OF THE INVENTION According to this invention, the resist composition which can form a resist pattern with favorable etching resistance, and the resist pattern formation method using the resist composition can be provided.

In the present specification and claims, "aliphatic" is a concept relative to aromatic, and is defined as meaning a group, compound, etc. that do not have aromaticity.

Unless otherwise specified, "alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The alkyl group in the alkoxy group is the same.

The "alkylene group" includes divalent saturated hydrocarbon groups of linear, branched and cyclic unless otherwise specified.

Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A "structural unit" means a monomer unit (monomer unit) constituting a high molecular compound (resin, polymer, copolymer).

When describing "you may have a substituent", both a case where a hydrogen atom (-H) is substituted with a monovalent group and a case where a methylene group (-CH ₂ -) is substituted with a divalent group is included.

"Exposure" is a concept including radiation irradiation in general.

The "acid-decomposable group" is a group having acid-decomposable properties in which at least a part of bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid.

As an acid-decomposable group whose polarity increases by the action of an acid, for example, a group which decomposes by the action of an acid to generate a polar group is exemplified.

As a polar group, a carboxy group, a hydroxyl group, an amino group, a sulfo group (-SO ₃ H), etc. are mentioned, for example.

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

The term "acid dissociable group" refers to (i) a group having acid dissociability in 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) by the action of an acid It refers to both groups in which the bond between the acid dissociable group and the atom adjacent to the acid dissociable group can be cleaved by further decarboxylation reaction after cleavage of some bonds.

The acid-dissociable group constituting the acid-dissociable group must be a group having a lower polarity than the polar group formed by dissociation of the acid-dissociable group, and thus, when the acid-dissociable group is dissociated by the action of an acid, it has a higher polarity than the acid-dissociable group A polar group is created and the polarity increases. As a result, the polarity of the whole component (A1) increases. As the polarity increases, the solubility with respect to the developer relatively changes, and solubility increases when the developer is an alkaline developer, and the solubility decreases when the developer is an organic developer.

A "base component" is an organic compound having film-forming ability. Organic compounds used as the base material are broadly classified into non-polymers and polymers. As a non-polymer, the thing of molecular weight 500 or more and less than 4000 is used normally. Hereinafter, when referred to as a "low molecular weight compound", molecular weights are 500 or more and less than 4000 nonpolymers. As a polymer, a thing with a molecular weight of 1000 or more is used normally. Hereinafter, when referred to as "resin", "polymer compound", or "polymer", a polymer having a molecular weight of 1000 or more is indicated. As molecular weight of a polymer, the mass average molecular weight of polystyrene conversion by GPC (gel permeation chromatography) shall be used.

"Structural unit derived" means a structural unit constituted by cleavage of multiple bonds between carbon atoms, for example, ethylenic double bonds.

In "acrylic acid ester", the hydrogen atom couple|bonded with the carbon atom at the α-position may be substituted with a substituent. ^{The substituent (R αx} ) for substituting the hydrogen atom bonded to the carbon atom at the α-position is an atom or group other than the hydrogen atom. In addition, ^{itaconic acid diesters in which the substituent (R αx} ) is substituted with a substituent containing an ester bond, and ^{α hydroxyacrylic esters in which the substituent (R αx} ) is substituted with a hydroxyalkyl group or a group modified with a hydroxyl group thereof are also included. do. In addition, unless otherwise indicated, the carbon atom at the alpha-position of an acrylic acid ester is a carbon atom to which the carbonyl group of acrylic acid is couple|bonded.

Hereinafter, the acrylic acid ester in which the hydrogen atom couple|bonded with the carbon atom at the α-position was substituted with a substituent may be referred to as an α-substituted acrylic acid ester.

The "derivative" is a concept including those in which the hydrogen atom at the α-position of the target compound is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. As those derivatives, the hydrogen atom of the hydroxyl group of the target compound in which the hydrogen atom at the α-position may be substituted with a substituent is substituted with an organic group; and those in which a substituent other than a hydroxyl group is bonded to the target compound in which the hydrogen atom at the α-position may be substituted with a substituent. In addition, the α-position refers to the first carbon atom adjacent to the functional group, unless otherwise specified.

Examples of the substituent for substituting the hydrogen atom at the α-position of hydroxystyrene include the same as those for ^{R αx .}

In this specification and claims, depending on the structure represented by the chemical formula, an asymmetric carbon may exist, and an enantiomer or a diastereomer may exist. In that case, one chemical formula represents those isomers. These isomers may be used independently and may be used as a mixture.

(resist composition)

The resist composition according to the first aspect of the present invention is a negative resist composition.

In one embodiment of such a resist composition, the base component (A) whose solubility in a developer changes due to the action of an acid (hereinafter also referred to as "component (A)"), and an acid generator that generates an acid upon exposure Component (B) (hereinafter also referred to as “component (B)”), a crosslinking agent (C) (hereinafter also referred to as “component (C)”), has one or two phenolic hydroxyl groups in the molecule, and has no carboxyl group and a resist composition containing an aromatic compound (Z) (hereinafter also referred to as “component (Z)”) that is not present.

In the resist composition of the present embodiment, component (A) includes a polymer compound (A1) having a structural unit (a10) represented by the general formula (a10-1) (hereinafter referred to as “component (A1)”). And (B) component contains the acid generator (B0) (henceforth "(B0) component") represented by general formula (b0-1).

When a resist film is formed using the resist composition of the present embodiment and the resist film is selectively exposed, an acid is generated in the exposed portion of the resist film, and by the action of the acid, the solubility of component (A) in a developer solution is performed. On the other hand, since the solubility of component (A) in the developer does not change in the unexposed portion of the resist film, a difference in solubility in the developer occurs between the exposed portion and the unexposed portion of the resist film. Therefore, when the resist film is developed with alkali, the unexposed portion of the resist film is dissolved and removed, and a negative resist pattern is formed.

In the present specification, the resist composition in which the resist film exposed portion is dissolved and removed to form a positive resist pattern is referred to as a positive resist composition, and the resist composition in which the unexposed portion of the resist film is dissolved and removed to form a negative resist pattern is referred to as a negative resist composition. It is called composition. The resist composition of the present embodiment is a negative resist composition.

<(A) component>

Component (A) is a base component whose solubility in a developing solution changes by the action of an acid.

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

Organic compounds used as the base material are broadly classified into non-polymers and polymers.

As a non-polymer, the thing of molecular weight 500 or more and less than 4000 is used normally. Hereinafter, when referred to as a "low molecular weight compound," a non-polymer having a molecular weight of 500 or more and less than 4000 is indicated. As a polymer, a thing with a molecular weight of 1000 or more is used normally. Hereinafter, when referred to as "resin", "polymer compound", or "polymer", a polymer having a molecular weight of 1000 or more is indicated. As molecular weight of a polymer, the weight average molecular weight of polystyrene conversion by GPC (gel permeation chromatography) shall be used.

In the resist composition of the present embodiment, at least a polymer compound (A1) having a structural unit (a10) represented by the general formula (a0-1) is used for the component (A), and a polymer other than the component (A1). A compound and/or a low molecular weight compound may be used together.

When a resist film is formed using a resist composition containing at least component (A1) and the resist film is selectively exposed to light, for example, the resist composition contains component (B) in the exposed portion of the resist film. In this case, an acid is generated from the component (B), and crosslinking occurs between the component (A1) through the structural unit (a10) having crosslinkability by the action of the acid, and as a result, the resist film exposed portion The solubility in alkaline developer decreases. Therefore, in the formation of a resist pattern, when a resist film obtained by applying the resist composition of the present embodiment on a support is selectively exposed to light, the resist film-exposed portion becomes poorly soluble in an alkali developer, while the unexposed portion of the resist film is Since it remains soluble and does not change with respect to an alkali developing solution, a negative resist pattern is formed by developing with an alkali developing solution.

・(A1) About component

The component (A1) is a polymer compound having a structural unit (a10) represented by the general formula (a0-1).

(A1) As a component, in addition to a structural unit (a10), the copolymer which has a structural unit (a11) which further contains an aromatic ring (except the aromatic ring to which the hydroxyl group couple|bonded) in a side chain is preferable.

Moreover, the component (A1) may have other structural units other than a structural unit (a10) and a structural unit (a11).

For the constituent unit (a10):

The structural unit (a10) is a structural unit represented by the following general formula (a10-1).

[Formula 4]

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ya ^x1 is a single bond or a divalent linking group. Wa ^x1 is an aromatic hydrocarbon group which may have a substituent. n _ax1 is an integer greater than or equal to 1.]

In said formula (a10-1), R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group.

The C1-C5 alkyl group for R is preferably a C1-C5 linear or branched alkyl group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. are mentioned.

The halogenated alkyl group having 1 to 5 carbon atoms for R is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferable.

R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group from the viewpoint of industrial availability, and a hydrogen atom or a methyl group more preferably, a methyl group is particularly preferable.

In the formula (a10-1), Ya ^x1 is a single bond or a divalent linking group.

In the above formula, the ^{divalent linking group for Ya x 1} is not particularly limited, and preferable examples include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.

· A divalent hydrocarbon group which may have a substituent:

When Ya ^{x 1} is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

... aliphatic hydrocarbon group for ^{Ya x1}

An aliphatic hydrocarbon group means a hydrocarbon group which does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and it is usually preferable that it is saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group having a ring in its structure.

... linear or branched aliphatic hydrocarbon group

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

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

The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.

The branched chain aliphatic hydrocarbon group is preferably a branched chain alkylene group, specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, Alkylmethylene groups, such as -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) _{2 -;} -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH _{3) 2} -CH ₂ - alkyl group such as ethylene; Alkyltrimethylene groups, such as -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH _{2 -;} Alkylalkylene groups, such as alkyltetramethylene groups, such as -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH _{2 -, etc. are mentioned.} As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

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.

... an aliphatic hydrocarbon group containing a ring in its structure

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

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

The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane is preferably a monocycloalkane having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a polycycloalkane having 7 to 12 carbon atoms, specifically adamantane, norbornane; isobornane, tricyclodecane, tetracyclododecane, and the like.

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, more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group or tert-butoxy group, and methoxy time, an ethoxy group is more preferable.

As a halogen atom as said substituent, a fluorine atom is preferable.

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

In the cyclic aliphatic hydrocarbon group, a part of carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As a substituent containing the hetero atom, -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O- are preferable. .

··Aromatic hydrocarbon group for ^{Ya x1}

The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. It is preferable that carbon number of an aromatic ring is 5-30, C5-C20 is more preferable, C6-C15 is still more preferable, C6-C12 is especially preferable. However, carbon number in a substituent shall not be included in the carbon number.

Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with hetero atoms. As a hetero atom in an aromatic heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.

Specific examples of the aromatic hydrocarbon group include groups in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (eg, biphenyl, fluorene, etc.); A group in which one hydrogen atom of the group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group) is substituted with an alkylene group (eg, benzyl group, phenethyl group, 1-naph group in which one hydrogen atom has been further removed from the aryl group in arylalkyl groups such as tylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group); It is preferable that carbon number of the alkylene group couple|bonded with the said aryl group or heteroaryl group is 1-4, It is more preferable that it is C1-C2, It is especially preferable that it is C1.

As for the said aromatic hydrocarbon group, the hydrogen atom which the said aromatic hydrocarbon group has may be substituted by the substituent. For example, the hydrogen atom couple|bonded with the aromatic ring in the said aromatic hydrocarbon group may be substituted by the 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, more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

Examples of the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as substituents for substituting a hydrogen atom in the cyclic aliphatic hydrocarbon group.

· A divalent linking group containing a hetero atom:

When Ya ^x1 is a divalent linking group containing a hetero atom, the linking group is preferably -O-, -C(=O)-O-, -OC(=O)-, -C(=O)- , -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with substituents, such as an alkyl group and an acyl group. ), -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, general formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(= O)-O-, -C(=O)-OY ²¹ -, -[Y ²¹ -C(=O)-O] _m" -Y ²² -, -Y ²¹ -OC(=O)-Y ²² - or a group represented by ^{-Y 21} -S(=O) ₂ -OY ^{22 - [wherein Y 21} and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m" is an integer of 0 to 3.] and the like.

The divalent linking group containing the hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)- In this case, H may be substituted with substituents, such as an alkyl group and acyl. It is preferable that carbon number is 1-10, as for the substituent (an alkyl group, an acyl group, etc.), it is more preferable that it is 1-8, It is especially preferable that it is 1-5.

Formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(=O)-OY ²¹ -, -[Y ²¹ -C(=O )-O] _m" -Y ²² -, -Y ²¹ -OC(=O)-Y ²² - or -Y ²¹ -S(=O) ₂ -OY ²² -, wherein Y ²¹ and Y ²² are each independently is a divalent hydrocarbon group which may have a substituent.The divalent hydrocarbon group includes the same (divalent hydrocarbon group which may have a substituent) in the description of the divalent linking group in ^{Ya x1 above.} .

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 still more preferable, and a methylene group or an ethylene group is particularly preferable.

As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group, or an alkylmethylene group is more preferable. A C1-C5 linear alkyl group is preferable, as for the alkyl group in this alkylmethylene group, a C1-C3 linear alkyl group is more preferable, A methyl group is the most preferable.

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 preferred. 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 -.} , a group represented by the formula -(CH ₂ ) _a' -C(=O)-O-(CH ₂ ) _b' - is preferable, wherein a' is an integer of 1 to 10, and 1 to 8 An integer is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is still more preferable, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, 1 The integer of -5 is more preferable, 1 or 2 is still more preferable, and 1 is the most preferable.

Among the above, as Ya ^x1 , a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a linear or branched alkylene group , or a combination thereof, and a single bond or an ester bond [-C(=O)-O-, -OC(=O)-] is more preferable.

In the formula (a10-1), Wa ^x1 is an aromatic hydrocarbon group which may have a substituent.

Aromatic hydrocarbon group in the Wa ^x1, there may be mentioned aromatic ring is also brought from a substituent _(ax1 n + 1) of a group removed a hydrogen atom. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. It is preferable that carbon number of an aromatic ring is 5-30, C5-C20 is more preferable, C6-C15 is still more preferable, C6-C12 is especially preferable. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with hetero atoms. As a hetero atom in an aromatic heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.

Further, ^{the aromatic hydrocarbon group for Wa x1} _{is a group obtained by removing (n ax1} +1) hydrogen atoms from an aromatic compound containing an aromatic ring optionally having two or more substituents (eg, biphenyl, fluorene, etc.) can be heard

Among the above, as Wa ^x1 _{, a group obtained by removing (n ax1} +1) hydrogen atoms from benzene, naphthalene, anthracene or biphenyl is preferable, and a group obtained by removing (n _ax1 +1) hydrogen atoms from benzene or naphthalene is more preferable, , a group in which (n _ax1 + 1) hydrogen atoms have been removed from benzene is more preferable.

The aromatic hydrocarbon group in Wa ^x1 may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group. Examples of the alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent include the same groups as the substituents for the cyclic aliphatic hydrocarbon group in ^{Ya x 1 .} The substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, still more preferably an ethyl group or a methyl group, and a methyl group is particularly preferred. It is preferable that the aromatic hydrocarbon group in Wa ^{x1 does not have a substituent.}

In the formula (a10-1), n _ax1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably 1, 2 or 3, and 1 or 2 is particularly preferred.

Specific examples of the structural unit (a10) represented by the formula (a10-1) are shown below.

In each of the following formulas, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

(A1) The number of structural units (a10) which a component has may be 1 type, or 2 or more types may be sufficient as it.

(A1) The proportion of the structural unit (a10) in the component is preferably 70 to 99 mol%, more preferably 75 to 99 mol% with respect to the total (100 mol%) of all the structural units constituting the component (A1). It is preferable, 80-99 mol% is more preferable, 85-95 mol% is especially preferable.

By making the ratio of the structural unit (a10) equal to or more than the lower limit, the developing characteristics and the lithographic characteristics are further improved. On the other hand, by setting it as below an upper limit, it becomes easy to balance with another structural unit.

For the constituent unit (a11):

(A1) component, in addition to the structural unit (a10) described above, further has a structural unit (a11) derived from a compound containing an aromatic ring (excluding the aromatic ring to which a hydroxyl group is bonded) in a side chain Copolymers are preferred.

As a compound containing an aromatic ring (except the aromatic ring to which the hydroxyl group couple|bonded) in a side chain, the compound represented, for example by the following general formula (a11-1) is mentioned preferably.

[Formula 9]

[In formula (a11-1), Ra ^x2 is a polymerizable group-containing group. Wa ^x2 is a (n _ax2 +1) valent aromatic hydrocarbon group. However, a condensed ring structure may be formed by ^{Ra x2} and Wa ^x2. Ra ^x02 is a substituent substituting a hydrogen atom constituting ^{Wa x2 (aromatic hydrocarbon group).} n _ax2 is an integer of 0-3. When n _ax2 is 2 or more, a plurality of Ra ^x02 may combine with each other to form a ring structure.]

In the formula (a11-1), Ra ^x2 is a polymerizable group-containing group.

The "polymerizable group" in Ra ^x2 is a group that enables a compound having a polymerizable group to polymerize by radical polymerization or the like, and refers to, for example, a group containing multiple bonds between carbon atoms such as ethylenic double bonds.

Examples of the polymerizable group include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a fluorovinyl group, a difluorovinyl group, a trifluorovinyl group, a difluorotrifluoromethylvinyl group, and a tri Fluoroallyl group, perfluoroallyl group, trifluoromethyl acryloyl group, nonylfluorobutyl acryloyl group, vinyl ether group, fluorinated vinyl ether group, allyl ether group, fluorinated allyl ether group, styryl group, A vinyl naphthyl group, a fluorinated styryl group, a fluorine-containing vinyl naphthyl group, a norbornyl group, a fluorine-containing norbornyl group, a silyl group, etc. are mentioned.

As a polymeric group-containing group, the contribution comprised only by a polymeric group may be sufficient, and the contribution comprised by a polymeric group and groups other than this polymeric group may be sufficient. As groups other than the polymerizable group, the divalent hydrocarbon group which may have a substituent, the divalent coupling group containing a hetero atom, etc. are mentioned.

As Ra ^x2 , for example, a group represented by the _{general formula: CH 2} =C(R)-Ya ^{x0 - is preferably exemplified.} Of the formula, R is a halogenated alkyl group of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms of, Ya ^x0 is a divalent linking group.

In the formula (a11-1), Wa ^x2 is an _{aromatic hydrocarbon group having a valence of (n ax2} +1), and examples of the same as those ^{of Wa x1 in (a10-1) are mentioned.}

However, a condensed ring structure may be formed by ^{Ra x2} and Wa ^x2.

When a condensed ring structure is formed by ^{Ra x2} and Wa ^x2 , an aromatic ring derived from ^{Wa x2 is included in the condensed ring structure.} Moreover, ^{multiple bonds between carbon atoms of the polymerizable group derived from Ra x2} are cleaved to form the main chain of component (A1). That is, a part of the carbon atoms constituting the condensed ring constitutes the main chain of component (A1).

In the formula (a11-1), Ra ^x02 is a substituent for substituting a hydrogen atom constituting ^{Wa x2 (aromatic hydrocarbon group).}

As ^{a substituent in Ra x02} , an alkyl group, an alkoxy group, an acyloxy group, etc. are mentioned, for example.

The ^{alkyl group as the substituent in Ra x02} is preferably an alkyl group having 1 to 5 carbon atoms, more 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 in Ra x02} is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group or tert-butoxy group. and a methoxy group and an ethoxy group are particularly preferable.

The ^{acyloxy group as a substituent in Ra x02} preferably has 2 to 6 carbon atoms, and CH ₃ C(=O)-O- (acetoxy group), C ₂ H ₅ C(=O)-O- is more preferable, and CH ₃ C(=O)-O- (acetoxy group) is particularly preferable.

In said formula (a11-1), n _ax2 is an integer of 0-3, 0, 1 or 2 is preferable, and 0 or 1 is more preferable.

When n _ax2 is 2 or more, a plurality of Ra ^x02 may be bonded to each other to form a ring structure. A hydrocarbon ring may be sufficient as the ring structure formed here, and a heterocyclic ring may be sufficient as it. For example, ring structures formed by (bond between carbon atoms), one side of the aromatic ring (Wa ^x2) and the two Ra ^x02 that, that the two Ra ^x02 bond bonded to the same aromatic ring in the Wa ^x2 can be heard

As such structural unit (a11), for example, structural units each represented by the following general formulas (a11-u1-1) to (a11-u1-6) are preferably exemplified.

[Formula 10]

[In the formula, R ^α is a hydrogen atom, a methyl group, or a trifluoromethyl group. R ^β is an alkyl group, an alkoxy group or an acyloxy group. n _ax2 is an integer of 0-3. When n _ax2 is 2 or more, a plurality of R ^β may be bonded to each other to form a ring structure. n ₂₁ , n ₂₂ , n ₂₄ and n ₂₅ are each independently 0 or 1. n ₂₃ and n ₂₆ are each independently 1 or 2.]

In the formulas (a11-u1-1) to (a11-u1-6), the alkyl group, alkoxy group, and acyloxy group for ^{R β} are exemplified as substituents for ^{Ra x02 in the formula (a11-1).} It is the same as an alkyl group, an alkoxy group, and an acyloxy group.

Specific examples of the structural unit (structural unit (a11)) derived from the compound represented by the general formula (a11-1) are shown below.

In each of the following formulas, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

Among the above examples, the structural unit (a11) is preferably at least one selected from the group consisting of structural units represented by the general formulas (a11-u1-1) to (a11-u1-3), and the general formula (a11-) The structural unit represented by u1-1) is more preferable.

Among these, the structural unit (a11) is preferably a structural unit represented by any of the formulas (a11-u1-11), (a11-u1-21) or (a11-u1-31).

(A1) The number of structural units (a11) which a component has may be one, or 2 or more types may be sufficient as it.

When the component (A1) has a structural unit (a11), the proportion of the structural unit (a11) in the component (A1) is 1 to (100 mol%) with respect to the total (100 mol%) of all the structural units constituting the component (A1). It is preferable that it is 30 mol%, 1-25 mol% is more preferable, 1-20 mol% is still more preferable, 5-15 mol% is especially preferable.

By making the ratio of the structural unit (a11) equal to or more than the lower limit, etch resistance and lithographic characteristics are further improved. On the other hand, by setting it as below an upper limit, it becomes easy to balance with another structural unit.

≪Other constituent units≫

(A1) The component may have other structural units other than a structural unit (a10) and a structural unit (a11).

As a compound which induces such other structural unit, For example, Monocarboxylic acids, such as acrylic acid, methacrylic acid, and a crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; 2-methacryloyloxyethylsuccinic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid having a carboxyl group and an ester bond methacrylic acid derivatives; (meth)acrylic acid alkyl esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; (meth)acrylic acid aryl esters, such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; Epoxy group-containing polymerizable compounds, etc. are mentioned.

In the resist composition of the present embodiment, the component (A) contains the polymer compound (A1) (component (A1)) having the structural unit (a10).

As a preferable component (A1), the high molecular compound which has a structural unit (a10) at least is mentioned. Specifically, a polymer compound having a repeating structure of the structural unit (a10) (a homopolymer comprising the structural unit (a10)); A polymer compound having a repeating structure of a structural unit (a10) and a structural unit (a11) is preferably exemplified.

(A1) The weight average molecular weight (Mw) of the component (based on polystyrene conversion by gel permeation chromatography (GPC)) is not particularly limited, preferably 500 to 50000, more preferably 1000 to 30000, and 2000 - 20000 are more preferable.

If the Mw of the component (A1) is below the preferable upper limit of this range, there is sufficient solubility in a resist solvent for use as a resist. If it is more than the preferable lower limit of this range, the dry etching resistance and resist pattern cross-sectional shape are better. becomes

(A1) The dispersion degree (Mw/Mn) of a component is not specifically limited, 1.0-4.0 are preferable, 1.0-3.0 are more preferable, 1.5-2.5 are especially preferable. In addition, Mn represents a number average molecular weight.

The component (A1) is obtained by dissolving a monomer inducing each structural unit in a polymerization solvent, and therein, for example, azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate (for example, V-601, etc.) ) can be produced by adding a radical polymerization initiator such as a polymerization initiator.

Alternatively, the component (A1) is obtained by dissolving a monomer that induces the structural unit (a10) and, if necessary, a monomer that induces a structural unit other than the structural unit (a10) in a polymerization solvent, and therein, the radicals as described above. It can manufacture by adding a polymerization initiator, superposing|polymerizing, and performing a deprotection reaction after that.

In addition, at the time of polymerization, for example, by using in combination with a chain transfer agent such as _{HS-CH 2} -CH ₂ -CH ₂ -C(CF ₃ ) _{2 -OH, -C(CF 3} ) ₂ -OH at the terminal may be introduced. As described above, a copolymer in which a hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group is substituted with a fluorine atom is introduced is effective in reducing development defects and LER (line edge roughness: unevenness of line sidewalls).

・(A2) About ingredients

The resist composition of the present embodiment is a component (A), a base component that does not correspond to component (A1) and whose solubility in a developer changes due to the action of an acid (hereinafter referred to as “component (A2)”). may be used together.

The component (A2) is not particularly limited, and may be arbitrarily selected from a number of conventionally known base components for chemically amplified resist compositions.

(A2) A component may be used individually by 1 type of a high molecular compound or a low molecular compound, and may be used in combination of 2 or more type.

25 mass % or more is preferable with respect to the total mass of (A) component, as for the ratio of (A1) component in (A) component, 50 mass % or more is more preferable, 75 mass % or more is still more preferable, 100 It may be mass %. When the ratio is 25 mass% or more, a resist pattern excellent in various lithography characteristics such as high sensitivity, resolution and roughness improvement is likely to be formed.

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

<(B) component>

・(B0) Component

(B) Component is an acid generator component which generate|occur|produces an acid by exposure. In the resist composition of the present embodiment, component (B) contains at least an acid generator (B0) (component (B0)) represented by the following general formula (b0-1).

[Formula 16]

[Wherein, Rb ¹ is an organic group. Rb ² is a group represented by the following general formula (b0-r-1) or the following general formula (b0-r-2).]

[Formula 17]

[In formula (b0-r-1), Rb ²⁰¹ and Rb ²⁰² are each independently an organic group. * indicates a bond. In the formula (b0-r-2), Xb is a group that together with -(O=)CNC(=O)- forms a cyclic group having a cyclic imide structure. * indicates a bond hand.]

In the present embodiment, the component (B0) is not particularly limited as long as it is a compound represented by the formula (b0-1), and is, for example, represented by the following general formulas (b0-1-1) to (b0-1-6). and at least one compound selected from the group consisting of.

[Formula 18]

[Wherein, Rb ¹¹ and Rb ²¹ are each independently a non-aromatic group.]

[Formula 19]

[In the formula, Rb ¹² is an alkyl group or a halogenated alkyl group. Rb ²² is an aromatic group.]

[Formula 20]

[In the formula, Rb ¹³ is a hydrocarbon group which may have substitution. nb3 is 2 or 3. Ab is a divalent or trivalent organic group.]

[Formula 21]

[Wherein, Rb ¹⁴ is an aromatic polycyclic hydrocarbon group, a saturated or unsaturated non-aromatic polycyclic hydrocarbon group, or a group of a substituted derivative thereof. Rb ²⁴ is an inert organic group.]

[Formula 22]

[In the formula, Rb ¹⁵ is a substituted or unsubstituted monovalent saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic group. Xb ⁵ is a group that together with -(O=)CNC(=O)- forms a cyclic group having a cyclic imide structure.]

[Formula 23]

[In the formula, Rb ¹⁶ is an optionally substituted alkyl group or an optionally substituted aromatic hydrocarbon group. Rb ²⁶¹ to Rb ²⁶³ are each independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. nb6 is an integer of 0 to 5.]

In the formula (b0-1-1), ^{the non-aromatic group for Rb 11} and Rb ²¹ is an alkyl group, a halogenoalkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an alkoxy group, a cycloalkoxy group and a A danthyl group etc. are mentioned.

The alkyl group for Rb ¹¹ and Rb ²¹ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, or n-butyl group. , isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-octyl group, n-dodecyl group, and the like.

Halogenoalkyl group in Rb ¹¹ and Rb ²¹ are, as for the number of halogen atoms is not particularly limited, and may be introduced into one, or may be introduced into a plurality. Moreover, as a halogen atom, any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom may be sufficient. As this halogenoalkyl group, a C1-C4 halogenoalkyl group, for example, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, 2-bromopropyl group, etc. are preferable.

Examples of the alkenyl group for Rb ¹¹ and Rb ²¹ include a linear or branched alkenyl group having 2 to 6 carbon atoms, for example, a vinyl group, 1-propenyl group, isopropenyl group, 2-butenyl group, and the like. desirable.

Examples of the cycloalkyl group for Rb ¹¹ and Rb ²¹ include a cycloalkyl group having 5 to 12 carbon atoms, for example, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclododecyl group, and the like. A C4-C8 cycloalkenyl group, for example, 1-cyclobutenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group, 1-cycloheptenyl group, 1-cyclooctenyl group, etc. are preferable.

The alkoxy group for Rb ¹¹ and Rb ²¹ is preferably an alkoxy group having 1 to 8 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.

The cycloalkoxy group for Rb ¹¹ and Rb ²¹ is preferably a cycloalkoxy group having 5 to 8 carbon atoms, for example, a cyclopentoxy group or a cyclohexyloxy group.

In the formula (b0-1-1), as Rb ¹¹ , an alkyl group, a halogenoalkyl group and a cycloalkyl group, particularly an alkyl group are preferable. Rb ²¹ is preferably an alkyl group, a cycloalkyl group and a cycloalkenyl group, particularly a cycloalkenyl group. Especially, it is more preferable that ^{Rb 11} is a C1-C4 alkyl group and Rb ^{21 is a cyclopentenyl group.}

Specific examples of the compound represented by the formula (b0-1-1) include α-(methylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclohexyl Cenylacetonitrile, α-(methylsulfonyloxyimino)-1-cycloheptenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclooctenylacetonitrile, α-(trifluoromethylsulfonyloxyi Mino)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-cyclohexylacetonitrile, α-(ethylsulfonyloxyimino)-ethylacetonitrile, α-(propylsulfonyloxyimino) Mino)-propylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclopentylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimino)- 1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(n- Butylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclohexenylaceto and nitrile and α-(n-butylsulfonyloxyimino)-1-cyclohexenylacetonitrile.

In the formula (b0-1-2), ^{the alkyl group for Rb 12} is a linear or branched alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, or isopropyl group. group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and the like.

Examples of the halogenated alkyl group for Rb ¹² include a halogenated alkyl group having 1 to 4 carbon atoms, for example, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, and a 2-bromopropyl group.

In the formula (b0-1-2), ^{the aromatic group in Rb 22} means a group exhibiting physical and chemical properties specific to an aromatic compound, and examples include a phenyl group, a naphthyl group, a furyl group, and a thienyl group. can In ^{the aromatic group for Rb 22} , a part of hydrogen atoms of an aromatic ring constituting the aromatic group may be substituted with a substituent. As the substituent, a halogen atom, an alkyl group, an alkoxy group, a nitro group, etc. are mentioned.

Specifically, as the compound represented by the formula (b0-1-2), α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonyloxyimino)-4-methoxyphenylacetonitrile , α-(methylsulfonyloxyimino)-4-methylphenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-4-methyl Toxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(propylsulfonyloxyimino)-4-methylphenylacetonitrile, α-(methylsulfonyloxyimino)-4 -Bromophenylacetonitrile, etc. are mentioned.

In the formula (b0-1-3), examples ^{of the hydrocarbon group for Rb 13} include an aromatic group or a non-aromatic hydrocarbon group. Here, the aromatic group preferably has 6 to 14 carbon atoms, for example, an aromatic hydrocarbon group such as a phenyl group, a tolyl group, a methoxyphenyl group, a xylyl group, a biphenyl group, a naphthyl group, and an anthryl group, a furanyl group, and a pyri group. Heterocyclic groups, such as a dil group and a quinolyl group, are mentioned. In addition, the non-aromatic hydrocarbon group includes a hydrocarbon group that does not have an aromatic ring such as a benzene ring, a naphthalene ring, a furan ring, a thiophene ring, and a pyridine ring, for example, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, for example Examples thereof include an alkyl group, an alkenyl group, a cycloalkyl group, and a cycloalkenyl group. Although linear or branched may be sufficient as this alkyl group and an alkenyl group, a C1-C12 thing and a C4-C12 thing of a cycloalkyl group and a cycloalkenyl group are preferable. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-octyl group, n-dodecyl group, etc. Examples of the nyl group include an ethenyl group, propenyl group, butenyl group, butadienyl group, hexenyl group, octadienyl group, and the like, and examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and a cyclododecyl group. , Examples of the cycloalkenyl group include 1-cyclobutenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group, 1-cycloheptenyl group and 1-cyclooctenyl group, respectively.

In the formula (b0-1-3), ^{the hydrocarbon group for Rb 13} may have a substituent. As the substituent, a halogen atom, a hydroxyl group, an alkoxy group, an acyl group, etc. are mentioned.

In the formula (b0-1-3), examples of the divalent or trivalent organic group for Ab include a divalent or trivalent aliphatic hydrocarbon group and an aromatic hydrocarbon group.

Specific examples of the compound represented by the formula (b0-1-3) are shown below.

[Formula 24]

[Formula 25]

In the formula (b0-1-4), ^{the aromatic polycyclic hydrocarbon group for Rb 14} includes, for example, 2-indenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthryl group and the like. and aromatic non-condensed polycyclic hydrocarbon groups such as an aromatic condensed polycyclic hydrocarbon group, a biphenyl group and a terphenyl group. Further, as the substituted derivative group, the aromatic ring of these groups is substituted with a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom, a nitro group, an amino group, a hydroxyl group, an alkyl group, an alkoxyl group, etc. For example, 5-hydroxy-1-naphthyl group, 4-amino-1-naphthyl group, etc. are mentioned.

In the formula (b0-1-4), ^{the saturated or unsaturated non-aromatic polycyclic hydrocarbon group for Rb 14} includes, for example, a polycyclic terpene residue and an adamantyl group, but the polycyclic terpene residue is desirable. Examples of the substituted derivative group include those having suitable substituents on the ring, such as a halogen atom such as a chlorine atom, a bromine atom, and an iodine atom, a nitro group, an amino group, a hydroxyl group, an oxo group, an alkyl group, an alkoxyl group, etc. . Examples of such a group include a camphor-3-yl group, a camphor-8-yl group, a camphor-10-yl group, and a 3-bromocamphor-10-yl group.

As this Rb ¹⁴ , a naphthyl group and a camphor-10-yl group are preferable, and 1-naphthyl group is especially preferable at the point excellent in resolution.

In the formula (b0-1-4), ^{the inactive organic group in Rb 24} is an organic group that is inactive to components coexisting under the conditions of use, and is not particularly limited, but is sensitive to excimer lasers, electron beams, and X-rays. An aromatic group is preferable at the point. As this aromatic group, a phenyl group, a naphthyl group, a furyl group, a thienyl group etc. are mentioned, for example. Moreover, these aromatic groups may have inactive substituents, such as a halogen atom like a chlorine atom, a bromine atom, and an iodine atom, an alkyl group, an alkoxyl group, and a nitro group.

Specific examples of the compound represented by the formula (b0-1-4) include α-(1-naphthylsulfonyloxyimino)-4-methoxybenzylcyanide, α-(2-naphthylsulfonyloxyimino)- 4-Methoxybenzylcyanide, α-(1-naphthylsulfonyloxyimino)benzylcyanide, α-(2-naphthylsulfonyloxyimino)benzylcyanide, α-(10-camphorsulfonyloxyimino)- 4-Methoxybenzylcyanide, α-(10-camphorsulfonyloxyimino)benzylcyanide, α-(3-camphorsulfonyloxyimino)-4-methoxybenzylcyanide, α-(3-bromo -10-camphorsulfonyloxyimino)-4-methoxybenzylcyanide etc. are mentioned.

In the formula (b0-1-5), ^{the substituted or unsubstituted monovalent saturated hydrocarbon group or unsaturated hydrocarbon group for Rb 15} is, for example, a linear or branched saturated or unsaturated group having 1 to 8 carbon atoms. Hydrocarbon groups and groups in which these are substituted with a halogen atom, a nitro group, an acetylamino group, a lower alkoxy group, a monocyclic aryl group, etc. are mentioned, but those having a substituent such as a halogen atom and a lower alkoxy group are particularly preferable. In addition, ^{the substituted or unsubstituted monovalent aromatic group for Rb 15} includes, for example, monocyclic or bicyclic ones, in particular, a benzene ring in which a vinyl group, an alkyl group, an alkoxy group, a halogen atom, or the like is substituted. it is preferable

In the formula (b0-1-5), ^{as the cyclic group having a cyclic imide structure formed by Xb 5 together} with -(O=)CNC(=O)-, a succinimide ring, a maleimide ring, glutarimide ring, phthalimide ring, 1,8-naphthalenedicarboxyimide ring, etc. are mentioned. The ^{cyclic group having a cyclic imide structure formed by Xb 5 together} with -(O=)CNC(=O)- may have a substituent. Examples of the substituent include a halogen atom, a nitro group, an acetylamino group, an alkoxy group, and a monocyclic aryl group.

Specific examples of the compound represented by the formula (b0-1-5) include N-methylsulfonyloxysuccinimide, N-isopropylsulfonyloxysuccinimide, N-chloroethylsulfonyloxysuccinimide, N-(p-methoxyphenyl)sulfonyloxysuccinimide, N-(p-vinylphenyl)sulfonyloxysuccinimide, N-naphthylsulfonyloxysuccinimide, N-phenylsulfonyloxysuccinimide , N-(2,4,6-trimethylphenyl)sulfonyloxysuccinimide, N-methylsulfonyloxymaleimide, N-isopropylsulfonyloxymaleimide, N-chloroethylsulfonyloxymaleimide, N -(p-methoxyphenyl)sulfonyloxymaleimide, N-(p-vinylphenyl)sulfonyloxymaleimide, N-naphthylsulfonyloxymaleimide, N-phenylsulfonyloxymaleimide, N-(2 ,4,6-trimethylphenyl)sulfonyloxymaleimide, N-methylsulfonyloxyphthalimide, N-isopropylsulfonyloxyphthalimide, N-chloroethylsulfonyloxyphthalimide, N-(p -Methoxyphenyl)sulfonyloxyphthalimide, N-(p-vinylphenyl)sulfonyloxyphthalimide, N-naphthylsulfonyloxyphthalimide, N-phenylsulfonyloxyphthalimide, N-( 2,4,6-trimethylphenyl)sulfonyloxyphthalimide, the compound described in paragraphs [0089] to [0091] of JP-A-10-097075, and the like.

In the formula (b0-1-6), ^{as the alkyl group for Rb 16} , a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, or an isopropyl group is preferable. , n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, octyl group, nonyl group , decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecyl group, and the like. .

Especially, ^{as an alkyl group in Rb 16} , a C1-C10 linear or branched alkyl group is preferable, and a C1-C5 linear or branched alkyl group is more preferable.

The alkyl group for Rb ¹⁶ may have a substituent. Examples of the substituent include a halogen atom, a halogenated alkyl group, CN, NO ₂ , a phenyl group, an alkoxy group, a carboxy group, a carbonyl group, a sulfonyl group, and an amino group.

In the formula (b0-1-6), examples ^{of the aromatic hydrocarbon group for Rb 16} include a phenyl group, a naphthyl group, a phenanthryl group, an anthracyl group, and a heteroaryl group. The aromatic hydrocarbon group for Rb ^{16 may have a substituent.} Examples of the substituent include a halogen atom, a halogenated alkyl group, CN, NO ₂ , a phenyl group, an alkoxy group, a carboxy group, a carbonyl group, a sulfonyl group, and an amino group.

Specific examples of the compound represented by the formula (b0-1-6) include a compound represented by the following formula (b0-1-61), the compounds of Examples 25 to 40 and 53 of Japanese Patent Application Laid-Open No. 2002-508774, and the like. can be heard

[Formula 26]

(B0) Other specific examples of the component include the compounds described in paragraphs [0056], [0058], [0060], and [0063] of Japanese Patent No. 4110392, paragraphs [0053] and [0054] of Japanese Patent No. 4000469 ], [0056], [0058], [0060]-[0062], and the like.

Among them, as the component (B1), the compound represented by the formula (b0-1-2), the compound represented by the formula (b0-1-3), the compound represented by the formula (b0-1-5), and the above At least one selected from the group consisting of compounds represented by the formula (b0-1-6) is preferable, and the compound represented by the formula (b0-1-2), the compound represented by the formula (b0-1-3), and the At least 1 type selected from the group which consists of a compound represented by a formula (b0-1-6) is more preferable.

Below, the preferable specific example of (B0) component is given.

[Formula 27]

The component (B0) contained in the resist composition of this embodiment may be used individually by 1 type, and may use 2 or more types together.

In the resist composition of the present embodiment, the content of component (B0) is preferably 50 parts by mass or less, more preferably 0.1 to 40 parts by mass, and still more preferably 0.1 to 30 parts by mass relative to 100 parts by mass of component (A). And 0.1-20 mass parts is especially preferable.

(B) By making content of a component into the said range, pattern formation is fully performed.

・(B1) About component

The resist composition of the present embodiment may contain, as component (B), an acid generator other than component (B0) (hereinafter referred to as “component (B1)”).

The component (B1) is not particularly limited, and those previously proposed as acid generators for chemically amplified resist compositions can be used.

As such an acid generator, Onium salt-type acid generators, such as an iodonium salt and a sulfonium salt, an oxime sulfonate-type acid generator; diazomethane-based acid generators such as bisalkyl or bisarylsulfonyldiazomethanes and poly(bissulfonyl)diazomethanes; and various kinds of nitrobenzylsulfonate-based acid generators and disulfone-based acid generators.

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

[Formula 28]

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

{Anion part}

· (b-1) the anion part of the component

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

Cyclic group which may have a substituent:

The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group which does not have aromaticity. Moreover, saturated or unsaturated may be sufficient as an aliphatic hydrocarbon group, and it is preferable that it is usually saturated.

The aromatic hydrocarbon group for R ¹⁰¹ is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. . However, carbon number in a substituent shall not be included in the carbon number.

Specifically, the aromatic ring of the aromatic hydrocarbon group for R ¹⁰¹ is benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic heterocyclic ring in which some of the carbon atoms constituting these aromatic rings are substituted with hetero atoms. and the like. As a hetero atom in an aromatic heterocyclic ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Specifically, the aromatic hydrocarbon group for R ¹⁰¹ is a group in which one hydrogen atom is removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), and one hydrogen atom in the aromatic ring is an alkylene group. Substituted groups (For example, arylalkyl groups, such as a benzyl group, a phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.) etc. are mentioned. It is preferable that carbon number of the said alkylene group (the alkyl chain in an arylalkyl group) is 1-4, C1-C2 is more preferable, C1 is especially preferable.

^Examples of the cyclic aliphatic hydrocarbon group for R 101 include an aliphatic hydrocarbon group having a ring in its structure.

Examples of the aliphatic hydrocarbon group containing a ring in this structure include an alicyclic hydrocarbon group (a group in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the terminus of a linear or branched aliphatic hydrocarbon group , a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group.

It is preferable that carbon number is 3-30, and, as for the said alicyclic hydrocarbon group, it is more preferable that carbon number is 3-20.

The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing one or more hydrogen atoms from a monocycloalkane is preferable. The monocycloalkane is preferably a monocycloalkane having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which one or more hydrogen atoms have been removed from the polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, examples of the polycycloalkane include polycycloalkanes having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane; A polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton is more preferable.

Among them, ^{the cyclic aliphatic hydrocarbon group for R 101} is preferably a group in which one or more hydrogen atoms are removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom is removed from a polycycloalkane, An adamantyl group, a norbornyl group, or a cyclic group having a steroid skeleton is particularly preferred, and an adamantyl group or a cyclic group having a steroid skeleton is most preferred.

The linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and still more preferably has 1 carbon atom. to 3 are particularly preferred.

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

The branched chain aliphatic hydrocarbon group is preferably a branched chain alkylene group, specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, Alkylmethylene groups, such as -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) _{2 -;} -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH _{3) 2} -CH ₂ - alkyl group such as ethylene; Alkyltrimethylene groups, such as -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH _{2 -;} Alkylalkylene groups, such as alkyltetramethylene groups, such as -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH _{2 -, etc. are mentioned.} As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

Moreover, ^{the cyclic hydrocarbon group for R 101} may contain a hetero atom like a heterocyclic ring. Specifically, the lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), and the general formulas (a5-r-1) to (a5-r-4), respectively -SO ₂ - containing cyclic groups shown, and heterocyclic groups each represented by the following formulas (r-hr-1) to (r-hr-16) are mentioned.

[Formula 29]

Examples of the substituent in the cyclic group of R ¹⁰¹ include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. As the alkyl group as the substituent, an alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group are most preferable.

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 iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and a methoxy group , an ethoxy group is most preferred.

As a halogen atom as a substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.

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

The carbonyl group as a substituent is a group that substitutes for the methylene group (-CH ₂ -) constituting the cyclic hydrocarbon group.

A chain alkyl group which may have a substituent:

The linear alkyl group for R ¹⁰¹ may be either linear or branched.

The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group , tetradecyl group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group and the like.

The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2 -Ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, etc. are mentioned.

A chain alkenyl group which may have a substituent:

The chain alkenyl group for R ¹⁰¹ may be either linear or branched, preferably having 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, still more preferably 2 to 4 carbon atoms. and having 3 carbon atoms is particularly preferable. As a linear alkenyl group, a vinyl group, a propenyl group (allyl group), a butynyl group etc. are mentioned, for example. As a branched alkenyl group, 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group etc. are mentioned, for example.

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

Examples of the substituent in the chain alkyl or alkenyl group for R ¹⁰¹ include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and a cyclic group for ^{R 101 .} can

Among them, R ¹⁰¹ is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, a group in which one or more hydrogen atoms have been removed from a phenyl group, a naphthyl group, or a polycycloalkane; lactone-containing cyclic groups each represented by the general formulas (a2-r-1) and (a2-r-3) to (a2-r-7); _{-SO 2} - containing cyclic groups each represented by the above general formulas (a5-r-1) to (a5-r-4) are preferable.

In the formula (b-1), Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, Y ¹⁰¹ may contain atoms other than an oxygen atom. As atoms other than an oxygen atom, a carbon atom, a hydrogen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example.

Examples of the divalent linking group containing such an oxygen atom include linking groups represented by the general formulas (y-al-1) to (y-al-8).

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

In the formula (b-1), V ¹⁰¹ is a single bond, an alkylene group, or a fluorinated alkylene group. The alkylene group and the fluorinated alkylene group for 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. It is preferable that it is a fluorine atom or a C1-C5 perfluoroalkyl group, and, as for R ^{102, it is more preferable that it is a fluorine atom.}

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

[Formula 30]

[wherein, R" ¹⁰¹ is an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group each represented by the formulas (r-hr-1) to (r-hr-6), or a substituent which may be It is a chain alkyl group. R" ¹⁰² is an optionally substituted aliphatic cyclic group, and a lactone represented by the general formulas (a2-r-1) and (a2-r-3) to (a2-r-7), respectively. _{a containing cyclic group, or a -SO 2} - containing cyclic group each represented by the general formulas (a5-r-1) to (a5-r-4). R" ¹⁰³ is an optionally substituted aromatic cyclic group, an optionally substituted aliphatic cyclic group, or an optionally substituted chain alkenyl group. V" ¹⁰¹ is a single bond, an alkyl having 1 to 4 carbon atoms. a lene group or a fluorinated alkylene group having 1 to 4 carbon atoms. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. v" is each independently an integer from 0 to 3, q" is each independently an integer from 1 to 20, and n" is 0 or 1.]

R ^"101, R" ¹⁰² and R "aliphatic cyclic group which may have a ¹⁰³ substituent group is a group exemplified as the aliphatic hydrocarbon group of annular in said R ¹⁰¹ is preferably In the above substituents, R ¹⁰¹ The same thing as the substituent which may substitute the cyclic aliphatic hydrocarbon group in this is mentioned.

R "aromatic cyclic group which may have a substituent in the ¹⁰³ is preferably a group exemplified as the aromatic hydrocarbon group in groups a hydrocarbon of type rings in the above-mentioned R ^101. As the substituent of the R ¹⁰¹ The same thing as the substituent which may substitute the aromatic hydrocarbon group is mentioned.

R "group of the chain which may have a substituent in the ^101, is due exemplified as the alkyl group of the chain-like in the above-mentioned R ¹⁰¹ is preferable. R" ¹⁰⁴ Al of chain which may have a substituent in the The kenyl group is preferably the group exemplified as the chain alkenyl group for ^{R 101 .}

V" ¹⁰¹ is preferably a single bond or a fluorinated alkylene group, more preferably a single bond or a fluorinated alkylene group having 1 to 3 carbon atoms. When V" ¹⁰¹ is a fluorinated alkylene group -V" ¹⁰¹ -C(F V" ¹⁰¹ in (R" ¹⁰² )-SO ₃ ^- _{is -CF 2} -, -CHF-, -CF ₂ CF ₂ -, -CHFCF ₂ -, -CF(CF ₃ )CF ₂ -, - It is preferable that it is CH(CF ₃ )CF _{2 -, and -CF 2} -, -CHF- are more preferable.

R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. It is preferable that it is a fluorine atom or a C1-C5 perfluoroalkyl group, and, as for R ^{102, it is more preferable that it is a fluorine atom.}

v" is an integer of 0-3, Preferably it is 0 or 1. q" is an integer of 1-20, Preferably it is an integer of 1-10, More preferably, it is an integer of 1-5 , more preferably 1, 2 or 3, particularly preferably 1 or 2. n" is 0 or 1.

-(b-2) anion part of component

In formula (b-2), R ¹⁰⁴ and R ¹⁰⁵ are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, The same thing as ^{R 101} in said Formula (b-1) is mentioned, respectively, 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 linear alkyl group which may have a substituent, and more preferably a linear or branched alkyl group, or a linear or branched 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 carbon number of the chain alkyl group of R ¹⁰⁴ and R ¹⁰⁵ is preferably smaller within the above carbon number range for reasons such as good solubility in the resist solvent. Also, R ^104, in the alkyl chain of R ^105, the more the number of hydrogen atoms being substituted by fluorine atoms, it is, preferable, since the strength of the strong acid. The proportion of fluorine atoms in the chain alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably, a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. to be.

In 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 as those ^{of V 101 in formula (b-1) can be mentioned.}

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

-(b-3) anion part of component

In formula (b-3), R ¹⁰⁶ to R ¹⁰⁸ are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, ^{The same thing as R 101} in Formula (b-1) is mentioned, respectively.

L ¹⁰³ to L ¹⁰⁵ are each independently a single bond, -CO-, or -SO ₂ -.

{Cathion part}

In formulas (b-1), (b-2) and (b-3), m is an integer of 1 or more, M' ^m+ is an m-valent onium cation, preferably a sulfonium cation or an iodonium cation Examples thereof include organic cations represented by the following general formulas (ca-1) to (ca-4).

[Formula 31]

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

Examples of the aryl group for R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² include an aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.

The alkyl group for 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 for 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 ²¹¹ to R ²¹² may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and the following general formula (ca-r-1 ) to (ca-r-7).

[Formula 32]

[ ^{Wherein, R'201} is each independently a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.]

The cyclic group which may have a substituent for R' ²⁰¹ , the chain alkyl group which may have a substituent, or the chain alkenyl group which may have a substituent is the same as ^{R 101 in the above formula (b-1).} Examples of the cyclic group which may have a substituent or the chain-like alkyl group which may have a substituent other than those mentioned above include those similar to the acid dissociable group represented by the above formula (a1-r-2).

When R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ , and R ²¹¹ to R ²¹² are bonded to each other to form a ring together with a sulfur atom in the formula, a hetero atom such as a sulfur atom, an oxygen atom or a nitrogen atom, or a carbonyl group; -SO-, -SO ₂ -, -SO ₃ -, -COO-, -CONH-, or -N(R _N )- (R _N is an alkyl group having 1 to 5 carbon atoms). You can do it. As a ring to be formed, it is preferable that it is a 3-10 membered ring including a sulfur atom, and it is especially preferable that one ring which contains the sulfur atom in the formula is a 5-7 membered ring. Specific examples of the ring to be formed include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring a ring, a thianthrene ring, a phenoxatiin ring, a tetrahydrothiophenium ring, a tetrahydrothiopyranium ring, etc. are mentioned.

R ²⁰⁸ to R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they become an alkyl group, they may combine with each other to form a ring.

R ²¹⁰ is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or -SO ₂ - containing cyclic group which may have a substituent.

Examples of the aryl group for R ²¹⁰ include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable.

The alkyl group for R ²¹⁰ is a chain or cyclic alkyl group, and preferably has 1 to 30 carbon atoms.

The ^{alkenyl group for R 210} preferably has 2 to 10 carbon atoms. As _{the -SO 2} - containing cyclic group which may have a substituent in ^{R 210} _{, "-SO 2} - containing polycyclic group" is preferable, and the group represented by the general formula (a5-r-1) is more preferable. Do.

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

Examples of the arylene group for Y ²⁰¹ include groups in which one hydrogen atom has been removed from the aryl group exemplified as the aromatic hydrocarbon group for ^{R 101} in Formula (b-1) to be described later.

Examples of the alkylene group and the alkenylene group for Y ²⁰¹ include groups in which one hydrogen atom has been removed from the groups exemplified as the chain alkyl group and chain alkenyl group for ^{R 101 in the formula (b-1) described above.} can

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

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

As the ^{divalent linking group for W 201} , a divalent hydrocarbon group which may have a substituent is preferable, and examples of the same divalent hydrocarbon group which may have a substituent as for ^{Ya 21 in the above-mentioned general formula (a2-1) are exemplified.} can The ^{divalent linking group for W 201} may be linear, branched or 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. As an arylene group, a phenylene group, a naphthylene group, etc. are mentioned, A phenylene group is especially 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. The ^{trivalent linking group for W 201} is preferably a group in which two carbonyl groups are bonded to an arylene group.

Specifically, as a preferable cation represented by the formula (ca-1), the following formulas (ca-1-1) to (ca-1-78), (ca-1-101) to (ca-1-149) and cations each represented by .

In the following formula, g1 represents the number of repetitions, and g1 is an integer of 1 to 5. g2 represents the number of repetitions, and g2 is an integer of 0-20. g3 represents the number of repetitions, and g3 is an integer of 0-20.

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Wherein, R" ²⁰¹ is a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, and cya, which ^{R 201} to R ²⁰⁷ and R ²¹¹ to R ^{212 may have.} and a no group, an amino group, an aryl group, and groups each represented by the general formulas (ca-r-1) to (ca-r-7).]

As a preferable cation represented by said formula (ca-2), specifically, a cation, diphenyliodonium cation, and bis(4) respectively represented by the following formulas (ca-2-1) to (ca-2-3) -tert- butylphenyl) iodonium cation is mentioned.

[Formula 43]

Specific examples of preferred cations represented by the formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-7).

[Formula 44]

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

[Formula 45]

Among the above, as for the cation moiety ((M ^m+ ) _1/m ), a cation represented by the general formula (ca-1) or (ca-2) is preferable, and the cation moiety ((M m+ ) 1/m ) is preferably a cation represented by the general formulas (ca-1-1) to (ca-1). -78), (ca-1-101) to (ca-1-149) and a cation represented by the formulas (ca-2-1) to (ca-2-3) are more preferable.

In the resist composition of this embodiment, the component (B1) may be used individually by 1 type, and may use 2 or more types together.

When the resist composition contains component (B1), the content of component (B1) in the resist composition is preferably 50 parts by mass or less, more preferably 0.1 to 40 parts by mass, based on 100 parts by mass of component (A), , 0.1-30 mass parts is more preferable, and 0.1-20 mass parts is especially preferable.

<(C) component>

(C) A component is a crosslinking agent. The component (C) is not particularly limited, and can be arbitrarily selected from those known as crosslinking agents for negative resist compositions. Examples of such an acid-crosslinking material include an amino resin having a hydroxyl group or an alkoxyl group, for example, a melamine resin, a urea resin, a guanamine resin, an acetoguanamine resin, a benzoguanamine resin, a glycoluril-formaldehyde resin, and succinate. nylamide-formaldehyde resin, ethylene urea-formaldehyde resin, etc. are mentioned. These are easily methylolated by reacting melamine, urea, guanamine, acetoguanamine, benzoguanamine, glycoluril, succinylamide, and ethyleneurea with formalin in boiling water, or alkoxylation by further reacting a lower alcohol with it. is obtained A practical phase can be obtained as melamine resins, such as Nikalac MX-750, Nikalac MW-30, and Nikalac MW100LM, and urea resins, such as Nikalac MX-290 (all are the Sanwa Chemicals make). Moreover, benzoguanamine resins, such as Cymel 1123 and Cymel 1128 (made by Mitsui Cyanad), can also be obtained as a commercial item.

In addition, as component (C), 1,3,5-tris(methoxymethoxy)benzene, 1,2,4-tris(isopropoxymethoxy)benzene, 1,4-bis(sec-butoxy) A phenol compound having an alkoxyl group, such as a benzene compound having an alkoxyl group such as methoxy)benzene, or a hydroxyl group or an alkoxyl group such as 2,6-dihydroxymethyl-p-tert-butylphenol can also be used.

Especially, as (C)component, _{it is preferable to have a -NCH 2 -OCH 3} group, the compound represented by following formula (c1-1) or (c1-2) is more preferable, following formula (c1-1) Or the compound which has a melamine skeleton represented by (c1-2) is more preferable.

[Formula 46]

[In the formula, nc1 and nc2 are each independently an integer of 1 to 3.]

(C) A component may be used individually by 1 type, and may be used in combination of 2 or more type. In the resist composition of the present embodiment, the content of component (C) is preferably from 1 to 50 parts by mass, more preferably from 3 to 40 parts by mass, and further from 3 to 30 parts by mass relative to 100 parts by mass of component (A). It is preferable, and 5-25 mass parts is the most preferable.

(C) Crosslinking formation fully advances that content of a component is more than a lower limit, and resolution performance and a lithographic characteristic improve more. Moreover, a favorable resist pattern with little swelling is obtained. Moreover, when it is below this upper limit, the storage stability of a resist composition is favorable and it becomes easy to suppress deterioration of sensitivity with time.

<(Z) component>

(Z) The component will not be specifically limited if it is an aromatic compound which has one or two phenolic hydroxyl groups in a molecule|numerator and does not have a carboxyl group.

As (Z) component, it is preferable to contain at least 1 sort(s) chosen from the group which consists of a compound represented by the following general formula (z1-1), and a compound represented by the following general formula (z2-1).

[Formula 47]

[In formula (z1-1), V _z ¹ is a divalent linking group having no hydroxy group and no carboxy group. In formula (z2-1), Rz ² is a hydrocarbon group. n1 is 1 or 2. n2 is an integer of 2-5. However, n1 + n2 ≤ 6.]

In the formula (z1-1), as the divalent linking group not having a hydroxy group or a carboxy group in _{V z} ^{1 , among the divalent linking groups in Ya x 1} in the general formula (a10-1) described above, The thing which does not have a hydroxyl group and a carboxy group is mentioned. In addition, as the _{divalent linking group of V z} ¹ , a part of the hydrogen atoms constituting the linear or branched aliphatic hydrocarbon group as the divalent linking group ^{in Ya x 1} in the above-mentioned general formula (a10-1) is and groups substituted with aromatic hydrocarbon groups.

As the linear or branched aliphatic hydrocarbon group in "a group in which a part of the hydrogen atoms constituting the linear or branched aliphatic hydrocarbon group is substituted with an aromatic hydrocarbon group", a methylene group [-CH ₂ -] , ethylene group [-(CH ₂ ) ₂ -], -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH _{Alkylmethylene groups, such as 3} )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, and -C(CH ₂ CH ₃ ) ₂ -, etc. are mentioned.

Examples of the aromatic hydrocarbon group in the "group in which a part of the hydrogen atoms constituting the linear or branched aliphatic hydrocarbon group are substituted with an aromatic hydrocarbon group" include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, etc. and groups in which one hydrogen atom has been removed from an aromatic ring.

The aromatic hydrocarbon group in "a group in which a part of hydrogen atoms constituting a linear or branched aliphatic hydrocarbon group is substituted with an aromatic hydrocarbon group" may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an arylalkyl group, and the like.

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.

As the alkoxy group, halogen atom and halogenated alkyl group as the substituent, in the ^{divalent linking group for Ya x1} in the above-mentioned general formula (a10-1), as a substituent for substituting a hydrogen atom possessed by the cyclic aliphatic hydrocarbon group, exemplified.

Examples of the arylalkyl group as the substituent include a benzyl group, a phenethyl group, a phenyl-t-butyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, and a 2-naphthylethyl group. The arylalkyl group may have a substituent such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, or an arylalkyl group.

As the compound represented by the formula (z1-1), a compound represented by the following general formula (z1-1-1) is preferable.

[Formula 48]

[In the formula, R _z ¹¹ and R _z ¹² are each independently a hydrogen atom or a hydrocarbon group which may have a substituent. R _z ¹¹ and R _z ¹² may combine with each other to form a ring.]

In the formula (z1-1-1), examples _{of the hydrocarbon group for R z} ¹¹ and R _z ¹² include a linear or branched alkyl group, an aromatic hydrocarbon group which may have a substituent, and the like.

The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 or 2 carbon atoms. Specifically, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. are mentioned. Among these, a methyl group, an ethyl group, or n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

It is preferable that carbon number is 3-10, and, as for this branched alkyl group, C3-C5 is more preferable. Specific examples thereof include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc., which are isopropyl group it is preferable

Examples _{of the aromatic hydrocarbon group for R z} ¹¹ and R _z ¹² include groups in which one hydrogen atom is removed from an aromatic ring such as benzene, fluorene, naphthalene, anthracene, phenanthrene, and biphenyl.

The aromatic hydrocarbon group in R _z ¹¹ and R _z ^{12 may have a substituent.} The substituent is the same as the substituent which the aromatic hydrocarbon group may have in the above "group in which a part of the hydrogen atoms constituting the linear or branched aliphatic hydrocarbon group is substituted with an aromatic hydrocarbon group".

In the formula (z1-1-1), R _z ¹¹ and R _z ¹² may be bonded to each other to form a ring. As a ring to be formed, aliphatic rings, such as a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring, are mentioned, for example.

In the formula (z1-1-1), R _z ¹¹ and R _z ¹² are a linear alkyl group having 1 to 5 carbon atoms or an aromatic hydrocarbon group which may have a substituent, or R _z ¹¹ and R _z ¹² are preferably bonded to each other to form an aliphatic ring, a methyl group, a phenyl group, or a 4-(4-hydroxyphenyl-t-butyl)phenyl group, or R _z ¹¹ and R _z ¹² are bonded to each other to form a cyclohexane ring It is more preferable to form

Examples ^{of the hydrocarbon group for Rz 2} in the formula (z2-1) include those exemplified as the hydrocarbon group for _{R z} ¹¹ and R _z ^{12 in the formula (z1-1-1).} Among these, as Rz ² , an aromatic hydrocarbon group is preferable, a phenyl group or a benzyl group is more preferable, and a phenyl group is still more preferable.

In said formula (z1-2), 1 is preferable for n1. 2 or 3 is preferable and, as for n2, 2 is more preferable.

As a compound represented by the said formula (z1-2), the compound represented by the following general formula (z1-2-1) is preferable.

[Formula 49]

[Wherein, Rz ²¹ and Rz ²² are each independently an aromatic hydrocarbon group.]

Examples ^{of the hydrocarbon group for Rz 2} in the formula (z1-2-1) include those exemplified as the hydrocarbon group for _{R z} ¹¹ and R _z ^{12 in the formula (z1-1-1).} Among these, as Rz ² , a phenyl group or a benzyl group is preferable, and a phenyl group is more preferable.

Specific examples of the component (Z) are given below.

[Formula 50]

(Z) It is preferable that it is 1000 or less, as for the mass average molecular weight (Mw) of component, it is more preferable that it is 100-950, It is still more preferable that it is 150-900.

(Z) When the mass average molecular weight of component is below the upper limit of the said preferable range, board|substrate adhesion|attachment performance will improve easily and wet etching resistance will improve easily.

The component (Z) contained in the resist composition of this embodiment may be used individually by 1 type, and may use 2 or more types together.

In the resist composition of the present embodiment, the content of component (Z) is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, and 3 to 20 parts by mass based on 100 parts by mass of component (A). more preferably.

When the ratio of the component (Z) is within the above-mentioned preferred range, the etching resistance is good and it is easy to form a pattern having a good shape.

<Optional ingredients>

≪(D) ingredient≫

In the resist composition of the present embodiment, in addition to component (A), component (B), component (C), and component (Z), an acid diffusion control agent component (hereinafter referred to as “component (D)”) .) may be included. Component (D) acts as a quencher (acid diffusion controlling agent) that traps acids generated by exposure in the resist composition.

As the component (D), for example, the nitrogen-containing organic compound (D1) (hereinafter “component (D1)”, decomposed by exposure that does not correspond to the component (D1), light decay that loses acid diffusion controllability) and base (D2) (hereinafter referred to as "component (D2)").) and the like.

By setting it as the resist composition containing component (D), when forming a resist pattern, the contrast of the exposed part and unexposed part of a resist film can be improved more.

・(D1) About component

Component (D1) is a base component and is a nitrogen-containing organic compound component that acts as an acid diffusion control agent in the resist composition.

It will not specifically limit as a component (D1), if it acts as an acid diffusion controlling agent, For example, an aliphatic amine, an aromatic amine, etc. are mentioned.

Among them, the aliphatic amine is preferably a secondary aliphatic amine or a tertiary aliphatic amine.

The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms.

Examples of the aliphatic amine include amines (alkylamines or alkylalcoholamines) or cyclic amines in which at least one hydrogen atom of _{ammonia NH 3 is substituted with an alkyl group having 12 or less carbon atoms or a hydroxyalkyl group.}

Specific examples of the alkylamine and the alkyl alcoholamine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; Trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri trialkylamines such as -n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcoholamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine and tri-n-octanolamine. Among these, a C5-C10 trialkylamine is more preferable, and tri-n-pentylamine or tri-n-octylamine is especially preferable.

As a cyclic amine, the heterocyclic compound which contains a nitrogen atom as a hetero atom is mentioned, for example. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine).

Specific examples of the aliphatic monocyclic amine include piperidine and piperazine. The aliphatic polycyclic amine preferably has 6 to 10 carbon atoms, and specifically, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0] -7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane, etc. are mentioned.

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

Examples of the aromatic amine include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, an aniline compound, and N-tert-butoxycarbonylpyrrolidine.

(D1) A component may be used individually by 1 type, and may be used in combination of 2 or more type. (D1) Among the above, an aromatic amine is preferable and, as for a component, an aniline compound is more preferable. Examples of the aniline compound include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline.

・(D2) About component

The component (D2) is not particularly limited as long as it decomposes upon exposure and loses acid diffusion controllability, and a compound represented by the following general formula (d2-1) (hereinafter referred to as “component (d2-1)”). , a compound represented by the following general formula (d2-2) (hereinafter referred to as “(d2-2) component”) and a compound represented by the following general formula (d2-3) (hereinafter referred to as “(d2-3) component”) .) at least one compound selected from the group consisting of

Components (d2-1) to (d2-3) do not act as a quencher because they are decomposed in the exposed portion of the resist film and lose acid diffusion controllability (basicity), but act as a quencher in the unexposed portion of the resist film.

[Formula 51]

[Wherein, Rd ¹ to Rd ⁴ are a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. However, it is assumed that the fluorine atom is not bonded to the carbon atom adjacent to the S atom ^{in Rd 2} in the general formula (d2-2). Yd ¹ is a single bond or a divalent linking group. m is an integer greater than or equal to 1, and M' ^m+ is each independently an m-valent onium cation.]

{(d2-1) component}

・Anion part

In formula (d2-1), Rd ¹ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, respectively, in the formula (b-1) ) in R ¹⁰¹ and the like.

Among these, as Rd ¹ , an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkyl group which may have a substituent is preferable. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, and a lactone-containing cyclic group each represented by the general formulas (a2-r-1) to (a2-r-7). , an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is included as a substituent, an alkylene group may be interposed, and as a substituent in this case, the linking group respectively represented by said formula (y-al-1) - (y-al-5) is preferable. Do.

Preferred examples of the aromatic hydrocarbon group include a polycyclic structure containing a phenyl group, a naphthyl group, and a bicyclooctane skeleton (eg, a polycyclic structure comprising a bicyclooctane skeleton and a ring structure other than this). can

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

The chain alkyl group preferably has 1 to 10 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, etc. A linear alkyl group of ; 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methyl group Branched alkyl groups, such as a pentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group, are mentioned.

When the above-mentioned chain alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the fluorinated alkyl group preferably has 1 to 11 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 4 carbon atoms. The fluorinated alkyl group may contain atoms other than a fluorine atom. As atoms other than a fluorine atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example.

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

Preferred specific examples of the anion moiety of component (d2-1) are shown below.

[Formula 52]

・Cathion

In formula (d2-1), M' ^m+ is an m-valent onium cation.

Examples of the onium cation for M' ^{m+ include} the same cations as those represented by the general formulas (ca-1) to (ca-4), preferably the cation represented by the general formula (ca-1). These are more preferable, and the cations respectively represented by said formula (ca-1-1) - (ca-1-78) and (ca-1-101) - (ca-1-149) are still more preferable.

(d2-1) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

{(d2-2) component}

・Anion part

In formula (d2-2), Rd ² is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, wherein the formula (b-1) ^{The same thing as R 101} in R 101 etc. is mentioned.

However, in Rd ² , a fluorine atom is not bonded to a carbon atom adjacent to the S atom (not substituted with fluorine). Thereby, the anion of (d2-2) component becomes a suitable weak acid anion, and the quenching ability as (D2) component improves.

Rd ² is preferably a chain alkyl group which may have a substituent or an aliphatic cyclic group which may have a substituent. As a chain|strand-type alkyl group, it is preferable that it is C1-C10, and it is more preferable that it is 3-10. Examples of the aliphatic cyclic group include a group (which may have a substituent) in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like; It is more preferable that it is the group which removed 1 or more hydrogen atoms from camphor etc.

The hydrocarbon group of Rd ² may have a substituent, and as the substituent, the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in ^{Rd 1 in the formula (d2-1) may have a substituent} can be the same as

Preferred specific examples of the anion moiety of the component (d2-2) are shown below.

[Formula 53]

・Cathion

In formula (d2-2), M' ^m+ is an onium cation of m valence, and is the same as ^{M' m+ in said formula (d2-1).}

(d2-2) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

{(d2-3) component}

・Anion part

In formula (d2-3), Rd ³ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and in the formula (b-1) Examples of the same include R ¹⁰¹ , and a cyclic group containing a fluorine atom, a chain alkyl group, or a chain alkenyl group is preferable. Especially, a fluorinated alkyl group is preferable, and the thing similar to the ^{said fluorinated alkyl group of said Rd 1 is more preferable.}

In formula (d2-3), Rd ⁴ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, wherein the formula (b-1) ^{The same thing as R 101} in R 101 etc. is mentioned.

Especially, it is preferable that they are an alkyl group which may have a substituent, an alkoxy group, an alkenyl group, and a cyclic group.

The alkyl group for Rd ⁴ is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. are mentioned. A part of the hydrogen atoms of the alkyl group of Rd ⁴ may be substituted with a hydroxyl group, a cyano group, or the like.

The alkoxy group for Rd ⁴ is preferably an alkoxy group having 1 to 5 carbon atoms, and specifically as an alkoxy group having 1 to 5 carbon atoms, a methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, n- butoxy group and tert-butoxy group. Especially, a methoxy group and an ethoxy group are preferable.

Examples of the alkenyl group for Rd ^{4 include the same as those for R 101} in the formula (b-1), and a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, and a 2-methylpropenyl group are preferable. . These groups may further have a C1-C5 alkyl group or a C1-C5 halogenated alkyl group as a substituent.

Examples of the cyclic group for Rd ^{4 include the same as R 101} in the formula (b-1), cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclo. An alicyclic group obtained by removing one or more hydrogen atoms from a cycloalkane such as dodecane, 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 dissolves favorably in the organic solvent, thereby improving the lithographic properties.

In formula (d2-3), Yd ¹ is a single bond or a divalent linking group.

Although it does not specifically limit as a divalent linking group in Yd ¹ , A divalent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent, a divalent linking group containing a hetero atom, etc. are mentioned. Examples of these are the same divalent hydrocarbon groups and divalent linking groups containing a hetero atom which may have a substituent, which are mentioned in the description of the divalent linking group for ^{Ya x1 in the formula (a10-1), respectively.}

Yd ¹ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. As an alkylene group, it is more preferable that it is a linear or branched alkylene group, and it is still more preferable that it is a methylene group or an ethylene group.

Preferred specific examples of the anion moiety of the component (d2-3) are shown below.

[Formula 54]

[Formula 55]

・Cathion

In formula (d2-3), M' ^m+ is an onium cation of m valence, and is the same as ^{M' m+ in said formula (d2-1).}

(d2-3) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

(D2) component may use only 1 type in any one of said (d2-1) - (d2-3) component, and may use it in combination of 2 or more type.

When the resist composition contains component (D2), the content of component (D2) in the resist composition is preferably 0.5 to 35 parts by mass, more preferably 1 to 25 parts by mass, based on 100 parts by mass of component (A), , 2-20 mass parts is more preferable, and 3-15 mass parts is especially preferable.

When the content of the component (D2) is equal to or more than the preferred lower limit, particularly favorable lithography characteristics and resist pattern shape are easily obtained. On the other hand, if it is below the upper limit, a balance with other components can be achieved, and various lithographic characteristics become favorable.

(D2) Method of Preparation of Component:

The manufacturing method of the said (d2-1) component and (d2-2) component is not specifically limited, It can manufacture by a well-known method.

Moreover, the manufacturing method of (d2-3) component is not specifically limited, For example, it carries out similarly to the method of US2012-0149916, and manufactures.

«Component (E): at least one compound selected from the group consisting of organic carboxylic acids and phosphorus oxo acids and derivatives thereof»

In the resist composition of the present embodiment, for the purpose of preventing sensitivity deterioration and improving resist pattern shape and stability over storage time, as optional components, from the group consisting of organic carboxylic acids and phosphorus oxo acids and derivatives thereof. At least one selected compound (E) (hereinafter referred to as “component (E)”) can be contained.

As organic carboxylic acid, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are preferable, for example.

Phosphoric acid, phosphonic acid, phosphinic acid etc. are mentioned as an oxo acid of phosphorus, Among these, phosphonic acid is especially preferable.

Examples of the derivative of phosphorus oxo acid include esters in which a 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, and the like. can be heard

Phosphoric acid esters, such as phosphoric acid di-n-butyl ester and phosphoric acid diphenyl ester, etc. are mentioned as a derivative|guide_body of phosphoric acid.

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

As a derivative of a phosphinic acid, a phosphinic acid ester, phenylphosphinic acid, etc. are mentioned.

In the resist composition of this embodiment, the component (E) may be used individually by 1 type, and may use 2 or more types together.

When the resist composition contains component (E), the content of component (E) is usually used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of component (A).

«Component (F): Fluorine additive component»

The resist composition of the present embodiment may contain a fluorine additive component (hereinafter referred to as "component (F)") in order to impart water repellency to the resist film or to improve lithography characteristics.

(F) As a component, Unexamined-Japanese-Patent No. 2010-002870, Unexamined-Japanese-Patent No. 2010-032994, Unexamined-Japanese-Patent No. 2010-277043, Unexamined-Japanese-Patent No. 2011-13569, Unexamined-Japanese-Patent No. The fluorinated polymer compound described in Publication No. 2011-128226 can be used.

(F) The polymer which has a structural unit (f1) represented by a following formula (f1-1) more specifically as a component is mentioned. As this polymer, the polymer (homopolymer) which consists only of the structural unit (f1) represented by a following formula (f1-1); a copolymer of the structural unit (f1) and the structural unit (a1); It is preferable that it is a copolymer of the structural unit (f1), the structural unit derived from acrylic acid or methacrylic acid, and the said structural unit (a1). Here, as the structural unit (a1) copolymerized with the structural unit (f1), a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, 1-methyl-1-adamantyl (meth) Structural units derived from acrylates are preferred.

[Formula 56]

[Wherein, R is the same as above, Rf ¹⁰² and Rf ¹⁰³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Rf ¹⁰² and Rf ¹⁰³ are the same It may or may not be different. nf ¹ is an integer of 1 to 5, and Rf ¹⁰¹ is an organic group containing a fluorine atom.]

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

In the formula (f1-1), examples ^{of the halogen atom for Rf 102} and Rf ¹⁰³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable. Examples of the alkyl group having 1 to 5 carbon atoms for Rf ¹⁰² and Rf ^{103 include} the same groups as the alkyl group having 1 to 5 carbon atoms for R, and a methyl group or an ethyl group is preferable. Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms for Rf ¹⁰² and Rf ¹⁰³ include groups in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. A fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as this halogen atom, A fluorine atom is especially preferable. Especially, as Rf ¹⁰² and Rf ¹⁰³ , a hydrogen atom, a fluorine atom, or a C1-C5 alkyl group is preferable, and a hydrogen atom, a fluorine atom, a methyl group, or an ethyl group is preferable.

Expression, nf ¹ of (f1-1) is an integer from 1 to 5, more preferably an integer of 1 to 3 is preferable, 1 or 2;

In formula (f1-1), Rf ¹⁰¹ is an organic group containing a fluorine atom, and is preferably a hydrocarbon group containing a fluorine atom.

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

Moreover, as for the hydrocarbon group containing a fluorine atom, it is preferable that 25% or more of the hydrogen atoms in the said hydrocarbon group are fluorinated, it is more preferable that 50% or more is fluorinated, that 60% or more is fluorinated, It is especially preferable at the point which the hydrophobicity of the resist film at the time of immersion exposure becomes high.

Especially, as Rf ¹⁰¹ , a C1-C6 fluorohydrocarbon group is more preferable, and a trifluoromethyl group, -CH ₂ -CF ₃ , -CH ₂ -CF ₂ -CF ₃ , -CH(CF ₃ ) ₂ , - CH ₂ -CH ₂ -CF ₃ , -CH ₂ -CH ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₃ are particularly preferred.

(F) 1000-50000 are preferable, as for the mass average molecular weight (Mw) (polystyrene conversion standard by gel permeation chromatography) of component, 5000-40000 are more preferable, and 10000-30000 are the most preferable. If it is below the upper limit of this range, there exists sufficient solubility with respect to the solvent for resists for use as a resist, and if it is more than the lower limit of this range, the water repellency of a resist film is favorable.

(F) 1.0-5.0 are preferable, as for the dispersion degree (Mw/Mn) of component, 1.0-3.0 are more preferable, 1.2-2.5 are the most preferable.

In the resist composition of this embodiment, the component (F) may be used individually by 1 type, and may use 2 or more types together.

When the resist composition contains component (F), the content of component (F) is usually used in an amount of 0.5 to 10 parts by mass with respect to 100 parts by mass of component (A).

≪(S) component: organic solvent component≫

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

As the component (S), each component to be used can be dissolved to form a uniform solution, and any solvent can be appropriately selected and used from conventionally known solvents for chemically amplified resist compositions.

(S) As a component, For example, lactones, such as (gamma)-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; A compound having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, monomethyl ether, monoethyl ether of the polyhydric alcohol or compound having an ester bond, Derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ethers such as monopropyl ether and monobutyl ether or monophenyl ether [among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferable]; cyclic ethers such as dioxane, esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; Anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitylene, etc. of aromatic organic solvents, dimethyl sulfoxide (DMSO), and the like.

In the resist composition of the present embodiment, the component (S) may be used singly or as a mixed solvent of two or more kinds.

Especially, PGMEA, PGME, (gamma)-butyrolactone, EL, and cyclohexanone are preferable.

Moreover, the mixed solvent which mixed PGMEA and the polar solvent is also preferable. The compounding ratio (mass ratio) may be appropriately determined in consideration of the compatibility of PGMEA and the polar solvent, etc., but 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. : is 2. Moreover, when mix|blending PGME as a polar solvent, the mass ratio of PGMEA:PGME becomes like this. Preferably it is 1:9-9:1, More preferably, 2:8-8:2, More preferably, 3:7- It is 7:3. Moreover, the mixed solvent of PGMEA, PGME, and cyclohexanone is also preferable.

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

(S) The usage-amount of component is not specifically limited, It is a density|concentration which can be apply|coated to a board|substrate etc., and it sets suitably according to the coating film thickness. In general, component (S) is used so that the solid content concentration of the resist composition is in the range of 0.1 to 50 mass%, preferably 10 to 50 mass%.

In the resist composition of the present embodiment, a miscible additive, for example, an additional resin for improving the performance of the resist film, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like may be suitably added to the resist composition of the present embodiment. , may be added.

In the resist composition of the present embodiment, after dissolving the resist material in the component (S), impurities and the like may be removed using a porous polyimide film, a porous polyamideimide film, or the like. For example, the resist composition may be filtered using a filter made of a porous polyimide film, a filter made of a porous polyamideimide film, a filter made of a porous polyimide film and a porous polyamideimide film, or the like. As said polyimide porous membrane and said polyamideimide porous membrane, the thing of Unexamined-Japanese-Patent No. 2016-155121 etc. are illustrated, for example.

The negative resist composition of the present embodiment comprises a polymer compound (A1), an acid generator (B0), a crosslinking agent (C), and an aromatic compound having one or two phenolic hydroxyl groups in the molecule and not having a carboxyl group. (Z) and contains.

As a result of the studies of the present invention, when a resist pattern is formed using a negative resist composition employing an alkali-soluble polyhydroxystyrene-based resin as a base component, a micron-order thick resist film is formed using wet etching resistance, When etching was performed by forming a resist pattern, the etching resistance was insufficient in some cases. It is considered that this is because the resist film formed using the negative resist composition has insufficient adhesion to the substrate interface.

In the resist composition of the present embodiment described above, it is presumed that component (Z) segregates in the lower layer of the resist film and contributes to the improvement of substrate adhesion. Therefore, it is estimated that the resist pattern formed using the negative resist composition of the present embodiment has good etching resistance.

(Resist pattern formation method)

A second aspect of the present invention includes a step (i) of forming a resist film on a support using the resist composition according to the first aspect, a step (ii) of exposing the resist film, and a resist film after exposure It is a resist pattern formation method which has the process (iii) of developing and forming a resist pattern.

As one embodiment of such a resist pattern formation method, the resist pattern formation method implemented as follows, for example is mentioned.

Process (i):

First, on a support body, the resist composition of the above-mentioned embodiment is apply|coated with a spinner etc., and a bake (post-apply bake (PAB)) process is carried out for 40 to 200 second under the temperature conditions of 80-160 degreeC, for example. , preferably for 60 to 150 seconds to form a resist film.

Process (ii):

Next, the resist film is selectively exposed by exposure or the like through a mask (mask pattern) in which a predetermined pattern is formed using an exposure apparatus such as a KrF exposure apparatus, for example, and then baked (post-exposure bake). (PEB)) process is, for example, 80-150 degreeC temperature condition for 40 to 150 second, Preferably it is for 60 to 120 second.

Process (iii):

Next, the resist film is developed. In the case of an alkali developing process, the developing treatment is performed using an alkali developing solution, and in the case of a solvent developing process, using the developing solution (organic type developing solution) containing an organic solvent.

After the developing treatment, preferably a rinse treatment is performed. As for the rinse treatment, in the case of an alkali developing process, a water rinse using pure water is preferable, and in the case of a solvent developing process, it is preferable to use the rinse liquid containing an organic solvent.

In the case of a solvent developing process, after the said developing process or a rinse process, you may perform the process which removes the developing solution or rinse liquid adhering on the pattern with a supercritical fluid.

Drying is performed after developing or rinsing. Moreover, you may implement a baking process (post-baking) after the said developing process depending on the case. The baking process (post-baking) here is 80 degreeC or more, for example, Preferably it is 90 to 120 degreeC temperature conditions for 10-120 second, Preferably it is 30 to 90 second.

In this way, a resist pattern can be formed.

It does not specifically limit as a support body, A conventionally well-known thing can be used, For example, the board|substrate for electronic components, the thing in which the predetermined wiring pattern was formed, etc. are mentioned. More specifically, a silicon wafer, a metal substrate, such as copper, chromium, iron, and aluminum, a glass substrate, etc. are mentioned. As a material of a wiring pattern, copper, aluminum, nickel, gold|metal|money, etc. can be used, for example.

Moreover, as a support body, the thing in which the film|membrane of the inorganic type and/or organic type was formed on the above-mentioned board|substrate may be sufficient. Examples of the inorganic film include an inorganic antireflection film (inorganic BARC). As an organic film|membrane, organic films, such as an organic antireflection film (organic BARC) and the lower layer organic film in a multilayer resist method, are mentioned.

Here, in the multilayer resist method, at least one organic film (lower organic film) and at least one resist film (upper resist film) are formed on a substrate, and the resist pattern formed on the upper resist film is used as a mask. It is a method of patterning the lower organic film, and it is said that a pattern with a high aspect ratio can be formed. That is, according to the multilayer resist method, since the required thickness can be ensured by the lower organic film, the resist film can be thinned and fine patterns with high aspect ratio can be formed.

In the multilayer resist method, basically, the upper resist film and the lower organic film have a two-layer structure (two-layer resist method), and one or more intermediate layers (such as a metal thin film) are formed between the upper resist film and the lower organic film. It is divided into a method of forming a multilayer structure of three or more layers (three-layer resist method).

The resist pattern forming method of the embodiment is a method useful when forming and performing a thick resist film. Even if the film thickness of the resist film formed in the said process (i) is 1-10 micrometers, for example, a resist pattern can be formed stably in a favorable shape.

The wavelength used for exposure is not particularly limited, and ultraviolet rays such as g-line and i-ray, ArF excimer laser light, KrF excimer laser light, F ₂ excimer laser light, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, soft X-rays, etc. can be used for carrying out.

The resist composition according to the first aspect described above has high utility for ultraviolet rays such as g-line and i-ray, KrF excimer laser light, ArF excimer laser light, EB or EUV, and ultraviolet rays such as g-line and i-ray, KrF The usefulness for excimer laser beams and ArF excimer laser beams is higher, and the usefulness for ultraviolet rays such as g-rays and i-rays and KrF excimer laser beams is particularly high. The resist pattern forming method according to the second aspect is particularly preferable when, in the step (ii), the resist film is irradiated with ultraviolet rays such as g-line or i-ray, or KrF excimer laser beam.

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

Liquid immersion exposure is an exposure method in which a space between a resist film and a lens at the lowest position of the exposure apparatus is previously filled with a solvent (immersion medium) having a refractive index greater than that of air, and exposure (immersion exposure) is performed in that state.

As the immersion medium, a solvent having a refractive index larger than the refractive index of air and smaller than the refractive index of the resist film to be exposed is preferable. The refractive index of the solvent is not particularly limited as long as it is within the above range.

Examples of the solvent having a refractive index greater 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 a liquid containing a fluorine-based compound such as _{C 3} HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , and C ₅ H ₃ F _{7 as a main component.} It is preferable that it is 70-180 degreeC, and, as for a boiling point, it is more preferable that it is 80-160 degreeC. If the fluorine-based inert liquid has a boiling point within the above range, it is preferable that the medium used for immersion can be removed by a simple method after the exposure is completed.

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

Further, specifically, as the perfluoroalkyl ether compound, perfluoro(2-butyl-tetrahydrofuran) (boiling point 102° C.) is exemplified, and as the perfluoroalkylamine compound, perfluoro and lotributylamine (boiling point 174°C).

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

As an alkali developing solution used for developing in an alkali developing process, 0.1-10 mass % tetramethylammonium hydroxide (TMAH) aqueous solution is mentioned, for example.

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

A ketone-based solvent is an organic solvent containing C-C(=O)-C in its structure. The ester solvent is an organic solvent containing C-C(=O)-O-C in its structure. The alcohol-based solvent is an organic solvent containing an alcoholic hydroxyl group in its structure. "Alcoholic hydroxyl group" means the hydroxyl group couple|bonded with the carbon atom of the aliphatic hydrocarbon group. The nitrile-based solvent is an organic solvent containing a nitrile group in its structure. The amide-based solvent is an organic solvent containing an amide group in its structure. The etheric solvent is an organic solvent containing C-O-C in its structure.

In the organic solvent, there is also an organic solvent containing a plurality of types of functional groups that characterize each of the above-mentioned solvents in the structure. In that case, however, it shall be applicable to any type of solvent containing a functional group which the organic solvent has. For example, diethylene glycol monomethyl ether shall correspond to any of the alcohol solvents and ether solvents in the said classification|category.

A hydrocarbon solvent is a hydrocarbon solvent which consists of hydrocarbons which may be halogenated and does not have substituents other than a halogen atom. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.

As the organic solvent contained in the organic developer, among the above, a polar solvent is preferable, and a ketone solvent, an ester solvent, a nitrile solvent, and the like are preferable.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, and diisobutyl. Ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone), and the like. Among these, as the ketone solvent, methyl amyl ketone (2-heptanone) is preferable.

As an ester solvent, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxy ethyl acetate, ethoxy ethyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3 -Methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl Acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl Acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, Ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, 2-hydroxypropionate methyl, 2 -ethyl hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc. are mentioned. . Among these, as an ester solvent, butyl acetate is preferable.

As a nitrile-type solvent, acetonitrile, propionitrile, valeronitrile, butyronitrile, etc. are mentioned, for example.

A well-known additive can be mix|blended with an organic type developing solution as needed. As the additive, surfactant is mentioned, for example. Although it does not specifically limit as surfactant, For example, ionic or nonionic fluorine type and/or silicone type surfactant etc. can be used. As surfactant, a nonionic surfactant is preferable, and a nonionic fluorochemical surfactant or a nonionic silicone type surfactant is more preferable.

When mix|blending surfactant, the compounding quantity is 0.001-5 mass % normally with respect to the whole quantity of an organic type developing solution, 0.005-2 mass % is preferable, and its 0.01-0.5 mass % is more preferable.

The developing treatment can be carried out by a known developing method, for example, a method in which the support is immersed in a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the support by surface tension and stopped for a certain period of time (puddle) method), a method of spraying a developer on the surface of a support (spray method), and a method of continuously drawing out a developer while scanning a developer extraction nozzle at a constant speed on a support rotating at a constant speed (dynamic dispensing method). .

As the organic solvent contained in the rinsing solution used for the rinsing treatment after the development in the solvent development process, for example, from among the organic solvents used for the above organic developer, those that do not dissolve the resist pattern are appropriately selected and used. can Usually, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. Among these, at least one selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents and amide solvents is preferable, and at least one solvent selected from alcohol solvents and ester solvents is more preferable, and alcohol Solvents are particularly preferred.

The alcohol solvent used for the rinse liquid is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched or cyclic. Specifically, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4 - Octanol, benzyl alcohol, etc. are mentioned. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferable, and 1-hexanol and 2-hexanol are more preferable.

These organic solvents may be used individually by any 1 type, and may use 2 or more types together. Moreover, you may use it, mixing with organic solvents and water other than the above. However, in consideration of the development characteristics, the amount of water in the rinse liquid is preferably 30 mass% or less, more preferably 10 mass% or less, still more preferably 5 mass% or less, and 3 mass% with respect to the total amount of the rinse liquid % or less is particularly preferred.

A well-known additive can be mix|blended with a rinse liquid as needed. As the additive, surfactant is mentioned, for example. As for surfactant, the thing similar to the above is mentioned, A nonionic surfactant is preferable, and a nonionic fluorochemical surfactant or a nonionic silicone type surfactant is more preferable.

When mix|blending surfactant, the compounding quantity is 0.001-5 mass % normally with respect to the whole quantity of a rinse liquid, 0.005-2 mass % is preferable, and its 0.01-0.5 mass % is more preferable.

The rinsing process (washing process) using a rinsing liquid can be performed by a well-known rinsing method. As a method of the rinsing treatment, for example, a method of continuously extracting a rinse solution on a support rotating at a constant speed (rotary coating method), a method of immersing the support in a rinse liquid for a certain period of time (dip method), on the surface of the support The method of spraying a rinse liquid (spray method), etc. are mentioned.

In the resist pattern formation method of the present embodiment described above, since the resist composition according to the first aspect described above is used, it is estimated that a resist pattern with good etching resistance can be obtained.

Example

Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.

<Preparation of resist composition>

(Examples 1 to 12, Comparative Examples 1 to 5)

Each component shown in Tables 1-2 was mixed and melt|dissolved, and the resist composition of each example was prepared, respectively.

In Tables 1 and 2, each abbreviation has the following meaning, respectively. Numerical values in [] are compounding amounts (parts by mass).

(A)-1: A high molecular compound represented by the following formula (A-1). This high molecular compound (A-1) was obtained by radical polymerization using a monomer that induces structural units constituting the high molecular compound in a predetermined molar ratio. For this high molecular compound (A-1), the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 2500, and the molecular weight dispersion (Mw/Mn) was 1.2. ^The copolymer composition ratio (ratio (molar ratio) of each structural unit in the structural formula) determined by 13 C-NMR was l/m = 90/10.

[Formula 57]

(A)-2: A high molecular compound (homopolymer) represented by the following formula (A-2). This high molecular compound (A-2) was obtained by radical polymerization of the monomer (hydroxystyrene) which induces|guides|derives the structural unit which comprises this high molecular compound. About this polymer compound (A-2), the weight average molecular weight (Mw) calculated|required by GPC measurement in conversion of standard polystyrene was 2500, and molecular weight dispersion degree (Mw/Mn) was 1.2.

[Formula 58]

(B)-1 to (B)-3: An acid generator comprising a compound represented by the following formulas (B-1) to (B-3).

[Formula 59]

(C)-1: A crosslinking agent comprising a compound represented by the following formula (C-1).

(D)-1: A nitrogen-containing organic compound comprising a compound represented by the following formula (D-1).

[Formula 60]

(Z)-1: A compound represented by the following formula (Z-1). The mass average molecular weight (Mw) is 268.36.

(Z)-2: A compound represented by the following formula (Z-2). The mass average molecular weight (Mw) was 352.43.

(Z)-3: A compound represented by the following formula (Z-3). The mass average molecular weight (Mw) is 246.31.

(Z)-11: A compound represented by the following formula (Z-11). The mass average molecular weight (Mw) is 230.22.

(Z)-12: A compound represented by the following formula (Z-12). The mass average molecular weight (Mw) was 278.22.

(Z)-13: A compound represented by the following formula (Z-13). The mass average molecular weight (Mw) was 286.33.

(S)-1: Propylene glycol monomethyl ether acetate.

[Formula 61]

<Method of forming resist pattern>

Process (i):

On a silicon substrate subjected to hexamethyldisilazane (HMDS) treatment, each resist composition is applied using a spinner, and a prebaking (PAB) treatment is performed at 90° C. for 90 seconds on a hot plate, By drying, a resist film with a film thickness of 3 µm was formed.

Process (ii):

Next, a high-pressure mercury-vapor lamp (365 nm) is masked with respect to the resist film by an i-line stepper (reduction projection exposure apparatus: NSR-2205i14E (manufactured by Nikon Corporation; NA (numerical aperture) = 0.57, σ = 0.67)). The pattern was interposed and investigated selectively.

Then, the post-exposure heating (PEB) process for 60 second was implemented at 110 degreeC.

Process (iii):

Then, alkali development was performed at 23 degreeC for 60 second conditions using 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, Tokyo Oka Kogyo Co., Ltd. make) as a developing solution.

Then, the baking process (post-baking) for 60 second was implemented at 100 degreeC.

As a result, an isolated line pattern (hereinafter referred to as an "IS pattern") having a space width of 600 nm was formed.

<Evaluation of undercut>

The cross-sectional shape of the IS pattern formed by the above <Resist pattern formation method> was observed with a scanning electron microscope (product name: S4500; manufactured by Hitachi, Ltd.), and undercut (resist itself at the bottom of the resist pattern formed on the substrate) cut) (nm) was evaluated. The results are shown in Tables 3 and 4.

<Wet etching resistance evaluation>

A part of the substrate on which the IS pattern was formed by the resist pattern formation method described above was cut out and immersed in 23% buffered hydrofluoric acid for 12 minutes.

The cross-sectional shape of the IS pattern after immersion was observed with a scanning electron microscope (product name: S4500; manufactured by Hitachi, Ltd.), and side etching (cut-out caused by etching at the interface between the resist film and the substrate) (µm) was evaluated. did. The results are shown in Tables 3 and 4.

From the results shown in Tables 3 and 4, it was confirmed that the resist patterns formed using the resist compositions of Examples 1 to 12 had good dry etching resistance and wet etching resistance.

As mentioned above, although the preferred Example of this invention was described, this invention is not limited to these Examples. In the range which does not deviate from the meaning of this invention, addition, omission, substitution, and other changes of a structure are possible. The present invention is not limited by the foregoing description, but only by the scope of the appended claims.

Claims (4)

A polymer compound (A1) having a structural unit (a10) represented by the following general formula (a10-1);
an acid generator (B0) represented by the following general formula (b0-1);
a crosslinking agent (C);
A negative resist composition comprising an aromatic compound (Z) having one or two phenolic hydroxyl groups in a molecule and not having a carboxyl group.

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Ya ^x1 is a single bond or a divalent linking group. Wa ^x1 is an aromatic hydrocarbon group which may have a substituent. n _ax1 is an integer greater than or equal to 1.]

[Wherein, Rb ¹ is an organic group. Rb ² is a group represented by the following general formula (b0-r-1) or the following general formula (b0-r-2).]

[In formula (b0-r-1), Rb ²⁰¹ and Rb ²⁰² are each independently an organic group. * indicates a bond. In the formula (b0-r-2), Xb is a group that together with -(O=)CNC(=O)- forms a cyclic group having a cyclic imide structure. * indicates a bond hand.] The method of claim 1,
A negative resist composition, wherein the aromatic compound (Z) contains at least one selected from the group consisting of a compound represented by the following general formula (z1-1) and a compound represented by the following general formula (z2-1).

[In formula (z1-1), V _z ¹ is a divalent linking group having no hydroxy group and no carboxy group. In formula (z2-1), Rz ² is a hydrocarbon group. n1 is 1 or 2. n2 is an integer of 2-5. However, n1 + n2 ≤ 6.] The method of claim 1,
The negative resist composition, wherein the content of the aromatic compound (Z) is 0.5 to 30 parts by mass based on 100 parts by mass of the high molecular compound (A1). A step of forming a resist film on a support using the resist composition according to any one of claims 1 to 3, a step of exposing the resist film, and a step of developing the resist film after the exposure to form a resist pattern. A method for forming a resist pattern.