KR20200004251A - Resist composition and method of forming resist pattern - Google Patents

Abstract

Provided is a resist composition, which has excellent lithography characteristics, excellent applicability, and has the suppressed foaming from a resist pattern when being baked in high temperature in a case of forming the resist pattern by forming a thick resist film. The resist composition of the present invention comprises: a polymer compound having a constituent unit represented by formula (a10-1) and a constituent unit including an acid-labile group having increased polarity by an action of acid; and an acid generator represented by formula (b1). In addition, the resist composition of the present invention has a solid concentration of 30 mass% or more. In the formula (a10-1), R is a hydrogen atom, an alkyl group or a halogenated alkyl group, Ya^x1 is a single bond or a bivalent linking group, Wa^x1 is an aromatic hydrocarbon group, and n_ax1 is an integer of 1 to 3. In the formula (b1), R^2011, R^2021, and R^2031 represent aryl groups, and two or more thereof may bind to each other to form a ring with a sulfur atom in the formula, and X^- represents a counter anion.

Description

Resist composition and resist pattern formation method {RESIST COMPOSITION AND METHOD OF FORMING RESIST PATTERN}

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

In the lithography technique, a process of forming a resist pattern of a predetermined shape in the resist film by, for example, forming a resist film made of a resist material on the substrate, selectively exposing the resist film, and performing a developing process. This is carried out. The resist material which changes to the characteristic which the exposure part of a resist film changes in the characteristic which melt | dissolves in a developing solution is called a positive type, and the resist material which changes in the characteristic which the exposure part of a resist film does not dissolve in a developing solution is called negative type.

In recent years, in manufacture of a semiconductor element and a liquid crystal display element, refinement | miniaturization of a pattern is progressing rapidly by the advance of the lithography technique. As a method of miniaturization, shortening of wavelength (high energy) of the exposure light source is generally performed. Specifically, ultraviolet rays typified by g-line and i-line have conventionally been used, but now mass production of semiconductor devices using KrF excimer laser light and ArF excimer laser light is performed. Moreover, examination is also performed about EUV (extreme ultraviolet-ray), EB (electron beam), X-rays, etc. which are shorter wavelength (high energy) than these excimer laser beam.

The resist material is required for lithographic characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern of fine dimensions.

As a resist material that satisfies such a requirement, a conventional chemically amplified resist composition containing a base component whose solubility in a developing solution changes under the action of an acid and an acid generator component which generates an acid upon exposure is used. have.

For example, in the case where the developer is an alkaline developer (alkali development process), the positive chemically amplified resist composition includes a resin component (base resin) and an acid generator in which solubility in an alkali developer is increased by the action of an acid. It is generally used to contain components. When the resist film formed using such a resist composition performs selective exposure at the time of resist pattern formation, an acid will generate | occur | produce in an exposure part, and the polarity of a base resin will increase by the action of the acid, The exposed portion of the resist film is soluble to the alkaline developer. Therefore, by alkali development, the positive pattern in which the unexposed part of a resist film remains as a pattern is formed.

On the other hand, when such a chemically amplified resist composition is applied to a solvent developing process using a developer (organic developer) containing an organic solvent, when the polarity of the base resin increases, solubility in the organic developer is relatively lowered. The unexposed portion of the resist film is dissolved and removed by the organic developer, so that a negative resist pattern in which the exposed portion of the resist film remains as a pattern is formed. Thus, the solvent developing process which forms a negative resist pattern may be called a negative developing process.

Until now, as a base resin of a chemically amplified resist composition, for example, polyhydroxy styrene (PHS) having high transparency and a hydroxyl group of KrF excimer laser light (248 nm) are protected with an acid dissociable, dissolution inhibiting agent. Resin (PHS type resin) or resin ((meth) acrylic-type resin) which protected the hydroxyl group in the carboxyl group of (meth) acrylic acid with an acid dissociable, dissolution inhibiting agent is used (for example, refer patent document 1).

Examples of the acid dissociable, dissolution inhibiting groups include tertiary alkyl groups represented by so-called acetal groups and tert-butyl groups such as cyclic ether groups represented by a 1-ethoxyethyl group or a cyclic ether group represented by a tetrahydropyranyl group. and tert-butoxycarbonyl groups, tertiary alkoxycarbonyl groups and the like are mainly used.

As the acid generator components used in the chemically amplified resist composition, various kinds have been proposed so far, for example, onium salt acid generators such as iodonium salts and sulfonium salts and oxime sulfonate acid generation. Secondly, diazomethane-based acid generators, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, disulfone-based acid generators and the like are known.

In recent years, photofabrication has become a mainstream of precision micromachining technology. With photofabrication, the chemically amplified resist composition is applied to the surface of a workpiece to form a resist film, a resist pattern having a predetermined shape is formed on the resist film, and chemical etching, electrolytic etching, or electroplating is used as a mask. It refers to a processing technology for producing various precision parts by performing electroforming mainly on the basis of the above.

In such photofabrication, a thick film resist film having a film thickness of 8 µm or more, for example, may be formed on the surface of a workpiece, and a resist pattern may be formed to perform etching or the like.

Japanese Laid-Open Patent Publication No. 4-211258

In the case where a thick film resist film is to be formed using the chemically amplified resist composition, the thicker the resist film becomes, the more difficult it is to apply the chemically amplified resist composition to the workpiece to a uniform thickness. In addition, in the resist pattern formed, there exists a problem that lithographic characteristics (for example, dimensional uniformity etc.) tend to worsen.

In addition, when the resist pattern is formed using the chemically amplified resist composition, the thicker the resist film is, the more difficult it is to maintain the sensitivity during exposure. On the contrary, for example, the sensitivity is improved by using a chemically amplified resist composition in which an iodonium salt is selected as an acid generator component.

However, in the examination of the present inventors, when the chemically amplified resist composition containing an iodonium salt is used, when the support body on which the resist film is formed is baked at a high temperature (180 ° C. or more) (for example, after developing or after rinsing treatment) The phenomenon that foaming occurs during the baking treatment (post bake) was confirmed. Thus, in the resist composition which is easy to cause foaming, there exists a problem that the removal effect of a residue is not enough, for example at the ashing process for rework.

This invention is made | formed in view of the said situation, In forming a resist pattern, especially when forming a thick-film resist film, it is excellent in lithography characteristic, favorable applicability | paintability, and from the resist pattern at the time of high temperature baking, An object of the present invention is to provide a resist composition in which foaming is suppressed and a method of forming a resist pattern using the same.

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

That is, the 1st aspect of this invention is a resist composition which generate | occur | produces an acid by exposure and changes solubility to a developing solution by the action of an acid, Comprising: The structural unit (a10) represented by following General formula (a10-1), and Solid content in a resist composition containing the high molecular compound (A1) which has a structural unit (a1) containing an acid-decomposable group whose polarity increases by the action of an acid, and the acid generator (B1) represented by the following general formula (b1) The density | concentration is 30 mass% or more, It is a resist composition characterized by the above-mentioned.

[Formula 1]

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ya ^x1 is a single bond or a divalent linking group. Wa ^x1 is a (n _ax1 +1) valent aromatic hydrocarbon group. n _ax1 is an integer of 1-3. R ²⁰¹¹ , R ²⁰²¹ and R ²⁰³¹ each independently represent an aryl group which may have a substituent. Two or more of R ²⁰¹¹ , R ^2021, and R ²⁰³¹ may be bonded to each other to form a ring together with a sulfur atom in the formula. X ^- represents a counter anion.]

According to a second aspect of the present invention, a step (i) of forming a resist film using the resist composition according to the first aspect, a step of exposing the resist film (ii), and a resist film after the exposure are developed on a support. It has a process (iii) of forming a resist pattern, The resist pattern formation method characterized by the above-mentioned.

According to the present invention, in the formation of a resist pattern, particularly in the case where a thick film resist film is formed, the resist composition has excellent lithography characteristics, good applicability, and suppressed foaming from the resist pattern during high temperature baking. And the resist pattern formation method using the same can be provided.

The resist composition and method of forming a resist pattern of the present invention are particularly useful for forming a resist pattern of a thick film.

In the present specification and claims, "aliphatic" is defined as meaning relative to aromatics, meaning groups, compounds, and the like having no aromaticity.

"Alkyl group" shall contain a linear, branched, and cyclic monovalent saturated hydrocarbon group unless otherwise specified. The alkyl group in an alkoxy group is also the same.

"Alkylene group" shall contain a bivalent, saturated, branched, cyclic, divalent hydrocarbon group unless otherwise specified.

The "halogenated alkyl group" is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms, and examples of the halogen atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The "fluorinated alkyl group" or the "fluorinated alkylene group" means a group in which part or all of the hydrogen atoms of the alkyl group or the alkylene group are substituted with fluorine atoms.

A "structural unit" means the monomeric unit (monomer unit) which comprises a high molecular compound (resin, a polymer, a copolymer).

When indicated as "or may have a substituent", in the case of substituting a hydrogen atom (-H) a monovalent group, and methylene group (-CH ₂ -) it includes both of the case of substituted bivalent.

"Exposure" is taken as the concept containing the irradiation of the whole radiation.

"(Meth) acrylic acid ester" means the one or both of the acrylic acid ester which the hydrogen atom couple | bonded with the (alpha) position, and the methacrylic acid ester which the methyl group couple | bonded with the (alpha) position.

"(Meth) acrylate" means one or both of the acrylate which the hydrogen atom couple | bonded with the (alpha) position, and the methacrylate which the methyl group couple | bonded with the (alpha) position.

"(Meth) acrylic acid" means one or both of acrylic acid which the hydrogen atom couple | bonded with the (alpha) position, and methacrylic acid which the methyl group couple | bonded with the (alpha) position.

The "structural unit guide | induced from an acrylate ester" means the structural unit in which the ethylenic double bond of an acrylate ester is cleaved and comprised.

"Acrylate ester" is, acrylic acid (CH ₂ = CH-COOH) is a compound substituted with a hydrogen atom of the carboxyl terminus of the organic.

In the acrylate ester, the hydrogen atom bonded to the carbon atom at the α position may be substituted with a substituent. The substituent (R ^α0 ) which substitutes the hydrogen atom bonded to the carbon atom at the α-position is an atom or group other than a hydrogen atom, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and the like. have. Moreover, it is also containing the itaconic acid diester substituted by the substituent which the substituent (R ( ^alpha ) ⁰ ) contains an ester bond, and the ( ^alpha ) hydroxyacrylester substituted by the group which the substituent (R ( ^alpha ) ⁰ ) modified by the hydroxyalkyl group or its hydroxyl group. do. In addition, the carbon atom of the (alpha) position of an acrylate ester means the carbon atom to which the carbonyl group of acrylic acid couple | bonds unless there is particular notice.

Hereinafter, the acrylate ester in which the hydrogen atom couple | bonded with the carbon atom of the (alpha) position substituted by the substituent may be called (alpha) substituted acrylate ester. In addition, acrylic ester and (alpha) substituted acrylate ester may be included and may be called "((alpha) substituted) acrylic acid ester".

The "structural unit derived from acrylamide" means the structural unit which the ethylenic double bond of acrylamide cleaves and is comprised.

As for acrylamide, the hydrogen atom couple | bonded with the carbon atom of the (alpha) position may be substituted by the substituent, and one or both hydrogen atoms of the amino group of acrylamide may be substituted by the substituent. In addition, the carbon atom of the (alpha) position of acrylamide means the carbon atom which the carbonyl group of acrylamide couple | bonds unless there is particular notice.

As a substituent which substitutes the hydrogen atom couple | bonded with the carbon atom of the (alpha) position of acrylamide, the thing similar to what was illustrated as a substituent of the ( ^alpha ) position in said (alpha) substituted acrylate ester (substituent (R ( ^alpha ) ⁰ )) is mentioned.

The "structural unit derived from hydroxy styrene" means the structural unit which is formed by cleaving the ethylenic double bond of hydroxy styrene. The "structural unit derived from a hydroxy styrene derivative" means the structural unit which is comprised by the cleavage of the ethylenic double bond of a hydroxy styrene derivative.

A "hydroxy styrene derivative" is taken as the concept containing the thing in which the hydrogen atom of the (alpha) position of hydroxy styrene was substituted by other substituents, such as an alkyl group and a halogenated alkyl group, and those derivatives. As these derivatives, what substituted the hydrogen atom of the hydroxyl group of the hydroxystyrene which the hydrogen atom of the (alpha) position may be substituted by the substituent; The thing etc. which the substituents other than a hydroxyl group couple | bonded with the benzene ring of hydroxystyrene which the hydrogen atom of the (alpha) position may be substituted by the substituent are mentioned. In addition, an alpha position (carbon atom of an alpha position) means the carbon atom to which the benzene ring couple | bonds unless there is particular notice.

As a substituent which substitutes the hydrogen atom of the (alpha) position of hydroxy styrene, the thing similar to what was illustrated as a substituent of the (alpha) position in said (alpha) substituted acrylate ester is mentioned.

The "structural unit derived from vinyl benzoic acid or a vinyl benzoic acid derivative" means a structural unit which is formed by cleaving the ethylenic double bond of vinyl benzoic acid or a vinyl benzoic acid derivative.

"Vinyl benzoic acid derivative" is taken as the concept containing the thing substituted by the other substituents, such as an alkyl group and a halogenated alkyl group, in the hydrogen position of the (alpha) position of vinyl benzoic acid, and those derivatives. As these derivatives, what substituted the hydrogen atom of the carboxy group of vinylbenzoic acid by which the hydrogen atom of the (alpha) position may be substituted by the substituent; The thing which the hydroxyl group and substituents other than a carboxyl group couple | bonded with the benzene ring of vinylbenzoic acid which the hydrogen atom of the (alpha) position may be substituted is mentioned. In addition, an alpha position (carbon atom of an alpha position) means the carbon atom to which the benzene ring couple | bonds unless there is particular notice.

"Styrene" is taken as the concept including what the styrene and the hydrogen atom of the (alpha) position of styrene substituted by other substituents, such as an alkyl group and a halogenated alkyl group.

A "styrene derivative" is taken as the concept containing the thing substituted by the other substituents, such as an alkyl group and a halogenated alkyl group, in the hydrogen position of the styrene position, and those derivatives. As these derivatives, the thing by which the substituent couple | bonded with the benzene ring of hydroxystyrene which the hydrogen atom of the (alpha) position may be substituted by the substituent is mentioned. In addition, an alpha position (carbon atom of an alpha position) means the carbon atom to which the benzene ring couple | bonds unless there is particular notice.

"Structural unit derived from styrene" and "structural unit derived from styrene derivative" mean a structural unit which is formed by cleaving ethylenic double bonds of styrene or styrene derivatives.

The alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, iso) Butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.

In addition, the halogenated alkyl group as a substituent of the (alpha) position specifically, mention | raise | lifted the group which substituted a part or all of the hydrogen atom of the said "alkyl group as a substituent of the (alpha) position" by the halogen atom. As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is especially preferable.

In addition, the hydroxyalkyl group as a substituent of the (alpha) position specifically, mention | raise | lifted the group which substituted one or all the hydrogen atoms of the said "alkyl group as a substituent of the (alpha) position" with the hydroxyl group. 1-5 are preferable and, as for the number of the hydroxyl groups in this hydroxyalkyl group, 1 is the most preferable.

In the present specification and the claims, depending on the structure represented by the chemical formula, subtitle carbon may exist, and there may be enantio or diastereomers. In that case, these isomers are represented by one chemical formula. These isomers may be used independently or may be used as a mixture.

(Resist composition)

The 1st aspect of this invention is the resist composition which produces | generates an acid by exposure and changes solubility to a developing solution by the action of an acid.

In one embodiment of such a resist composition, the base component (A) (hereinafter also referred to as "(A) component") in which the solubility in a developing solution changes by the action of an acid, and an acid generator which generates an acid by exposure The resist composition containing component (B) (henceforth "(B) component") and organic solvent component (S) (henceforth "(S) component") is mentioned. In the resist composition of the present embodiment, the component (A) contains the specific polymer compound (A1), the component (B) contains the specific acid generator (B1), and the solid content concentration in the resist composition is 30. It is mass% or more.

The resist composition of this embodiment is suitable for resist pattern formation which exposes using a KrF excimer laser.

Moreover, the resist composition of this embodiment is suitable for forming a resist film of 1-10 micrometers, for example on a support body, Especially it is suitable for formation of the resist pattern formed by forming a thick film resist film. The thick film referred to herein means a film having a thickness of 6 μm or more. The resist composition of the present embodiment is preferably used to form a resist film having a thickness of 6 μm or more, and a thickness of 7 μm or more and more preferably 8 μm or more in this range.

When a resist film is formed using the resist composition of this embodiment, and selective exposure is performed to the resist film, an acid is generated from the component (B) in the exposed portion of the resist film, and the action of the acid causes component (A). The solubility of the developer film in the resist film changes while the solubility in the developer of the component (A) does not change in the unexposed part of the resist film, so that a difference in solubility in the developer occurs between the exposed part and the unexposed part of the resist film. . Therefore, when the resist film is developed, the resist film exposed portion is dissolved and removed when the resist composition is positive, and the resist film unexposed portion is dissolved and removed when the resist composition is negative. A resist pattern of the type is formed.

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

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

Moreover, the resist composition of this embodiment may be for the alkali developing process which uses an alkaline developing solution for the developing process at the time of resist pattern formation, and the solvent developing process which uses the developing solution (organic developing solution) containing an organic solvent for the developing process. It may be easy.

The resist composition of this embodiment has an acid generating ability which generate | occur | produces an acid by exposure, and in addition to (B) component, (A) component may generate an acid by exposure.

When (A) component produces an acid by exposure, this (A) component becomes "the base component which produces | generates an acid by exposure and changes solubility with respect to a developing solution by the action of an acid." When the component (A) generates an acid by exposure and is a base component whose solubility in a developer is changed by the action of an acid, the component (A1) described later generates an acid by exposure, and It is preferable that it is a high molecular compound in which the solubility to a developing solution changes by the action of an acid. As such a high molecular compound, resin which has a structural unit which generate | occur | produces an acid by exposure is mentioned. A well-known thing can be used for the monomer which guide | induces the structural unit which generate | occur | produces an acid by exposure.

<(A) component>

(A) component is a base material component whose solubility with respect to a developing solution changes with the action of an acid.

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

The organic compound used as a base component is largely divided into a nonpolymer and a polymer.

As a nonpolymer, the thing of molecular weight 500-4000 is normally used. Hereinafter, when called a "low molecular weight compound", the nonpolymer whose molecular weight is 500 or more and less than 4000 is shown.

As a polymer, the thing of molecular weight 1000 or more is used normally. Hereinafter, when referring to "resin", a "polymer compound", or a "polymer," the polymer whose molecular weight is 1000 or more is shown.

As a molecular weight of a polymer, the weight average molecular weight of polystyrene conversion by GPC (gel permeation chromatography) shall be used.

As (A) component used for the resist composition of this embodiment, at least (A1) component is used and you may use another high molecular compound and / or a low molecular compound together with this (A1) component.

In the resist composition of the present embodiment, the component (A) increases in polarity by the action of a specific polymer compound (A1), that is, a structural unit (a10) represented by general formula (a10-1) described later and an acid. It contains the high molecular compound (A1) (henceforth "the (A1) component") which has a structural unit (a1) containing an acid-decomposable group.

When the resist film formed using the resist composition containing such a component (A1) is exposed, the structural unit (a1) cleaves at least one bond in its structure by the action of an acid, thereby increasing its polarity. For this reason, the resist composition of this embodiment becomes negative in the case where a developing solution is an organic type developing solution (solvent developing process), and becomes a positive type in the case of an alkaline developing solution (alkali developing process). Since the polarity of the component (A1) changes before and after exposure, by using the component (A1), good development contrast can be obtained not only in the alkali development process but also in the solvent development process.

In other words, in the case of applying the alkali developing process, the component (A1) is poorly soluble in the alkaline developing solution before exposure. For example, if an acid is generated from the component (B) by exposure, the action of the acid causes polarity. This increase increases the solubility in the alkaline developer. Therefore, in the formation of the resist pattern, when the resist composition is selectively exposed to the resist film obtained by applying the resist composition onto the support, the resist film exposure portion changes from poorly soluble to soluble to an alkaline developer, while resist film minnows. Since the mining portion does not change while being insoluble in alkali, a positive resist pattern is formed by alkali development.

On the other hand, in the case of applying the solvent developing process, the component (A1) has high solubility with respect to the organic developer before exposure, and when an acid is generated from the component (B) by exposure, the polarity becomes high due to the action of the acid, resulting in an organic system. Solubility in the developer is reduced. Therefore, in the formation of the resist pattern, when the resist composition is selectively exposed to the resist film obtained by applying the resist composition on the support, the resist film exposure portion changes from soluble to poorly soluble to the organic developer, while resist film minnows. Since the light portion does not change while being soluble, by developing with an organic developer, a contrast can be provided between the exposed portion and the unexposed portion, and a negative resist pattern is formed.

About (A1) component

(A1) A component is a high molecular compound which has a structural unit (a10) represented by general formula (a10-1), and a structural unit (a1) containing an acid-decomposable group whose polarity increases by the action of an acid.

`` Structural unit (a10) ''

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

[Formula 2]

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ya ^x1 is a single bond or a divalent linking group. Wa ^x1 is a (n _ax1 +1) valent aromatic hydrocarbon group. n _ax1 is an integer of 1-3.]

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 of R is preferably a C1-C5 linear or branched alkyl group, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl And tert-butyl group, pentyl group, isopentyl group and neopentyl group. The C1-C5 halogenated alkyl group of R is group in which one part or all of the hydrogen atoms of the said C1-C5 alkyl group were substituted by the halogen atom. As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is especially preferable.

As R, a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 fluorinated alkyl group is preferable, and a hydrogen atom or a methyl group is most preferable from industrial availability.

In said formula (a10-1), Ya ^x1 is a single bond or a bivalent coupling group.

As a bivalent coupling group in Ya <^x1> , a bivalent hydrocarbon group which may have a substituent, and the bivalent coupling group containing a hetero atom are mentioned as a preferable thing, for example.

Divalent hydrocarbon groups which may have a substituent:

When Ya ^x1 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

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

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

Linear or branched aliphatic hydrocarbon groups

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- ], and 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 3 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.

As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) _2- , Alkylmethylene groups such as -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, and -C (CH ₂ CH ₃ ) _2- ; -CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂ CH _{3) 2} -CH ₂ - alkyl group such as ethylene; Alkyltrimethylene groups such as -CH (CH ₃ ) CH ₂ CH ₂ -and -CH ₂ CH (CH ₃ ) CH _2- ; _{-CH (CH 3) CH 2 CH} 2 CH 2 - and the like can be mentioned alkyl groups such as alkyl groups, such as tetramethylene _{-, -CH 2 CH (CH 3} ) CH 2 CH 2. As an alkyl group in an alkylalkylene group, a C1-C5 linear alkyl group is preferable.

Said linear or branched aliphatic hydrocarbon group may or may not have a substituent. As this substituent, a C1-C5 fluorinated alkyl group substituted with the fluorine atom, a fluorine atom, a carbonyl group, etc. are mentioned.

Aliphatic hydrocarbon groups containing rings in the structure

As the aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group (group except two hydrogen atoms from the aliphatic hydrocarbon ring) which may include a substituent containing a hetero atom in the ring structure, the cyclic aliphatic The group which the hydrocarbon group couple | bonded with the terminal of a linear or branched aliphatic hydrocarbon group, the group in which the said cyclic aliphatic hydrocarbon group interposes in the middle of a linear or branched aliphatic hydrocarbon group, etc. are mentioned. As said linear or branched aliphatic hydrocarbon group, the same thing as the above is mentioned.

It is preferable that it is C3-C20, and, as for a cyclic aliphatic hydrocarbon group, it is more preferable that it is C3-C12.

The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, the group remove | excluding two hydrogen atoms from monocycloalkane is preferable. As this monocycloalkane, a C3-C6 thing is preferable, A cyclopentane, a cyclohexane, etc. are mentioned specifically ,. As a polycyclic alicyclic hydrocarbon group, the group remove | excluding two hydrogen atoms from polycycloalkane is preferable, As the polycycloalkane, a C7-12 thing is preferable, Specifically, adamantane, norbornane, Isobornane, tricyclodecane, tetracyclododecane and the like.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. As this substituent, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, etc. are mentioned.

As an alkyl group as said substituent, a C1-C5 alkyl group is preferable and it is most preferable that they are a methyl group, an ethyl group, a propyl group, n-butyl group, and a tert- butyl group.

As the alkoxy group as the substituent, an alkoxy group having 1 to 5 carbon atoms is preferable, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group are more preferable. The period and ethoxy group are most preferred.

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

As a halogenated alkyl group as said substituent, the group by which one part or all part of the hydrogen atom of the said alkyl group was substituted by the said halogen atom is mentioned.

In the cyclic aliphatic hydrocarbon group, a part of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As a substituent containing this hetero atom, -O-, -C (= O) -O-, -S-, -S (= O) _2- , -S (= O) ₂ -O- is preferable. .

Aromatic hydrocarbon groups in 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 pi electrons, and may be monocyclic or polycyclic. It is preferable that carbon number of an aromatic ring is 5-30, 5-20 are more preferable, 6-15 are more preferable, and 6-12 are especially preferable. However, the carbon number does not include the carbon number in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene and phenanthrene; And an aromatic hetero ring in which part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. As a hetero atom in an aromatic hetero ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Specifically as an aromatic hetero ring, a pyridine ring, a thiophene ring, etc. are mentioned.

Specific examples of the aromatic hydrocarbon group include groups in which two hydrogen atoms are removed from the aromatic hydrocarbon ring or the aromatic hetero ring (arylene group or hetero arylene group); A group excluding two hydrogen atoms from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.); Groups in which one of the hydrogen atoms of a group (aryl group or heteroaryl group) excluding one hydrogen atom from the aromatic hydrocarbon ring or aromatic hetero ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naph And a group in which one hydrogen atom is further removed from an aryl group in an arylalkyl group such as a methylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group). It is preferable that carbon number of the alkylene group couple | bonded with 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-C1.

The hydrogen atom which the said aromatic hydrocarbon group has may be substituted by the said aromatic hydrocarbon group 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. As this substituent, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group etc. are mentioned, for example.

As an alkyl group as said substituent, a C1-C5 alkyl group is preferable and it is most preferable that they are a methyl group, an ethyl group, a propyl group, n-butyl group, and a tert- butyl group.

As an alkoxy group, a halogen atom, and a halogenated alkyl group as said substituent, what was illustrated as a substituent which substitutes the hydrogen atom which the said cyclic aliphatic hydrocarbon group has is mentioned.

Divalent linking groups containing hetero atoms:

When Ya ^x1 is a divalent linking group containing a hetero atom, preferred as the linking group are -O-, -C (= 0) -O-, -C (= 0)-, -OC (= 0) -O. -, -C (= O) -NH-, -NH-, -NH-C (= NH)-(H may be substituted with a substituent such as an alkyl group, 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 -Y ²¹ -S (= O) _Group represented by _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; Can be mentioned.

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

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 -Y ²¹ -S (= O) ₂ -OY ^22- , Y ²¹ and Y ²² are each independently It is a bivalent hydrocarbon group which may have a substituent The thing similar to the (divalent hydrocarbon group which may have a substituent) illustrated by description as said bivalent coupling group is mentioned.

As Y <^21> , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a C1-C5 linear alkylene group is still more preferable, and a methylene group or ethylene group is especially 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. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

In the group represented by the formula-[Y ²¹ -C (= O) -O] _{m "} -Y ^22- , m" is an integer of 0-3, it is preferable that it is an integer of 0-2, and 0 or 1 is more preferable. 1 is particularly preferable. In other words, as the group represented by the formula-[Y ²¹ -C (= O) -O] _{m "} -Y ^22- , the group represented by the formula -Y ²¹ -C (= O) -OY ²² -is particularly preferable. , Group represented by the formula-(CH ₂ ) _{a '} -C (= O) -O- (CH ₂ ) _b' -is preferable, in which a 'is an integer of 1-10, An integer is preferable, the integer of 1-5 is more preferable, 1 or 2 is more preferable, and 1 is the most preferable 1. b 'is an integer of 1-10, the integer of 1-8 is preferable, 1 The integer of -5 is more preferable, 1 or 2 is more preferable, and 1 is the most preferable.

As Ya ^x1 , a single bond, an ester bond [-C (= O) -O-], an ether bond (-O-), -C (= O) -NH-, a linear or branched alkylene group, Or a combination of these is preferable, and especially a single bond is more preferable.

In the formula (a10-1), ^x1 is Wa, _(ax1 n + 1) is a divalent aromatic hydrocarbon group.

Aromatic hydrocarbon group in the Wa ^x1, there may be mentioned groups except the (n _ax1 + 1) hydrogen atoms from the aromatic ring. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 pi 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 further 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 an aromatic hetero ring in which part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. As a hetero atom in an aromatic hetero ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Specifically as an aromatic hetero ring, a pyridine ring, a thiophene ring, etc. are mentioned.

In said formula (a10-1), n _ax1 is an integer of 1-3, 1 or 2 is preferable and 1 is more preferable.

The specific example of the structural unit represented by the said general formula (a10-1) is shown below.

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

[Formula 3]

The structural unit (a10) which the (A1) component has may be 1 type or 2 or more types.

Among the above-mentioned, the structural unit containing a hydroxy styrene skeleton is preferable, and, as for a structural unit (a10), the structural unit represented by the following general formula (a10-1-1) is especially preferable.

[Formula 4]

[Wherein, R ^st represents a hydrogen atom or a methyl group. m ₀₁ represents an integer of 1 to 3.]

10-95 mol% is preferable with respect to the total (100 mol%) of all the structural units which comprise the (A1) component, and, as for the ratio of a structural unit (a10) in (A1) component, 30-90 mol% Is more preferable, and 50-85 mol% is especially preferable.

By making ratio of a structural unit (a10) more than the lower limit of the said preferable range, lithographic characteristics, such as image development characteristic and EL margin, are improved more, and below the upper limit of the said preferable range, the balance with another structural unit is balanced. It is easy to get drunk.

`` Structural unit (a1) ''

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

An "acid-decomposable group" is a group having an acid-decomposable property that at least a part of the bonds in the structure of the acid-decomposable group can cleave due to the action of an acid.

As an acid-decomposable group in which polarity increases by the action of an acid, the group which decomposes by the action of an acid and produces | generates a polar group is mentioned, for example.

A polar group, for example carboxyl group, there may be mentioned hydroxyl group, an amino group, a sulfo group (-SO ₃ H) or the like. Among these, the polar group (Hereinafter, it may be called "OH containing polar group") in a structure is preferable, A carboxyl group or a hydroxyl group is more preferable, A carboxyl group is especially preferable.

As an acid-decomposable group, the group by which the said polar group was protected by the acid dissociable group (for example, the group which protected the hydrogen atom of OH containing polar group by the acid dissociable group) is mentioned.

An "acid dissociable group" is group which has acid dissociation property which (i) the bond between the said acid dissociable group and the atom adjacent to this acid dissociable group can cleave by action of an acid, or (ii) After a part of the bond cleaves by the action of an acid, a decarboxylation reaction occurs, whereby both of the groups capable of cleaving the bond between the acid dissociable group and an atom adjacent to the acid dissociable group are referred to.

The acid dissociable group constituting the acid-decomposable group needs to be a group having a lower polarity than the polar group produced by dissociation of the acid dissociable group, whereby the acid dissociable group dissociates when the acid dissociable group dissociates due to the action of acid. A polar group having a polarity higher than that of the genitals is generated and the polarity is increased. As a result, the polarity of the whole (A1) component increases. As the polarity increases, solubility in the developing solution relatively changes, solubility increases when the developing solution is an alkaline developing solution and decreases in solubility when the developing solution is an organic developing solution.

As an acid dissociable group, what has been proposed as an acid dissociable group of the base resin for chemically amplified resist so far is mentioned.

As an acid dissociable group of the base resin for chemically amplified resists, specifically, the "acetal acid dissociable group", the "tertiary alkyl ester type acid dissociable group" described below, and "tertiary alkyl" Oxycarbonyl acid dissociable group ”.

Acetal acid dissociative group:

As an acid dissociable group which protects a carboxyl group or a hydroxyl group among the said polar groups, the acid dissociable group represented by the following general formula (a1-r-1) (Hereinafter, it may be called "acetal type acid dissociable group"). Can be mentioned.

[Formula 5]

[In the formula, Ra ^'1, Ra' ² is a hydrogen atom or an alkyl group. Ra ' ³ is a hydrocarbon group, and Ra' ³ may be bonded to any of Ra ' ¹ and Ra' ² to form a ring.]

In Formula (a1-r-1), at least one of Ra ' ¹ and Ra' ² is preferably a hydrogen atom, and more preferably both of them are hydrogen atoms.

When Ra ' ¹ or Ra' ² is an alkyl group, the alkyl group may be the same as the alkyl group exemplified as a substituent which may be bonded to a carbon atom in the α-position in the description of the α-substituted acrylate ester. The alkyl group of -5 is preferable. Specifically, a linear or branched alkyl group is preferable. More specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. are mentioned, A methyl group or an ethyl group is mentioned. More preferably, a methyl group is especially preferable.

Expression may be mentioned (a1-r-1) of, Ra 'is a hydrocarbon group of ^3, linear or branched alkyl group, a hydrocarbon-type ring.

The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. 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 ethyl group is more preferable.

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

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

As an aliphatic hydrocarbon group which is a monocyclic group, the group remove | excluding one hydrogen atom from monocycloalkane is preferable. As this monocycloalkane, a C3-C6 thing is preferable, A cyclopentane, a cyclohexane, etc. are mentioned specifically ,.

As an aliphatic hydrocarbon group which is a polycyclic group, the group remove | excluding one hydrogen atom from polycycloalkane is preferable, As the polycycloalkane, a C7-12 thing is preferable, Specifically, adamantane, norbornane, and iso Bornan, tricyclodecane, tetracyclo dodecane, etc. are mentioned.

When the cyclic hydrocarbon group of Ra ' ³ is an aromatic hydrocarbon group, 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 pi 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 further 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 an aromatic hetero ring in which part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. As a hetero atom in an aromatic hetero ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Specifically as an aromatic hetero ring, a pyridine ring, a thiophene ring, etc. are mentioned.

Specific examples of the aromatic hydrocarbon group for Ra ′ ³ include groups in which one hydrogen atom is removed from the aromatic hydrocarbon ring or aromatic hetero ring (aryl group or heteroaryl group); A group in which one hydrogen atom is removed from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.); Groups in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic hetero ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2- Aryl alkyl groups, such as a naphthyl ethyl group, etc.) etc. are mentioned. It is preferable that carbon number of the alkylene group couple | bonded with the said aromatic hydrocarbon ring or aromatic heterocyclic ring is 1-4, It is more preferable that it is C1-C2, It is especially preferable that it is C1-C1.

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

Tertiary alkyl ester type acid dissociable group:

As an acid dissociable group which protects a carboxyl group in the said polar group, the acid dissociable group represented by the following general formula (a1-r-2) is mentioned, for example.

In addition, what consists of an alkyl group among the acid dissociable groups represented by following formula (a1-r-2) may be called "tertiary alkyl ester type acid dissociable group" for convenience.

[Formula 6]

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

Examples of the hydrocarbon group for Ra ′ ⁴ to Ra ′ ^{6 include} the same groups as those for Ra ′ ³ .

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

[Formula 7]

[In the formula, Ra ^'10 is an alkyl group having 1 to 10 carbon atoms. Ra is a group that forms an aliphatic cyclic group with ^'11 is Ra, the carbon atom ¹⁰ is bonded. Ra ^'12 to Ra' ¹⁴ each independently represent a hydrocarbon group.]

Equation (a1-r2-1) of, groups exemplified as the "Ra in the alkyl group is formulas (a1-r-1) of 1 to 10 carbon atoms in the ^{10 '3} linear or branched alkyl group of Ra desirable. Equation (a1-r2-1) of, Ra 'is Ra ^11' to ¹⁰ aliphatic cyclic group formed together with the carbon atoms bonded to the formula (a1-r-1) Ra '3 sentence of monocyclic or polycyclic in Groups exemplified as the aliphatic hydrocarbon group being a group are preferable.

In formula (a1-r2-2), Ra ^'12 and Ra' ¹⁴ are each independently an alkyl group having 1 to 10 carbon atoms, and the alkyl group is Ra ' ³ in formula (a1-r-1). The group exemplified as the linear or branched alkyl group of is more preferable, a linear alkyl group having 1 to 5 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable.

Equation (a1-r2-2) of, Ra 'is ^13, formula (a1-r-1) of the Ra in the' a linear or branched alkyl group, a monocyclic or polycyclic sentence of the example as a hydrocarbon group of ³ It is preferable that it is an aliphatic hydrocarbon group which is a group. Of these, Ra 'is ^13, Ra' is more preferably a linear or branched alkyl groups exemplified as the hydrocarbon group of ^3.

Specific examples of the group represented by the formula (a1-r2-1) are given below. * Represents a bond (the same in this specification below).

[Formula 8]

[Formula 9]

The specific example of group represented by said formula (a1-r2-2) is given to the following.

[Formula 10]

Tertiary alkyloxycarbonyl acid dissociable groups:

As an acid dissociable group which protects a hydroxyl group among the said polar groups, for example, the acid dissociable group represented by the following general formula (a1-r-3) (when it is called "tertiary alkyloxycarbonyl acid dissociable group" for convenience). There is a).

[Formula 11]

[Wherein Ra ' ⁷ to Ra' ⁹ are each an alkyl group.]

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

Moreover, it is preferable that it is 3-7, as for carbon number of the sum total of each alkyl group, it is more preferable that it is 3-5, and it is most preferable that it is 3-4.

Among the above, as an acid dissociable group of the base resin for chemically amplified resists, since the combination effect with (B) component (resolution, dimensional uniformity (CDU) in a support surface (Shot), etc.) is easy to be obtained, , A tertiary alkyl ester type acid dissociable group is preferable, an acid dissociable group represented by the formula (a1-r-2) is more preferable, and a group represented by the general formula (a1-r2-2) is more preferable.

Among the groups represented by general formula (a1-r2-2), groups represented by the above formula (r-pr-c1), formula (r-pr-c2) or formula (r-pr-c3) are preferable.

As structural unit (a1), the structural unit derived from the structural unit derived from the acrylate ester which the hydrogen atom couple | bonded with the carbon atom of the (alpha) position may be substituted by the substituent, the structural unit derived from acrylamide, the structure derived from hydroxy styrene or a hydroxy styrene derivative Hydrogen in -C (= O) -OH of a structural unit derived from a structural unit, vinylbenzoic acid or a vinylbenzoic acid derivative, at least a part of the hydrogen atom of the hydroxyl group of the unit protected by a substituent containing the acid-decomposable group The structural unit etc. which at least one part of the atom protected by the substituent containing the said acid-decomposable group are mentioned.

As a structural unit (a1), the structural unit derived from the acrylate ester in which the hydrogen atom couple | bonded with the carbon atom of the (alpha) position may be substituted by the substituent is preferable among the above.

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

[Formula 12]

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Va ¹ is a divalent hydrocarbon group which may have an ether bond. n _a1 is an integer of 0-2. Ra ¹ is an acid dissociable group represented by the above formula (a1-r-1) or (a1-r-2). Wa ¹ is a n _a2 + monovalent hydrocarbon group. n _a2 is an integer of 1-3. Ra ² is an acid dissociable group represented by the above formula (a1-r-1) or (a1-r-3).]

In said formula (a1-1), the C1-C5 alkyl group of R is preferably a C1-C5 linear or branched alkyl group, and specifically, methyl group, ethyl group, propyl group, isopropyl Group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. are mentioned. The C1-C5 halogenated alkyl group is group in which one part or all of the hydrogen atoms of the said C1-C5 alkyl group were substituted by the halogen atom. As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is especially preferable.

As R, a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 fluorinated alkyl group is preferable, and a hydrogen atom or a methyl group is most preferable from industrial availability.

In said formula (a1-1), the bivalent hydrocarbon group which may have an ether bond of Va < ¹ > is the same as when Ya ^x1 in said formula (a10-1) becomes a divalent hydrocarbon group which may have an ether bond as a substituent. Do.

In the formula (a1-2), _a2 group n + 1 valent hydrocarbon in the Wa ^1, and the contribution to the aliphatic hydrocarbon, and aromatic hydrocarbon contribution. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, may be saturated or unsaturated, and is preferably saturated. As said aliphatic hydrocarbon group, a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or a linear or branched aliphatic hydrocarbon group and a aliphatic hydrocarbon group containing a ring in the structure are combined One may be mentioned.

2-4 is preferable and, as for said n _a2 + 1 number, divalent or trivalent is more preferable.

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

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

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

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

[Formula 18]

The structural unit (a1) which the (A1) component has may be 1 type or 2 or more types.

In the component (A1), the proportion of the structural unit (a1) is preferably 5 to 90 mol%, and 10 to 70 mol% with respect to the total (100 mol%) of all the structural units constituting the (A1) component. Is more preferable, and 15-50 mol% is especially preferable.

By making ratio of a structural unit (a1) more than the lower limit of the said preferable range, the contrast of the exposed part and unexposed part of a resist film will become higher, and the resolution will improve. On the other hand, it becomes easy to balance with the other structural unit by using below the upper limit of the said preferable range.

≪Other structural units≫

(A1) A component may have other structural units other than the structural unit (a10) and structural unit (a1) which were mentioned above.

That in other structural units, for example, a lactone-containing cyclic group, -SO ₂ - containing a structural unit (a2) containing the cyclic group or a carbonate-containing cyclic group (provided that the structural units (a10) or the constituent units (a1) (A4), a structural unit derived from styrene, a structural unit derived from styrene, and a structural unit derived from styrene derivative (however, The structural unit (except all the structural units mentioned above) containing a polar group containing aliphatic hydrocarbon group, etc. are mentioned.

Construction unit (a2)

The structural unit (a2) is a structural unit containing a lactone-containing cyclic group, a -SO ₂ -containing cyclic group, or a carbonate-containing cyclic group (except those corresponding to the structural unit (a10) or the structural unit (a1)). to be.

The lactone-containing cyclic group, the -SO ₂ -containing cyclic group, or the carbonate-containing cyclic group of the structural unit (a2) is effective in enhancing the adhesion of the resist film to the substrate when the component (A1) is used for formation of the resist film. . Moreover, when (A1) component has a structural unit (a2), in the alkali image development process, the solubility to the alkali developing solution of a resist film at the time of image development becomes high.

A "lactone containing cyclic group" represents the cyclic group containing the ring (lactone ring) containing -O-C (= O)-in the ring skeleton. When a lactone ring is counted as a 1st ring and it is only a lactone ring, when it has only a monocyclic group and when it has another ring structure, it is called polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

The lactone-containing cyclic group in the structural unit (a2) is not particularly limited, and any one can be used. Specifically, the group represented by the following general formula (a2-r-1) (a2-r-7) is mentioned, respectively.

[Formula 19]

[Wherein, Ra ^'21 are each independently hydrogen atom, alkyl group, alkoxy group, halogen atom, halogenated alkyl group, a hydroxyl group, -COOR ", -OC (= O ) R", hydroxy group or cyano group. R ″ is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a —SO ₂ -containing cyclic group. A ″ may contain an oxygen atom (-O-) or a sulfur atom (-S-) It is a C1-C5 alkylene group, an oxygen atom, or a sulfur atom to become. n 'is an integer of 0-2, m' is 0 or 1.]

In the general formula (a2-r-1) ~ (a2-r-7), the alkyl group in Ra ^'21 is an alkyl group having 1 to 6 carbon atoms are preferred. It is preferable that this alkyl group is a linear or branched chain type. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, etc. are mentioned. Among these, a methyl group or an ethyl group is preferable and a methyl group is especially preferable.

Ra 'The alkoxy group in ²¹ is preferably an alkoxy group having 1 to 6 carbon atoms. It is preferable that this alkoxy group is linear or branched chain form. Specifically, there is a group with an oxygen atom (-O-) exemplified as the alkyl group in the above-mentioned Ra ^'21 include groups attached.

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

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

In the ^{Ra '21 -COOR ", -OC (} = O) R" in, R "is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ₂ - containing a cyclic group.

As an alkyl group in R ", any of a linear, branched or cyclic ring may be sufficient, and carbon number is 1-15.

When R "is a linear or branched alkyl group, it is preferable that it is C1-C10, It is more preferable that it is C1-C5, It is especially preferable that it is a methyl group or an ethyl group.

When R "is a cyclic alkyl group, it is preferable that it is C3-C15, It is more preferable that it is C4-C12, Most preferably, C5-C10 is specifically, Substituted by a fluorine atom or a fluorinated alkyl group Group which remove | excluded 1 or more hydrogen atoms from the monocyclo alkan which may be sufficient and may not be substituted; the group etc. which removed 1 or more hydrogen atoms from polycycloalkane, such as bicycloalkane, tricycloalkane, and tetracycloalkane, are illustrated More specifically, groups excluding one or more hydrogen atoms from monocycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like The group remove | excluding one or more hydrogen atoms from the polycycloalkane of etc. are mentioned.

Examples of the lactone-containing cyclic group in R ″ include the same groups as those represented by general formulas (a2-r-1) to (a2-r-7).

As a carbonate-containing cyclic group in R ", it is the same as the carbonate-containing cyclic group mentioned later, and the group specifically, shown by general formula (ax3-r-1)-(ax3-r-3) is mentioned, respectively.

R "-SO ₂ of the-containing cyclic group, which will be described later -SO ₂ - containing cyclic group with the same and, specifically, each by the formula (a5-r-1) ~ (a5-r-4) The group represented is mentioned.

The hydroxyalkyl group for Ra ′ ²¹ preferably has 1 to 6 carbon atoms, and specific examples include groups in which at least one hydrogen atom of the alkyl group in Ra ′ ²¹ is substituted with a hydroxyl group.

In the general formulas (a2-r-2), (a2-r-3) and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A ″ may be linear or branched. The alkylene group of is preferable, and a methylene group, an ethylene group, n-propylene group, an isopropylene group, etc. are mentioned, When the alkylene group contains an oxygen atom or a sulfur atom, as the specific example, the said alkylene group And groups which -O- or -S- are interposed between the terminal or the carbon atom of, for example -O-CH _2- , -CH ₂ -O-CH _2- , -S-CH ₂ -,- CH ₂ -S-CH ₂ -and the like. As A ″, an alkylene group having 1 to 5 carbon atoms or —O— is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is most preferred. .

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

[Formula 20]

[Formula 21]

"-SO ₂ - containing cyclic group" means, -SO ₂ during the ring backbone - represents a cyclic group containing a ring containing, specifically, -SO ₂ - a cyclic sulfur atom (S) in the It is a cyclic group which forms part of the ring skeleton of. In the ring skeleton, a ring containing -SO ₂ -is counted as the first ring, and in the case of only the ring, a ring group is referred to as a monocyclic group, and in the case of having another ring structure, it is called a polycyclic group regardless of the structure. The -SO ₂ -containing cyclic group may be a monocyclic group or a polycyclic group.

-SO ₂ - containing cyclic group are, in particular, those in the ring skeleton -O-SO ₂ - sultone (sultone) of the -OS- of forms part of the ring backbone-cyclic group containing, i.e. -O-SO ₂ It is preferable that it is a cyclic group containing a ring.

-SO ₂ - containing a cyclic group, there may be mentioned more specifically the following formula (a5-r-1) ~ (a5-r-4) to an indicating respectively.

[Formula 22]

[In formula, Ra ^'51 is respectively independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR ", -OC (= O) R", a hydroxyalkyl group, or a cyano group. R "is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ₂ -.-Containing cyclic group A" is an oxygen atom, or may contain a sulfur atom, an alkylene group having 1 to 5 carbon atoms, the oxygen of which is Atom or sulfur atom. n 'is an integer of 0-2.]

In General Formulas (a5-r-1) to (a5-r-2), A ″ is represented by General Formulas (a2-r-2), (a2-r-3), and (a2-r-5). Is the same as A "

Ra ^'51 alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, -COOR in ", -OC (= O) R ", a hydroxyl group, each of the above general formula (a2-r-1) ~ (a2 -r-7) it can be given in the same as those exemplified in the description of the Ra ^'21.

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

[Formula 23]

[Formula 24]

[Formula 25]

The "carbonate-containing cyclic group" refers to a cyclic group containing a ring (carbonate ring) containing -O-C (= O) -O- in its ring skeleton. A carbonate ring is counted as a 1st ring, and when it is only a carbonate ring, when it has a monocyclic group and when it has another ring structure, it is called a polycyclic group regardless of the structure. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group.

The carbonate ring-containing cyclic group is not particularly limited, and any one can be used. Specifically, the group represented by the following general formula (ax3-r-1) (ax3-r-3)-is mentioned, respectively.

[Formula 26]

[In formula, ^Ra'x31 is respectively independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR ", -OC (= O) R", a hydroxyalkyl group, or a cyano group. R "is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or -SO ₂ -.-Containing cyclic group A" is an oxygen atom, or may contain a sulfur atom, an alkylene group having 1 to 5 carbon atoms, the oxygen of which is Atom or sulfur atom. p 'is an integer of 0-3, q' is 0 or 1.]

In General Formulas (ax3-r-2) to (ax3-r-3), A ″ represents the general formulas (a2-r-2), (a2-r-3), and (a2-r-5). Is the same as A "

Ra ^'31 alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, -COOR in ", -OC (= O) R ", a hydroxyl group, each of the above general formula (a2-r-1) ~ (a2 -r-7) it can be given in the same as those exemplified in the description of the Ra ^'21.

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

[Formula 27]

Especially as a structural unit (a2), the structural unit derived from the acrylate ester which the hydrogen atom couple | bonded with the carbon atom of the (alpha) position may be substituted by the substituent is preferable.

It is preferable that such a structural unit (a2) is a structural unit represented with the following general formula (a2-1).

[Formula 28]

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ya ²¹ is a single bond or a divalent linking group. La ²¹ is -O-, -COO-, -CON (R ')-, -OCO-, -CONHCO- or -CONHCS-, and R' represents a hydrogen atom or a methyl group. However, when La ²¹ is -O-, Ya ²¹ is not -CO-. Ra ²¹ is a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ₂ -containing cyclic group.]

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

Examples of the divalent linking group for Ya ^{21 include} the same divalent linking groups for Ya ^x1 in General Formula (a10-1) described above. Especially, as Ya ^{21, it} is preferable that they are a single bond, ester bond [-C (= O) -O-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof. Do.

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

The lactone-containing cyclic group, -SO ₂ -containing cyclic group, and carbonate-containing cyclic group for Ra ²¹ are each represented by general formulas (a2-r-1) to (a2-r-7) described above. And groups represented by general formulas (a5-r-1) to (a5-r-4), and groups represented by general formulas (ax3-r-1) to (ax3-r-3), respectively.

Among them, the lactone-containing cyclic group or -SO ₂ - containing cyclic group is preferred, and the formula (a2-r-1), (a2-r-2), (a2-r-6) or (a5-r Groups respectively represented by -1) are more preferable. Specifically, the chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-18), and (r-lc) -6-1), which is respectively represented by (r-sl-1-1) and (r-sl-1-18) is more preferable.

1 type may be sufficient as the structural unit (a2) which (A1) component has, and 2 or more types may be sufficient as it.

When (A1) component has a structural unit (a2), the ratio of a structural unit (a2) among the (A1) components is with respect to the total (100 mol%) of all the structural units which comprise this (A1) component, It is preferable that it is 1-40 mol%, 2-20 mol% is more preferable, 5-10 mol% is further more preferable.

By making ratio of a structural unit (a2) more than the lower limit of the said preferable range, the effect by containing a structural unit (a2) is fully acquired. On the other hand, by below the upper limit of the said preferable range, it becomes easy to balance with the other structural unit, and various lithographic characteristics and pattern shape become favorable.

Construction unit (a4)

Structural unit (a4) is a structural unit containing an acid non-aliphatic cyclic group.

When the (A1) component has a structural unit (a4), the dry etching tolerance of the formed resist pattern improves. Moreover, the hydrophobicity of (A) component becomes high. The improvement of hydrophobicity contributes to improvement of resolution, resist pattern shape, etc., especially in the case of resist pattern formation by a solvent image development process.

The "acid non-lipophilic cyclic group" in the structural unit (a4) has an acid function when acid is generated in the resist composition by exposure (for example, when acid is generated from component (B) described later). It is a cyclic group which remains in the said structural unit without dissociating even if it is.

As the structural unit (a4), for example, a structural unit derived from an acrylate ester containing an acid non-aliphatic alicyclic group is preferable. The aliphatic cyclic group is used for resin components of resist compositions such as for ArF excimer laser and KrF excimer laser (preferably for ArF excimer laser), and a number of conventionally known ones can be used.

It is especially preferable at the point which is at least 1 type chosen from the group which consists of a tricyclodecyl group, an adamantyl group, a tetracyclo dodecyl group, an isobornyl group, and a norbornyl group, and is easy to obtain industrially. These polycyclic groups may have a C1-C5 linear or branched alkyl group as a substituent.

As a structural unit (a4), the structural unit represented by the following general formula (a4-1) (a4-7)-can be illustrated specifically ,.

[Formula 29]

[Wherein, R ^α is the same as above.]

The structural unit (a4) which (A1) component has may be 1 type, or 2 or more types may be sufficient as it.

When (A1) component has a structural unit (a4), the ratio of a structural unit (a4) among the (A1) components is with respect to the total (100 mol%) of all the structural units which comprise the (A1) component, It is preferable that it is 1-30 mol%, and 3-20 mol% is more preferable.

By making ratio of a structural unit (a4) more than the lower limit of the said preferable range, the effect by containing a structural unit (a4) is fully acquired. On the other hand, it becomes easy to balance with the other structural unit by using below the upper limit of the said preferable range.

Structural units derived from styrene

When (A1) component has a structural unit derived from styrene, the ratio of the structural unit guide | induced from styrene among (A1) component is to the sum total (100 mol%) of all the structural units which comprise the (A1) component. It is preferable that it is 1-30 mol%, and 3-20 mol% is more preferable.

In the resist composition of the embodiment, the component (A) contains a polymer compound (A1) having a structural unit (a10) and a structural unit (a1).

As such (A1) component, the high molecular compound which has a repeating structure of a structural unit (a10) and a structural unit (a1) is preferable, Among these, the structure derived from a structural unit (a10), a structural unit (a1), and styrene Particular preference is given to high molecular compounds having a repeating structure of units.

5000-20000 are preferable, as for the weight average molecular weight (Mw) of the component (A1) (gel permeation chromatography (GPC)), 7000-15000 are more preferable, 8000-13000 are more preferable. .

When Mw of (A1) component is below the upper limit of the said preferable range, it becomes easy to suppress that the viscosity of a resist composition becomes high too much, and the applicability | paintability to the support body of a resist composition improves more. In addition, it becomes easy to have solubility in the resist solvent sufficient for use as a resist, and also becomes easy to become high in sensitivity. On the other hand, the resist film of a thick film is easily formed as it is more than the lower limit of the said preferable range. In addition, the dry etching resistance and the resist pattern cross-sectional shape become more favorable.

The dispersion degree (Mw / Mn) of (A1) 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.

As the component (A1) contained in the resist composition, one type may be used alone, or two or more types may be used in combination.

As for the ratio of (A1) component in (A) component, 25 mass% or more is preferable with respect to the gross mass of (A) component, 50 mass% or more is more preferable, 75 mass% or more is more preferable, 100 Mass% may be sufficient. When the ratio of the component (A1) is equal to or greater than the lower limit of the above preferred range, a resist pattern excellent in high sensitivity, resolution, dimensional uniformity (CDU) and other lithography characteristics in the support surface (Shot) is easily formed.

In the resist composition of embodiment, it is preferable that it is 15-50 mass% with respect to the total amount (100 mass%) of a resist composition, as for the density | concentration of the said high molecular compound (A1), 25-45 mass% is more preferable, 30 40 mass% is more preferable.

If the density | concentration of (A1) component in a resist composition is more than the lower limit of the said preferable range, a thick film resist film will be formed easily, On the other hand, if it is below the upper limit of the said preferable range, it will suppress that the viscosity of a resist composition becomes too high. Easier

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

What is necessary is just to adjust content of (A) component in the resist composition of this embodiment according to the resist film thickness etc. which are formed.

<(B) component>

In addition to (A) component, the resist composition of this embodiment contains an acid generator component (B) (henceforth "a component (B)").

Such a component (B) contains a specific acid generator (B1), that is, an acid generator (B1) (hereinafter also referred to as "(B1) component") represented by general formula (b1) described later. By including the component (B1), foaming at high temperature baking is suppressed in forming a resist pattern. In addition, when forming a resist pattern, favorable sensitivity becomes easy to be maintained and lithographic characteristics (dimension uniformity etc.) improve.

About (B1) component

(B1) A component is an acid generator represented by the following general formula (b1).

[Formula 30]

[ ^Wherein , R ²⁰¹¹ , R ²⁰²¹ and R ²⁰³¹ each independently represent an aryl group which may have a substituent. Two or more of R ²⁰¹¹ , R ^2021, and R ²⁰³¹ may be bonded to each other to form a ring together with a sulfur atom in the formula. X ^- represents a counter anion.]

In the formula ^{(b1), R 2011, R} 2021 and R ²⁰³¹ are each independently an aryl group which may have a substituent.

R ^2011, R ^2021, and the aryl group in R ²⁰³¹ has, there may be mentioned an aryl group of non-substituted having from 6 to 20 carbon atoms, preferably a phenyl group, a naphthyl group.

R ^2011, a substituent which may have an aryl group in R ²⁰²¹ and R ²⁰³¹ may be, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, the general formula (ca-r in to And groups represented by -1) to (ca-r-7), respectively.

The alkyl group as the substituent here is preferably an alkyl group having 1 to 5 carbon atoms, and preferably a linear or branched alkyl group.

The halogenated alkyl group as the substituent here is preferably a halogenated alkyl group having 1 to 5 carbon atoms, and preferably a linear or branched halogenated alkyl group.

The aryl group as a substituent here is a C6-C20 aryl group, A phenyl group and a naphthyl group are preferable.

[Formula 31]

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

In the formulas (ca-r-1) to (ca-r-7), each of R ′ ²⁰¹ independently represents a hydrogen atom, a cyclic group which may have a substituent, or 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 the hydrocarbon group which does not have aromaticity. In addition, the aliphatic hydrocarbon group may be saturated or unsaturated, it is preferable that it is usually saturated.

The aromatic hydrocarbon group in R ′ ²⁰¹ is a hydrocarbon group having an aromatic ring. The carbon number of the aromatic hydrocarbon group is preferably 3 to 30, 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. Do. However, the carbon number does not include the carbon number in the substituent.

R 'as an aromatic ring which group is an aromatic hydrocarbon in the ²⁰¹ Specifically, benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a portion of carbon atoms constituting these aromatic ring is a heteroatom-substituted aromatic Heterocyclic ring etc. are mentioned. As a hetero atom in an aromatic hetero ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned.

Specific examples of the aromatic hydrocarbon group for R ′ ²⁰¹ include a group in which one hydrogen atom is removed from the aromatic ring (an aryl group: for example, a phenyl group or a naphthyl group) and one of the hydrogen atoms in the aromatic ring is alkylene. Groups substituted with the group (for example, an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group). It is preferable that carbon number of the said alkylene group (alkyl chain in an arylalkyl group) is 1-4, It is more preferable that it is 1-2, It is especially preferable that it is 1.

^Examples of the cyclic aliphatic hydrocarbon group for R ′ ²⁰¹ include aliphatic hydrocarbon groups containing a ring in the structure.

Examples of the aliphatic hydrocarbon group containing a ring in this structure include an alicyclic hydrocarbon group (a group excluding one hydrogen atom from an aliphatic hydrocarbon ring) and an alicyclic hydrocarbon group bonded to a terminal of a linear or branched aliphatic hydrocarbon group. And groups 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 3-20, and, as for the said alicyclic hydrocarbon group, it is more preferable that it is C3-C12.

The alicyclic hydrocarbon group may be a polycyclic group or may be a monocyclic group. As a monocyclic alicyclic hydrocarbon group, the group remove | excluding one or more hydrogen atoms from monocycloalkane is preferable. As this monocycloalkane, a C3-C6 thing is preferable, A cyclopentane, a cyclohexane, etc. are mentioned specifically ,. As a polycyclic alicyclic hydrocarbon group, the group remove | excluding one or more hydrogen atoms from polycycloalkane is preferable, and as the polycycloalkane, a C7-30 thing is preferable. Among these, examples of the polycycloalkane include polycycloalkanes having a polycyclic skeleton of a crosslinked ring system such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane; More preferred are polycycloalkanes having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.

Especially, as the cyclic aliphatic hydrocarbon group for R ′ ²⁰¹ , a group in which one or more hydrogen atoms are removed from monocycloalkane or polycycloalkane is preferable, and a group in which one hydrogen atom is removed from polycycloalkane is more preferable. , Adamantyl group and norbornyl group are particularly preferred, and adamantyl group is most preferred.

The linear or branched aliphatic hydrocarbon group which may be bonded to an 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 more preferably 1 carbon atom. 3 is the most preferable.

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- ], and a trimethylene group [-( CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ], and the like.

As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) _2- , Alkylmethylene groups such as -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, and -C (CH ₂ CH ₃ ) _2- ; -CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂ CH _{3) 2} -CH ₂ - alkyl group such as ethylene; Alkyltrimethylene groups such as -CH (CH ₃ ) CH ₂ CH ₂ -and -CH ₂ CH (CH ₃ ) CH _2- ; _{-CH (CH 3) CH 2 CH} 2 CH 2 - and the like can be mentioned alkyl groups such as alkyl groups, such as tetramethylene _{-, -CH 2 CH (CH 3} ) CH 2 CH 2. As an alkyl group in an alkylalkylene group, a C1-C5 linear alkyl group is preferable.

In addition, the cyclic hydrocarbon group for R ' ²⁰¹ may contain a hetero atom, such as a hetero ring. Specifically, the lactone-containing cyclic groups represented by general formulas (a2-r-1) to (a2-r-7), respectively, and the general formulas (a5-r-1) to (a5-r-4), respectively represents -SO ₂ - containing cyclic group, there may be mentioned the other the formula (r-hr-1) ~ a complex cyclic group represents respectively the (r-hr-16) of the.

[Formula 32]

Moreover, the thing similar to the acid dissociable group represented by above-mentioned Formula (a1-r-2) is mentioned as a cyclic group which may have a substituent.

R 'with a substituent in the cyclic group ²⁰¹ is, for example, there may be mentioned an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group and the like.

As an alkyl group as a substituent, a C1-C5 alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, n-butyl group, and tert- butyl group are more preferable.

As an alkoxy group as a substituent, a C1-C5 alkoxy group is preferable, A methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group are more preferable, A methoxy group And ethoxy groups are 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.

As a halogenated alkyl group as a substituent, the group by which one part or all hydrogen atoms, such as a C1-C5 alkyl group, for example, a methyl group, an ethyl group, a propyl group, n-butyl group, tert- butyl group, were substituted by the said halogen atom is mentioned. have.

Group as a substituent, a methylene group constituting the hydrocarbon ring of the type -, a group substituted with a (-CH _2).

Chain alkyl group which may have a substituent:

The chain alkyl group of R ′ ²⁰¹ may be either a straight chain or a branched chain.

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

The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. 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.

Moreover, the same thing as the acid dissociable group represented by Formula (a1-r-2) mentioned above as a linear alkyl group which may have a substituent is mentioned.

Chain alkenyl groups which may have a substituent:

The linear alkenyl group of R ′ ²⁰¹ may be either linear or branched, preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, furthermore 2 to 4 carbon atoms. It is preferable and C3 is especially preferable. As a linear alkenyl group, a vinyl group, a propenyl group (allyl group), 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 a linear alkenyl group, a linear alkenyl group is preferable among the above, A vinyl group and a propenyl group are more preferable, A vinyl group is especially preferable.

R 'with a substituent in groups alkyl or alkenyl chain of the ²⁰¹ type, for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, wherein R', such as cyclic group of the ²⁰¹ Can be mentioned.

Among the above, R ' ²⁰¹ is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, the group remove | excluding one or more hydrogen atoms from the phenyl group, naphthyl group, and polycycloalkane; Lactone-containing cyclic groups represented by general formulas (a2-r-1) to (a2-r-7), respectively; The -SO ₂ -containing cyclic groups represented by general formulas (a5-r-1) to (a5-r-4) are preferable. In particular, R 'is ^201, more preferably an from poly cycloalkane which may have a substituent, except for at least one hydrogen atom.

In the embodiment of the component (B1) containing the resist composition, at least one of the general formula R ^2011, R ²⁰²¹ and R ²⁰³¹ in (b1), is preferably an aryl group having a substituent. When at least one of R ²⁰¹¹ , R ²⁰²¹ and R ²⁰³¹ is an aryl group having a substituent, the foaming at high temperature bake becomes easy to be suppressed, so that the solubility in an organic solvent is increased, so that precipitation during development does not occur easily. do. In addition, the process margin at the time of pattern formation tends to be large, and for example, the depth of focus width (DOF) characteristic is easily improved.

In this case, R ^2011, the R substituent having ²⁰²¹ and an aryl group in R ^2031, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and the general formula (ca-r-1 of the It is preferable that it is one or more selected from the group which consists of groups respectively represented by-(ca-r-7).

Two or more of said R ²⁰¹¹ , R ^2021, and R ²⁰³¹ may combine with each other, and may form a ring with the sulfur atom in a formula.

When a ring is formed in this way, a hetero atom such as a sulfur atom, an oxygen atom, a nitrogen atom, or a carbonyl group, -SO-, -SO _2- , -SO _3- , -COO-, -CONH- or -N (R _You may bond through functional groups, such as _N )-(where _RN is a C1-C5 alkyl group).

As a ring formed, it is preferable that one ring which contains the sulfur atom in a formula in the ring skeleton is a 3-10 membered ring including a sulfur atom, and it is especially preferable that it is a 5-7 membered ring. As a specific example of the ring formed, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, 9H- thioxanthene ring, thioxanthone Ring, thianthrene ring, phenoxatiin ring, tetrahydrothiophenium ring, tetrahydrothiopyranium ring and the like.

Specifically as a preferable cation in the acid generator represented by the said general formula (b1), the cation represented by the following general formula (ca-1-1) (ca-1-55) can be mentioned, respectively. .

[Formula 33]

[Formula 34]

[Formula 35]

[In formula, g1, g2, g3 represents a repeating number, g1 is an integer of 1-5, g2 is an integer of 0-20, g3 is an integer of 0-20.]

[Formula 36]

In said formula (b1), X <^-> represents a counter anion.

There is no restriction | limiting in particular as this X <^-> , The anion known as an anion part of the acid generator component for resist compositions can be used suitably.

For example, as X <^-> , the anion represented by the following general formula (b1-a1), the anion represented by general formula (b1-a2), or the anion represented by general formula (b1-a3) is mentioned.

[Formula 37]

[In formula, R <^101> , R <^104> -R <^108> is respectively independently the cyclic group which may have a substituent, the linear alkyl group which may have a substituent, or the linear 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 divalent linking group containing a single bond or an oxygen atom. V ¹⁰¹ to V ¹⁰³ each independently represent a single bond, an alkylene group, or a fluorinated alkylene group. L ¹⁰¹ to L ¹⁰² each independently represent a single bond or an oxygen atom. L ¹⁰³ to L ¹⁰⁵ are each independently a single bond, -CO-, or -SO _2- .]

Anion represented by general formula (b1-a1)

In formula (b1-a1), 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, and each of the above formulas (ca -r-1) ~ (ca- r-7) of the R 'can be given in ²⁰¹ to the same.

Among the above, 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, the group remove | excluding one or more hydrogen atoms from the phenyl group, naphthyl group, and polycycloalkane; Lactone-containing cyclic groups represented by general formulas (a2-r-1) to (a2-r-7), respectively; Preferred are -SO ₂ -containing cyclic groups represented by general formulas (a5-r-1) to (a5-r-4).

In Formula (b1-a1), Y ¹⁰¹ is a divalent linking group containing a single bond or an oxygen atom.

When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, the Y ¹⁰¹ may contain 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.

As a bivalent coupling group containing an oxygen atom, an oxygen atom (ether bond: -O-), an ester bond (-C (= O) -O-), an oxycarbonyl group (-OC (= O)- ), Hydrogen atom-containing oxygen atom-containing linking group such as amide bond (-C (= O) -NH-), carbonyl group (-C (= O)-), carbonate bond (-OC (= O) -O-) ; And combinations of the non-hydrocarbon based oxygen atom-containing linking groups with alkylene groups. The sulfonyl group (-SO _2- ) may be further connected to this combination. As a bivalent coupling group containing such an oxygen atom, the coupling group represented by the following general formula (y-al-1) (y-al-7), respectively is mentioned, for example.

[Formula 38]

[In formula, ^V'101 is a single bond or a C1-C5 alkylene group, and ^V'102 is a C1-C30 divalent saturated hydrocarbon group.]

V 'group is a divalent saturated hydrocarbon group of the ^102, preferably an alkylene group of 1 to 30 carbon atoms, more preferably an alkylene group of 1 to 10 carbon atoms, more preferably an alkylene group of 1 to 5 carbon atoms.

V alkylene group in the ^"101 and V" ^102, respectively, and alkylene contribution of linear and branched alkylene contribution of, is preferably an alkylene group of a linear.

V as an alkylene group in the ^"101 and V" ^102, specifically, a methylene group [-CH ₂ -]; -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH _{2 CH 2 CH 3) -, -C} (CH 2 CH 3) 2 - alkyl, such as methylene group; Ethylene group [-CH ₂ CH _2- ]; _{-CH (CH 3) CH 2 -} , -CH (CH 3) CH (CH 3) -, -C (CH 3) 2 CH 2 -, -CH (CH 2 CH 3) CH 2 - such as the ethylene-alkyl ; Trimethylene group (n-propylene group) [-CH ₂ CH ₂ CH _2- ]; Alkyltrimethylene groups such as -CH (CH ₃ ) CH ₂ CH ₂ -and -CH ₂ CH (CH ₃ ) CH _2- ; Tetramethylene group [-CH ₂ CH ₂ CH ₂ CH _2- ]; Alkyltetramethylene groups such as -CH (CH ₃ ) CH ₂ CH ₂ CH ₂ -and -CH ₂ CH (CH ₃ ) CH ₂ CH _2- ; Pentamethylene groups [—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —] and the like.

In addition, or may V 'or ¹⁰¹ V' ¹⁰² portion of the methylene groups in the alkylene groups of the, optionally substituted by a divalent aliphatic cyclic group with a carbon number of 5-10. The aliphatic cyclic group further removes one hydrogen atom from the cyclic aliphatic hydrocarbon group of Ra ' ³ in the formula (a1-r-1) (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group). A divalent group is preferable and a cyclohexylene group, a 1, 5- adamantylene group or a 2, 6- adamantylene group is more preferable.

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

In formula (b1-a1), V ¹⁰¹ is a single bond, an alkylene group, or a fluorinated alkylene group. Group is an alkylene group, a fluorinated alkylene group in V ^101, preferably having a carbon number of 1-4. 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. Especially, it is preferable that V <^101> is a single bond or a C1-C4 fluorinated alkylene group.

R <^102> is a fluorine atom or a C1-C5 fluorinated alkyl group in formula (b1-a1). R ¹⁰² is preferably a fluorine atom or a C 1-5 perfluoroalkyl group, and more preferably a fluorine atom.

As a specific example of the anion part represented by said Formula (b1-a1), when ^Y101 becomes a single bond, for example, fluorination, such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion, etc. Alkylsulfonate anion is mentioned. When ^Y101 is a bivalent coupling group containing an oxygen atom, the anion represented by any of the following general formula (an-1) (an-3)-is mentioned.

[Formula 39]

[Wherein, R ″ ¹⁰¹ is an aliphatic cyclic group which may have a substituent, a group represented by the formulas (r-hr-1) to (r-hr-6), or a chain alkyl group which may have a substituent, respectively. R ″ ¹⁰² is an aliphatic cyclic group which may have a substituent, a lactone-containing cyclic group represented by general formulas (a2-r-1) to (a2-r-7), or the general formula (a5-r). -1) ~ (-SO ₂ represent respectively a5-r-4) - containing a cyclic group. R ″ ¹⁰³ is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent. V ″ ¹⁰¹ is a single bond or an alkyl having 1 to 4 carbon atoms. 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 "are each independently an integer of 0-3, q" is each independently an integer of 1-20, 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 in the cyclic aliphatic hydrocarbon group 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 hydrocarbons, cyclic 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.

The chain alkyl group which may have a substituent in R ″ ¹⁰¹ is preferably a group exemplified as the chain alkyl group in R ^{101 described} above. A chain type egg which may have a substituent in R ″ ¹⁰³ . It is preferable that a kenyl group is group which was illustrated as a chain alkenyl group in said R <^101> .

In the formulas (an-1) to (an-3), V ″ ¹⁰¹ is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. V ″ ¹⁰¹ is a single bond, A C1 alkylene group (methylene group) or a C1-C3 fluorinated alkylene group is preferable.

R <^102> is a fluorine atom or a C1-C5 fluorinated alkyl group in said Formula (an-1)-(an-3). R ¹⁰² is preferably a C 1-5 perfluoroalkyl group or a fluorine atom, and more preferably a fluorine atom.

V "is an integer of 0-3, Preferably it is 0 or 1 in said Formula (an-1)-(an-3). Q" is an integer of 1-20, Preferably it is 1-2 It is an integer of 10, More preferably, it is an integer of 1-5, More preferably, it is 1, 2 or 3, Especially preferably, it is 1 or 2. n "is 0 or 1;

Anion represented by general formula (b1-a2)

In formula (b1-a2), 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 Formula (b1-a1) is mentioned, respectively. However, R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring.

R ¹⁰⁴ and R ¹⁰⁵ are each 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.

It is preferable that carbon number of this linear alkyl group is 1-10, More preferably, it is C1-C7, More preferably, it is C1-C3. ^{Carbon number} of the chain alkyl group of R <^104> , R <^105> is so preferable that it is small in the range of the said carbon number, for the reason that the solubility with respect to the solvent for resists is also favorable. Moreover, in the chain alkyl group of R <^104> , R <^105> , since the number of the hydrogen atoms substituted by the fluorine atom increases, the intensity | strength of an acid becomes strong, and it is preferable.

The proportion of the 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.

Formula (b1-a2) of the, V ^102, V ^103, can each independently represent, a single bond, an alkylene group or fluorinated alkylene group, that, respectively, equal to ¹⁰¹ V in the formula (b1-a1).

In formula (b1-a2), L ¹⁰¹ and L ¹⁰² each independently represent a single bond or an oxygen atom.

Anion represented by general formula (b1-a3)

In formula (b1-a3), 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 (b1-a1) is mentioned, respectively.

In formula (b1-a3), L ¹⁰³ to L ¹⁰⁵ are each independently a single bond, -CO-, or -SO _2- .

Among the above, as an anion part of (B1) component, the anion represented by general formula (b1-a1) is preferable. When (B1) component which uses this anion as an anion part is used, in a resist pattern formation, the dimensional uniformity in a support surface becomes higher. For example, when the pattern of space and line is formed, the deviation of the dimension CD of space width is small, and the pattern of uniform width becomes easy to be formed with high precision.

Among these anions, anions represented by any of the above general formulas (an-1) to (an-3) are more preferable, and anions represented by any of general formulas (an-1) or (an-2). This is more preferable, and anion represented by general formula (an-1) is especially preferable.

The specific example of a preferable (B1) component is given to the following.

[Formula 40]

(B1) component which a resist composition contains may be used individually by 1 type, and may use 2 or more types together.

As for the ratio of (B1) component in (B) component, 50 mass% or more is preferable with respect to the gross mass of (B) component, 75 mass% or more is more preferable, and 100 mass% may be sufficient as it. When the ratio of the component (B1) is equal to or greater than the lower limit of the above preferred range, foaming at high temperature baking is more suppressed. In addition, when forming a resist pattern, favorable sensitivity becomes easy to be maintained and lithographic characteristics (dimension uniformity etc.) improve.

In the resist composition of this embodiment, it is preferable that content of (B1) component is 1-40 mass parts with respect to 100 mass parts of (A) component, It is more preferable that it is 1.5-35 mass parts, It is 2-30 mass parts More preferred.

When content of (B1) component is more than the lower limit of the said preferable range, foaming at the time of high temperature baking is suppressed more. In addition, when forming a resist pattern, favorable sensitivity becomes easy to be maintained and lithographic characteristics (dimension uniformity etc.) improve. On the other hand, when it is below the upper limit of the said preferable range, when each component of a resist composition is melt | dissolved in the organic solvent, a uniform solution will be easy to be obtained, and storage stability as a resist composition will become higher.

About (B2) component

The resist composition of this embodiment may contain acid generator components other than (B1) component (henceforth "a component (B2)") in the range which does not impair the effect of this invention.

It does not specifically limit as (B2) component, What has been proposed as an acid generator for chemically amplified resist compositions can be used so far.

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; Nitrobenzyl sulfonate-type acid generators, iminosulfonate-type acid generators, disulfone-based generators, etc. are mentioned various types.

As an onium salt type acid generator, For example, the compound represented by the following general formula (b-1) (hereinafter also called "(b-1) component"), and the compound represented by general formula (b-2) (hereinafter " (b-2) component "or a compound represented by the general formula (b-3) (hereinafter also referred to as" component (b-3) ").

[Formula 41]

[In formula, R <^101> , R <^104> -R <^108> is respectively independently the cyclic group which may have a substituent, the linear alkyl group which may have a substituent, or the linear 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 divalent linking group containing a single bond or an oxygen atom. V ¹⁰¹ to V ¹⁰³ each independently represent a single bond, an alkylene group, or a fluorinated alkylene group. L ¹⁰¹ to L ¹⁰² each independently represent a single bond or an oxygen atom. L ¹⁰³ to L ¹⁰⁵ are each independently a single bond, -CO-, or -SO _2- . m is an integer of 1 or more, and M ' ^{m +} is m-valent onium cation.]

{No part}

The anion part of (b-1) component is the same as the anion represented by general formula (b1-a1) mentioned above.

The anion part of (b-2) component is the same as the anion represented by general formula (b1-a2) mentioned above.

The anion part of (b-3) component is the same as the anion represented by general formula (b1-a3) mentioned above.

{Cateonbu}

In said Formula (b-1), Formula (b-2), and Formula (b-3), M'm ⁺ represents m-valent onium cation (However, the cationic in the said general formula (b1) Except for cation corresponding to warmth). Among these, sulfonium cation and iodonium cation are preferable.

m is an integer of 1 or more.

As preferable cation part ((M'm ⁺ ) _{1 / m} ), the organic cation represented by the following general formula (ca-1)-(ca-4), respectively is mentioned.

[Formula 42]

[Wherein, R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² each independently represent an aryl group, alkyl group or alkenyl group which may have a substituent. R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ , and R ²¹¹ to R ²¹² may be bonded to each other to form a ring together with a sulfur atom in the formula. R ²⁰⁸ to R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ²¹⁰ is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a -SO ₂ -containing cyclic group which may have a substituent. L ²⁰¹ represents -C (= 0)-or -C (= 0) -O-. 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) valence group.]

Examples of the aryl group for R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² in the general formulas (ca-1) to (ca-4) include an unsubstituted aryl group having 6 to 20 carbon atoms, Phenyl group and naphthyl group are preferable.

As an alkyl group in R <^201> -R <^207> and R <^211> -R <^212> , a C1-C30 thing is preferable as a chain type or a cyclic alkyl group.

As an alkenyl group in R <^201> -R <^207> and R <^211> -R <^212> , it is preferable that carbon number is 2-10.

Examples of the substituent which R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and the above general formula (ca-r And groups represented by -1) to (ca-r-7), respectively.

In the above general formulas (ca-1) to (ca-4), 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 Hetero atom such as sulfur atom, oxygen atom, nitrogen atom, carbonyl group, -SO-, -SO _2- , -SO _3- , -COO-, -CONH- or -N (R _N )-(that R _N May be bonded via a functional group such as an alkyl group having 1 to 5 carbon atoms. As a ring formed, it is preferable that one ring which contains the sulfur atom in a formula in the ring skeleton is a 3-10 membered ring including a sulfur atom, and it is especially preferable that it is a 5-7 membered ring. As a specific example of the ring formed, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, 9H- thioxanthene ring, thioxanthone Ring, thianthrene ring, phenoxatiin ring, tetrahydrothiophenium ring, tetrahydrothiopyranium ring and the like.

R ²⁰⁸ to R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and in the case of being an alkyl group, may be bonded to each other to form a ring.

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

As an aryl group in R <^210> , a C6-C20 unsubstituted aryl group is mentioned, A phenyl group and a naphthyl group are preferable.

As an alkyl group in R <^210> , a C1-C30 thing is preferable as a linear or cyclic alkyl group.

As an alkenyl group in R <^210> , it is preferable that carbon number is 2-10.

-SO ₂ that is, may have a substituent in R ²¹⁰ - by-containing cyclic group "-SO ₂ - containing the cyclic group" is preferable, and more preferably groups represented by the above-mentioned formula (a5-r-1) Do.

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

Examples of the arylene group in Y ²⁰¹ include a group in which one hydrogen atom is removed from the aryl group exemplified as the aromatic hydrocarbon group in R ¹⁰¹ in formula (b1-a1) described above.

The alkylene group and alkenylene group for Y ²⁰¹ include groups excluding one hydrogen atom from the groups exemplified as the chain alkyl group and the chain alkenyl group in R ¹⁰¹ in the formula (b1-a1) described above. Can be.

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

W ²⁰¹ is (x + 1) which is a bivalent or trivalent coupling group.

As the divalent linking group for W ²⁰¹ , a divalent hydrocarbon group which may have a substituent is preferable, and the divalent hydrocarbon group which may have the same substituent as Ya ²¹ in General Formula (a2-1) described above will be exemplified. Can be. The divalent linking group for W ²⁰¹ may be any of linear, branched, and cyclic, and is preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of the 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 of hydrogen atom from the divalent linking group of 1 except in, in addition to the divalent linking group, and the like which combines the divalent connecting group. As the trivalent linking group for W ²⁰¹ , a group in which two carbonyl groups are bonded to an arylene group is preferable.

Specifically as a preferable cation represented by said formula (ca-1), the cation represented by the following general formula (ca-1-56)-(ca-1-71) is mentioned, respectively.

[Formula 43]

[Formula 44]

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

As a preferable cation represented by said formula (ca-2), a diphenyl iodonium cation, bis (4-tert- butylphenyl) iodonium cation, etc. are mentioned specifically ,.

Specifically as a preferable cation represented by said formula (ca-3), the cation shown by the following formula (ca-3-1)-(ca-3-6) is mentioned, respectively.

[Formula 45]

Specifically as a preferable cation represented by said formula (ca-4), the cation shown by the following formula (ca-4-1)-(ca-4-2) is mentioned, respectively.

[Formula 46]

Among the above-mentioned, the cation part ((M'm ⁺ ) _{1 / m} ) has the preferable cation represented by general formula (ca-1).

In the resist composition of this embodiment, (B2) component may be used individually by 1 type, and may use 2 or more types together.

When a resist composition contains (B2) component, less than 50 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (B2) component, in a resist composition, 1-20 mass parts is more preferable. , 1-10 parts by mass is more preferable.

Pattern formation is fully performed by making content of (B2) component into said preferable range. Moreover, when each component of a resist composition is melt | dissolved in the organic solvent, since a uniform solution is easy to be obtained and storage stability as a resist composition becomes favorable, it is preferable.

<(S) component>

In the resist composition of the present embodiment, as the organic solvent component (S) (component (S)), any component to be blended may be dissolved to form a uniform solution, and conventionally, a solvent of a chemically amplified resist composition. Arbitrary things can be suitably selected from a well-known thing, and can be used.

As (S) 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; Compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate; Derivatives of polyhydric alcohols such as compounds having ether bonds such as monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether and monobutyl ether or monophenyl ether of the above polyhydric alcohols or compounds having ester bonds [In these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are 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 methoxy propionate and ethyl ethoxypropionate; Anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phentol, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, isopropyl benzene, toluene, xylene, cymene, mesitylene Aromatic organic solvents, such as these; Dimethyl sulfoxide (DMSO) etc. are mentioned.

In the resist composition of this embodiment, (S) component may be used individually by 1 type, and may be used as 2 or more types of mixed solvents.

Among the above, as (S) component, PGMEA, PGME, (gamma) -butyrolactone, EL, and cyclohexanone are preferable.

Moreover, the mixed solvent which mixed PGMEA and a polar solvent is also preferable. The blending ratio (mass ratio) may be appropriately determined in consideration of the compatibility of PGMEA and the polar solvent, and the like, but is preferably in the range of 1: 9-9: 1, more preferably 2: 8-8: 2. desirable.

More specifically, when mix | blending EL or cyclohexanone as a polar solvent, the mass ratio of PGMEA: EL or cyclohexanone becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2 In addition, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2. Moreover, the mixed solvent of PGMEA, PGME, and cyclohexanone is also preferable.

Moreover, as (S) component, the mixed solvent of at least 1 sort (s) chosen from PGMEA and EL and (gamma) -butyrolactone other than that is also preferable. In this case, as a mixing ratio, the mass ratio of the former and the latter becomes like this. Preferably it is 70: 30-95: 5.

In the resist composition of this embodiment, (S) component is used so that solid content concentration in a resist composition may be 30 mass% or more. That is, solid content concentration in a resist composition is 30 mass% or more, Preferably it is 30-50 mass%, More preferably, it is 30-40 mass%.

If solid content concentration is more than the lower limit of the said range, it becomes easy to form a resist film of a thick film uniformly on a support body. On the other hand, if it is below the upper limit of the said preferable range, the viscosity of a resist composition can be aimed at and applicability | paintability to a support body, etc. will become high.

Moreover, it is preferable that the density | concentration of the said high molecular compound (A1) in the whole solid content in the resist composition of this embodiment is 90 mass% or more, It is more preferable that it is 90-99 mass%, It is 95-99 mass% More preferred.

If the density | concentration of (A1) component in the whole solid content is more than the lower limit of the said preferable range, a thick film resist film can be easily formed on a support body.

<Optional component>

The resist composition of this embodiment may further contain components (optional component) other than the above-mentioned (A) component, (B) component, and (S) component.

As such an optional component, the (D) component, (E) component, (F) component shown below, etc. are mentioned, for example.

`` (D) Component: Acid Diffusion Control Agent Component ''

(D) component acts as a quencher (acid diffusion control agent) which traps the acid generate | occur | produced by exposure in a resist composition.

As the component (D), for example, a photodegradable base (D1) (hereinafter referred to as "(D1) component") that decomposes upon exposure and loses acid diffusion controllability, does not correspond to the component (D1). Nitrogen-containing organic compound (D2) (henceforth "(D2) component") etc. are mentioned.

About (D1) component

By setting it as the resist composition containing (D1) component, when forming a resist pattern, the contrast of the exposed part and unexposed part of a resist film can be improved more.

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

The components (d1-1) to (d1-3) do not act as a quencher because they decompose in the exposed portion of the resist film and lose acid diffusion controllability (basic), respectively, and act as a quencher in the unexposed portion of the resist film.

[Formula 47]

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

{(d1-1) component}

Anonbu

In formula (d1-1), 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, and is each said Formula (b1-a1) The same thing as R <^{101> is} mentioned.

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 represented by General Formulas (a2-r-1) to (a2-r-7), respectively. , Ether bonds, ester bonds, or a combination thereof. When including an ether bond and an ester bond as a substituent, you may pass through the alkylene group, and as a substituent in this case, the coupling group represented by said formula (y-al-1)-(y-al-5), respectively is preferable. Do.

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

As said aliphatic cyclic group, it is more preferable to remove one or more hydrogen atoms from polycycloalkane, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

The chain alkyl group preferably has 1 to 10 carbon atoms, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and the like. Linear alkyl groups; 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methyl And branched alkyl groups such as pentyl group, 2-methylpentyl group, 3-methylpentyl group, and 4-methylpentyl group.

When the chain alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the carbon number of the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8 carbon atoms, and even 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 part or all of the hydrogen atoms constituting the linear alkyl group are substituted with fluorine atoms, and the fluorinated alkyl group in which all hydrogen atoms constituting the linear alkyl group are substituted with fluorine atoms ( It is especially preferable that it is a linear perfluoroalkyl group.

Below, the preferable specific example of the anion part of (d1-1) component is shown.

[Formula 48]

Cation Division

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

As organic cation of M ^{m +} , the thing similar to the cation represented by the said general formula (ca-1)-(ca-4), respectively is mentioned preferably, The cation represented by the said general formula (ca-1) is More preferably, the cations represented by the formulas (ca-1-1) to (ca-1-71) are more preferable.

(d1-1) A component may be used individually by 1 type, and may be used in combination of 2 or more type.

{(d1-2) component}

Anonbu

In formula (d1-2), 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, and said formula (b1-a1) The same thing as R <^{101> is} mentioned.

However, it is assumed that a fluorine atom is not bonded (not substituted with fluorine) to a carbon atom adjacent to the S atom in Rd ² . Thereby, the anion of the component (d1-2) becomes a suitable weak acid anion, and the quenching ability as the component (D) is improved.

Roneun Rd ^2, is preferably an aliphatic cyclic group which may have an alkyl group, or a substituent of the type chain which may have a substituent. As a linear alkyl group, it is preferable that it is C1-C10, and it is more preferable that it is 3-10. As an aliphatic cyclic group, group (you may have a substituent) remove | excluding one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclo dodecane, etc .; It is more preferable that it is group except one or more hydrogen atoms from camphor etc.

The hydrocarbon group of Rd ² may have a substituent and the substituent may have a hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in Rd ¹ of formula (d1-1). And the same thing as.

Below, the specific example of the anion part of a component (d1-2) is shown.

[Formula 49]

Cation Division

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

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

{(d1-3) component}

Anonbu

In the formula (d1-3) of, Rd ³ is an alkenyl group of chain which may have a cyclic, chain-like alkyl group which may have a substituent, or a substituent which may have a substituent group, the formula (b1-a1) The same thing as R <^101> is mentioned, It is preferable that it is a cyclic group containing a fluorine atom, a linear alkyl group, or a linear alkenyl group. Among them, a fluorinated alkyl group and more preferably the same as that of the fluorinated alkyl group Rd ^1.

Formula (d1-3) of, Rd ⁴ is cyclic group which may have a substituent, an alkyl group of chain-type which may have a substituent, or an alkenyl group of chain which may have a substituent group, the formula (b1-a1) The same thing as R <^{101> is} mentioned.

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

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

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

Alkenyl Rd in the ⁴ groups, there may be mentioned the same ones as R ¹⁰¹ in the formula (b1-a1), a vinyl group, a propenyl group (allyl group), 1-methyl propenyl group, 2-propenyl 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 in Rd ⁴ include the same as those described for R ¹⁰¹ in the formula (b1-a1), and include cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclo An alicyclic group except one or more hydrogen atoms from cycloalkanes such as dodecane or an aromatic group such as a phenyl group or a naphthyl group is preferable. In the case where Rd ⁴ is an alicyclic group, the resist composition is satisfactorily dissolved in the organic solvent, whereby the lithographic characteristics are improved. Also, Rd is ⁴ when an aromatic group, and that a resist composition excellent in light-absorbing efficiency, it is excellent in sensitivity and the lithographic properties.

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

Group connection divalent in Yd ¹ is not particularly limited, there may be mentioned a divalent hydrocarbon group which may have a substituent (the aliphatic hydrocarbon group, an aromatic hydrocarbon group), a divalent connecting group, such as containing a hetero atom. These are the same as the divalent linking group containing the divalent hydrocarbon group which may have a substituent, and the hetero atom illustrated in the description about the divalent linking group in Ya ^x1 in general formula (a10-1) mentioned above, respectively. Can be mentioned.

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 ethylene group.

Below, the preferable specific example of the anion part of (d1-3) component is shown.

[Formula 50]

[Formula 51]

Cation Division

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

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

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

When a resist composition contains (D1) component, 0.5-10 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (D1) component, in a resist composition, 0.5-8 mass parts is more preferable , 1-8 mass parts is more preferable.

If content of (D1) component is more than the lower limit of the said preferable range, especially favorable lithography characteristic and resist pattern shape will be easy to be obtained. On the other hand, if it is below the upper limit of the said preferable range, a sensitivity can be maintained favorable and throughput is also excellent.

About (D2) component

As an acid diffusion control agent component, you may contain the nitrogen-containing organic compound component (henceforth "(D2) component") which does not correspond to said (D1) component.

The component (D2) is not particularly limited as long as it acts as an acid diffusion control agent and does not correspond to the component (D1), and may be used arbitrarily from known ones. Especially, an aliphatic amine is preferable and especially a secondary aliphatic amine and tertiary aliphatic amine are more preferable.

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

Examples of the aliphatic amines include amines (alkylamines or alkylalcoholamines) or cyclic amines in which at least one hydrogen atom of ammonia NH ₃ is substituted with a C12 or less alkyl group or a hydroxyalkyl group.

Specific examples of the alkylamine and the alkyl alcohol amine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, 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 (triamylamine), tri-n-hexylamine, tri-n-heptylamine, tri-n Trialkylamines such as -octylamine, tri-n-nonylamine, tri-n-decylamine and tri-n-dodecylamine; Alkyl alcohol amines, such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine, are mentioned. Among these, trialkylamines having 5 to 10 carbon atoms are more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

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

Specific examples of the aliphatic monocyclic amines include piperidine and piperazine.

As the aliphatic polycyclic amine, one having 6 to 10 carbon atoms is preferable, and specifically 1,5-diazabicyclo [4.3.0] -5-nonene and 1,8-diazabicyclo [5.4.0] -7-undecene, hexamethylenetetramine, 1, 4- diazabicyclo [2.2.2] octane, etc. are mentioned.

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

Moreover, you may use an aromatic amine as (D2) component.

Examples of the aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, and the like. Can be mentioned.

As the component (D2), one type may be used alone, or two or more types may be used in combination.

When the resist composition contains the component (D2), the content of the component (D2) in the resist composition is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A). By making content of (D2) component into said preferable range, a resist pattern shape, time-lapse stability after exposure, etc. improve.

<< (E) component: At least 1 sort (s) of compound chosen from the group which consists of organic carboxylic acid, the oxo acid of phosphorus, and its derivative (s) >>

The resist composition of the present embodiment includes, as an optional component, an organic carboxylic acid, an oxo acid of phosphorus and a derivative thereof as an optional component for the purpose of preventing sensitivity deterioration, improving the resist pattern shape, stability after exposure and the like. At least 1 sort (s) of compound (E) (henceforth "(E) component") chosen 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 oxo acid of phosphorus, Among these, phosphonic acid is especially preferable.

As a derivative of the oxo acid of phosphorus, the ester etc. which substituted the hydrogen atom of the said oxo acid with a hydrocarbon group are mentioned, for example, As a hydrocarbon group, a C1-C5 alkyl group, a C6-C15 aryl group, etc. are mentioned, for example. Can be mentioned.

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

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

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

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

When a resist composition contains (E) component, it is preferable that content of (E) component is the range of 0.01-5 mass parts with respect to 100 mass parts of (A) component.

≪ (F) component: Fluorine additive component≫

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

As (F) 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, Japan Unexamined-Japanese-Patent The fluorine-containing polymer compound described in publication 2011-128226 can be used.

More specifically, as a component (F), the polymer which has a structural unit (f1) represented by following formula (f1-1) is mentioned. As said polymer, Polymer (homopolymer) which consists only of structural unit (f1) represented by following formula (f1-1); Copolymers 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 said structural unit (a1) copolymerized with the structural unit (f1), the structural unit derived from 1-ethyl-1- cyclooctyl (meth) acrylate, 1-methyl-1- adamantyl (meth) Preferred are structural units derived from acrylates.

[Formula 52]

[Wherein, R is the same as described 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; You may or may differ. nf ¹ is an integer of 1 to 5, and Rf ¹⁰¹ is an organic group containing a fluorine atom.]

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

In formula (f1-1), as a halogen atom of Rf ¹⁰² and Rf ¹⁰³ , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, Especially a fluorine atom is preferable. Examples of the alkyl group having 1 to 5 carbon atoms for Rf ¹⁰² and Rf ^{103 include} the same alkyl groups having 1 to 5 carbon atoms for R, and a methyl group or an ethyl group is preferable. A halogenated alkyl group having a carbon number of Rf 1 and Rf ^{102 103} 1-5, and specifically there may be a part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms, a halogen atom-substituted group. As this halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is especially preferable. In particular, the Rf and Rf ^{102 103} is a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms are preferred, and preferably a hydrogen atom, a fluorine atom, a methyl group or an ethyl group.

In formula (f1-1), nf ¹ is an integer of 1-5, the integer of 1-3 is preferable, and 1 or 2 is more preferable.

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

As a hydrocarbon group containing a fluorine atom, either linear, branched, or cyclic may be sufficient, it is preferable that carbon number is 1-20, it is more preferable that it is C1-C15, and C1-C10 is Particularly preferred.

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

Of these, Rf roneun ^101, more preferably a fluorinated hydrocarbon group having 1 to 6 carbon atoms, and a trifluoromethyl _{group, -CH 2 -CF 3, -CH 2} -CF 2 -CF 3, -CH (CF 3) 2, - Particular preference is given to CH ₂ -CH ₂ -CF ₃ , -CH ₂ -CH ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₃ .

As for the weight average molecular weight (Mw) (polystyrene conversion basis by gel permeation chromatography) of (F) component, 1000-50000 are preferable, 5000-40000 are more preferable, 10000-30000 are especially preferable. If Mw of (F) component is below the upper limit of the said preferable range, there exists sufficient solubility to the solvent for resist to use as a resist, and if it is more than the lower limit of the said preferable range, dry etching resistance and a resist pattern cross section The shape becomes better, and the water repellency of the resist film surface is well expressed.

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

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

When a resist composition contains (F) component, it is preferable that content of (F) component is 0.5-10 mass parts with respect to 100 mass parts of (A) component.

The resist composition of the present embodiment may further contain miscible additives such as additive resins, surfactants, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, and dyes, as desired, for improving the performance of the resist film. And the like can be appropriately added.

(Resist pattern formation method)

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

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

Process (i):

First, on the support body, the resist composition of the above-mentioned embodiment is apply | coated with a spinner etc., and baking (post application bake (PAB)) process is carried out for 40 to 120 second by the temperature conditions of 80-150 degreeC, for example. Preferably, it is carried out for 60 to 90 seconds to form a resist film.

Process (ii):

Next, the resist film is subjected to selective exposure by exposure through a mask (mask pattern) in which a predetermined pattern is formed, for example using an exposure apparatus such as a KrF exposure apparatus, and then baked (post exposure bake). (PEB)) The process is performed for 40 to 120 seconds, for example, 60 to 90 seconds on the temperature conditions of 80-150 degreeC, for example.

Process (iii):

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

After the development treatment, a rinse treatment is preferably performed. In the case of an alkali developing process, the 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 the solvent developing process, after the said developing process or the rinse process, you may perform the process which removes the developing solution or rinse liquid adhering on a pattern with a supercritical fluid.

After the development treatment or the rinse treatment, drying is performed. In some cases, a bake treatment (post bake) may be performed after the developing treatment. The baking process (post-baking) here is performed for 40 to 120 second, Preferably it is 60 to 90 second on 180 degreeC or more, Preferably it is 180-200 degreeC temperature conditions.

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 here, etc. are mentioned. More specifically, the board | substrate made from metals, such as a silicon wafer, copper, chromium, iron, aluminum, a glass substrate, etc. are mentioned. As a material of a wiring pattern, copper, aluminum, nickel, gold, etc. can be used, for example.

As the support, an inorganic and / or organic film may be formed on the substrate as described above. An inorganic antireflection film (inorganic BARC) is mentioned as an inorganic film. As an organic film | membrane, organic films, such as an organic antireflection film (organic BARC) and an underlayer organic film in a multilayer resist method, are mentioned.

Here, the multilayer resist method forms at least one layer of organic film (lower layer organic film) and at least one layer of resist film (upper layer resist film) on a substrate, using a resist pattern formed on the upper layer resist film as a mask. It is believed that a pattern having a high aspect ratio can be formed by a method of patterning the lower organic film. 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 pattern formation with a high aspect ratio becomes possible.

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

The resist pattern formation method of embodiment is a method useful when forming and performing a thick film resist film. Even if the film thickness of the resist film formed in the said process (i) is 1-10 micrometers, for example, in this range, even if it is 6 micrometers or more, Furthermore, 7 micrometers or more, especially 8 micrometers or more, a resist pattern Can be stably formed in a good shape.

Wavelength used for exposure is not particularly limited, ArF excimer laser light, KrF excimer laser light, F ₂ excimer laser light, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X This can be done using radiation such as a line.

The resist composition according to the first aspect described above has high usefulness for KrF excimer laser light, ArF excimer laser light, EB or EUV, higher usefulness for KrF excimer laser light, ArF excimer laser light, and for KrF excimer laser light. The usefulness as is especially high. The resist pattern formation method which concerns on a 2nd aspect is especially preferable at the time of irradiating KrF excimer laser light to the said resist film in the said process (ii).

The exposure method of a resist film may be normal exposure (dry exposure) performed in inert gas, such as air and nitrogen, or liquid immersion exposure (Liquid Immersion Lithography) may be sufficient.

Liquid immersion exposure is an exposure method which fills between the resist film and the lens of the lowest position of an exposure apparatus previously with the solvent (immersion medium) which has a refractive index larger than the refractive index of air, and performs exposure (immersion exposure) in that state.

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

As a solvent which has a refractive index larger than the refractive index of air and smaller than the refractive index of the said resist film, water, a fluorine-type inert liquid, a silicone type solvent, a hydrocarbon type solvent, etc. are mentioned, for example.

Specific examples of the fluorine-based inert liquid include liquids containing fluorine-based compounds such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , and C ₅ H ₃ F ₇ as main components. It is preferable that a boiling point is 70-180 degreeC, and it is more preferable that it is 80-160 degreeC. If the fluorine-based inert liquid has a boiling point in the above range, it is preferable from the fact that after the completion of the exposure, the medium used for the liquid immersion can be removed by a simple method.

Especially as a fluorine-type inert liquid, the perfluoroalkyl compound in which all the hydrogen atoms of the alkyl group were substituted by the fluorine atom is preferable. As a perfluoroalkyl compound, a perfluoroalkyl ether compound and a perfluoroalkylamine compound are mentioned specifically ,.

Specifically, as the perfluoroalkyl ether compound, perfluoro (2-butyl-tetrahydrofuran) (boiling point 102 ° C) may be mentioned, and as the perfluoroalkylamine compound, perfluoro Rotributylamine (boiling point 174 degreeC) is mentioned.

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

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

As an organic solvent which the organic developing solution used for image development processing in a solvent image development process contains, it should just be able to melt | dissolve component (A) (component (A) before exposure), and it can select suitably from well-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.

The ketone solvent is an organic solvent containing C-C (= 0) -C in its structure. An ester solvent is an organic solvent containing C-C (= O) -O-C in a structure. The alcohol solvent is an organic solvent containing an alcoholic hydroxyl group in the structure. "Alcoholic hydroxyl group" means the hydroxyl group couple | bonded with the carbon atom of an aliphatic hydrocarbon group. The nitrile solvent is an organic solvent containing a nitrile group in its structure. The amide solvent is an organic solvent containing an amide group in its structure. The ether solvent is an organic solvent containing C-O-C in its structure.

Among the organic solvents, there are also organic solvents containing plural kinds of functional groups that characterize the above-mentioned solvents in the structure, and in this case, it is assumed that they correspond to any solvent species containing the functional groups of the organic solvent. For example, diethylene glycol monomethyl ether shall correspond to all of the alcohol solvents and ether solvents in the said classification | combination.

The hydrocarbon solvent is a hydrocarbon solvent composed of a hydrocarbon which may be halogenated and does not have a substituent 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 an organic solvent which an organic developing solution contains, a polar solvent is preferable among the above, and a ketone solvent, an ester solvent, a nitrile solvent, etc. are preferable.

As a ketone solvent, For example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl Ketones, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, Isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone) and the like. Among these, as a 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, isoam acetate, methoxy acetate, ethyl ethoxy 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 Metok Cybutyl 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, propionate Ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3- Oxypropionate, propyl-3-methoxypropionate, and the like. Among these, butyl acetate is preferable as the ester solvent.

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

A well-known additive can be mix | blended with an organic developing solution as needed. As the additive, a surfactant is mentioned, for example. Although it does not specifically limit as surfactant, For example, ionic and nonionic fluorine type and / or silicone type surfactant etc. can be used. As surfactant, a nonionic surfactant is preferable and a nonionic fluorine-type surfactant or 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 of immersing the support in a developer for a certain time (dip method), a method of mounting the developer on the surface of the support by surface tension for a fixed time (paddle) Method), a method of spraying a developer onto the surface of the support (spray method), a method of continuously deriving the developer while scanning the developer extracting nozzle at a constant speed on a support rotated at a constant speed, and the like (dynamic dispensing method). .

As an organic solvent which the rinse liquid used for the rinsing process after image development processing in a solvent image development process contains, for example, the thing which does not dissolve a resist pattern well among the organic solvents illustrated as an organic solvent used for the said organic type developing solution, is appropriately selected. Can be used. Usually, at least 1 sort (s) of solvent chosen from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is used. Among these, at least one selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent is preferable, and at least one species selected from an alcohol solvent and an ester solvent is more preferable, and an alcohol solvent 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 1 type, and may use 2 or more types together. Moreover, you may mix and use with the organic solvent and water of that excepting the above. However, in consideration of the development characteristics, the blending amount of water in the rinse liquid is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, based on the total amount of the rinse liquid. Mass% or less is especially preferable.

A well-known additive can be mix | blended with a rinse liquid as needed. As the additive, a surfactant is mentioned, for example. The thing similar to the above is mentioned as surfactant, A nonionic surfactant is preferable, A nonionic fluorine-type 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 amount of a rinse liquid, 0.005-2 mass% is preferable, and its 0.01-0.5 mass% is more preferable.

The rinse treatment (cleaning treatment) using the rinse liquid can be performed by a known rinse method. As the method of the rinse treatment, for example, a method of continuously drawing a rinse liquid on a support rotating at a constant speed (rotary coating method), a method of immersing the support in a rinse liquid for a predetermined time (dip method), and a surface of the support The method of spraying a rinse liquid (spray method), etc. are mentioned.

The resist composition of this embodiment demonstrated above contains the high molecular compound (A1) which has a structural unit (a10) and a structural unit (a1), and the acid generator (B1) which has a cation part of a specific structure, and is in a resist composition Solid content concentration is 30 mass% or more.

And in the formation of the resist pattern using the resist composition which has these (A1) component and (B1) component together, and solid content concentration is 30 mass% or more, especially when forming by forming a thick film resist film, for example, a pattern The lithography characteristics are excellent, such as the uniformity of dimensions can be improved. Moreover, the applicability | paintability to a support body is also favorable and can form a resist film of uniform thickness easily. Moreover, foaming from the resist pattern at the time of the high temperature baking which was a problem conventionally is suppressed. Thus, according to the resist composition of this embodiment, the resist pattern of a thick film can be formed stably in a favorable shape.

Such a resist composition and a method of forming a resist pattern are useful for applications in which a thick film resist film is required, for example. In addition, such a resist composition and a resist pattern forming method are useful for processing a multi-stage staircase structure, and by applying the present invention, stacking of memory films (three-dimensionalization, production of large-capacity memories) can be realized with high accuracy. have.

Example

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

<Preparation of a resist composition>

(Example 1, Comparative Examples 1-4)

Each component shown in Table 1 was mixed and dissolved in the mixed solvent (propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 8/2 (mass ratio)), and the resist composition of each case was prepared, respectively. Solid content concentration in the resist composition of each example was shown in Table 1.

In Table 1, each symbol has the following meanings, respectively. The numerical values in [] are compounding quantities (mass part).

(A) -1: A high molecular compound represented by the following general formula (A1-1). The weight average molecular weight (Mw) of the standard polystyrene conversion calculated | required by GPC measurement is 10000, and molecular weight dispersion degree (Mw / Mn) is 1.8. ^The copolymerization composition ratio (proportion (molar ratio) of each structural unit in the structural formula) determined by ¹³ C-NMR was l / m / n = 60/20/20.

(A) -2: Polymer compound represented by chemical formula (A1-2) shown below. The weight average molecular weight (Mw) of the standard polystyrene conversion calculated | required by GPC measurement is 20000, and molecular weight dispersion degree (Mw / Mn) is 1.8. ^The copolymerization composition ratio (proportion (molar ratio) of each structural unit in the structural formula) determined by ¹³ C-NMR was l / m / n = 60/20/20.

[Formula 53]

(B1) -1: the compound represented by chemical formula (B1-1) shown below.

(B2) -1: the compound represented by chemical formula (B2-1) shown below.

(B2) -2: N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide.

[Formula 54]

(D) -1: triamylamine.

(E) -1: Phenylphosphonic acid.

<Formation of Resist Pattern>

Process (i):

Film thickness 65 by apply | coating organic type anti-reflective film composition "DUV-42P" (brand name, Brewer Science Co., Ltd.) using a spinner on an 8-inch silicon wafer, baking it on a hotplate for 60 second and drying for 60 second, and drying it An nm organic antireflection film was formed.

The resist composition of each example was apply | coated using the spinner on this organic type antireflection film, and it dried by performing a prebaking (PAB) process for 140 degreeC 90 second on a hotplate, and formed the resist film with a film thickness of 8 micrometers. It was.

In addition, when the resist composition of the comparative example 4 was used, since the resist film with a film thickness of 8 micrometers could not be formed, the operation after this was not performed.

Process (ii):

Subsequently, KrF excimer laser light (248 nm) was subjected to a mask pattern (6% half) by KrF exposure apparatus NSR-S205C (manufactured by Nikon Corporation; NA (number of openings) = 0.68, sigma = 0.60) with respect to the resist film. Tone) was selectively irradiated with the optimum exposure amount (Eop) of each resist composition.

Then, post-exposure heating (PEB) process was performed for 115 degreeC 90 second.

Process (iii):

Subsequently, alkali image development was performed on the conditions for 60 second at 23 degreeC using 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (brand name, Tokyo-Oka Industry Co., Ltd. product) as a developing solution.

Thereafter, water was rinsed for 30 seconds using pure water, followed by shaking off and drying.

As a result of the above-mentioned <formation of a resist pattern>, in all the examples (Example 1, Comparative Examples 1-3), the pattern of the space-and-line of a space width of 3.75 micrometers and a pitch width of 7.5 micrometers in the said resist film (following) The "SL pattern" was formed.

[Evaluation of Dimensional Uniformity (CDU) in Support Surface (Shot)]

About each obtained SL pattern, the SL pattern was observed from above by the SEM (scanning electron microscope, acceleration voltage 300V, brand name: S-9380, the Hitachi High-Technologies Corporation), and the space in the SL pattern was observed. The width (nm) was measured. Three arrangements (3σ) of the standard deviation (σ) calculated from the measurement result were calculated | required, and the dimensional uniformity (CDU) in support surface Shot was evaluated according to the following evaluation criteria. This evaluation result was shown in Table 2 as "CDU."

Evaluation standard

(Double-circle): 3σ is 15 nm or less.

(Circle): 3σ is more than 15 nm and 20 nm or less.

X: 3σ is over 20 nm.

The smaller the value of 3σ obtained in this way, the higher the dimension (CD) uniformity of the space width formed in the resist film.

[Evaluation of Film Thickness Uniformity in Support Surface (Shot)]

In the above-mentioned [Evaluation of Dimensional Uniformity (CDU) in Support Surface (Shot)], each of the resist compositions of Example 1, Comparative Example 1, and Comparative Example 3, in which the results were satisfactory, the formation of the above <resist pattern was formed. The film thickness uniformity of the resist film with a film thickness of 8 micrometers after the prebaking (PAB) process in> (i) of> was evaluated as follows.

The film thickness of the resist film at ten points (equal intervals) between both ends of the diameter of the silicon wafer was measured using Nanospec 7001-0066XPW (product name, manufactured by Nanometrics Japan) and evaluated as follows. According to the criteria, the film thickness uniformity in the support surface Shot was evaluated. This evaluation result was shown in Table 2 as "film thickness uniformity."

Evaluation standard

(Circle): Film thickness uniformity is high (when the difference of the film thickness in Shot is ± 25 nm or less).

X: film thickness uniformity is low (when the difference of the film thickness in Shot exceeds +/- 25 nm).

[Evaluation of the presence of foaming]

In the above-mentioned [evaluation of film thickness uniformity], for each resist composition of Example 1 and Comparative Example 1, which had good results, the steps (i) and (ii) in the above <formation of resist pattern> and After (iii), that is, after being shaken and dried, further heating (post bake) was performed at 180 ° C. for 60 seconds, and the presence or absence of foaming from the resist pattern at that time was visually evaluated. This result was shown in Table 2 as "the presence or absence of foaming."

From the results shown in Table 2, when the resist pattern was formed using the resist composition of Example 1 to which the present invention was applied, the lithography characteristics were excellent, the coating property was good, and the foaming from the resist pattern at the time of high temperature baking was It can confirm that it is suppressed.

Claims (6)

As a resist composition which generate | occur | produces an acid by exposure and changes solubility to a developing solution by the action of an acid,
Polymer compound (A1) which has a structural unit (a1) containing the structural unit (a10) represented by the following general formula (a10-1), and an acid-decomposable group whose polarity increases by the action of an acid, and following general formula (b1) It contains the acid generator (B1) represented by
The resist composition whose solid content concentration in a resist composition is 30 mass% or more.

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ya ^x1 is a single bond or a divalent linking group. Wa ^x1 is a (n _ax1 +1) valent aromatic hydrocarbon group. n _ax1 is an integer of 1-3. R ²⁰¹¹ , R ²⁰²¹ and R ²⁰³¹ each independently represent an aryl group which may have a substituent. Two or more of R ²⁰¹¹ , R ^2021, and R ²⁰³¹ may be bonded to each other to form a ring together with a sulfur atom in the formula. X ^- represents a counter anion.] The method of claim 1,
At least one of R ²⁰¹¹ , R ^2021, and R ²⁰³¹ in the general formula (b1) is an aryl group having a substituent,
The substituent is selected from the group consisting of alkyl groups, halogen atoms, halogenated alkyl groups, carbonyl groups, cyano groups, amino groups, aryl groups, and groups represented by general formulas (ca-r-1) to (ca-r-7) shown below. At least one resist composition.

[In formula, ^R'201 is respectively independently a hydrogen atom, the cyclic group which may have a substituent, the chain alkyl group which may have a substituent, or the chain alkenyl group which may have a substituent.] The method of claim 1,
The resist composition in which the density | concentration of the said high molecular compound (A1) in the whole solid content in a resist composition is 90 mass% or more. The method of claim 1,
The weight average molecular weight of the said high molecular compound (A1) is 5000-20000, The resist composition. Process (i) of forming a resist film using the resist composition of any one of Claims 1-4 on the support body, process (ii) of exposing the said resist film, and developing the resist film after exposure, and developing a resist The resist pattern formation method which has a process (iii) of forming a pattern. The method of claim 5,
In the step (ii), the resist pattern is formed by irradiating KrF excimer laser light on the resist film.