KR20130001138A - Resist composition and method of forming resist pattern - Google Patents

Abstract

PURPOSE: A resist composition and a method for forming a resist pattern are provided to suppress size change according to the influence of the passage of time. CONSTITUTION: A resist composition contains a compound(G) having a monovalent group represented chemical formula g1 or chemical formula g2, and a compound(H) having a monovalent group represented by chemical formula h1 or chemical formula h2. In the chemical formula g1, R2 is a single bond or - C (=O) -O-. However, if R2 is a single bond, the bondage between N^- and -C(=O)- is not included in the (G) component. M^+ is respectively organic cation.

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 method of forming a resist pattern.

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 in which the exposed portion of the resist film is changed to the characteristic in which the exposed portion is dissolved in the developing solution is positive, and the resist material in which the exposed portion is changed in the characteristic that is not dissolved in the developing solution is called negative.

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.

In general, as a method for miniaturization, short wavelength (high energy) of an exposure light source has been achieved. Specifically, ultraviolet rays typified by g-line and i-line have conventionally been used, but mass production of semiconductor devices using KrF excimer lasers and ArF excimer lasers is now disclosed. Moreover, examination is also made about EUV (ultra-ultraviolet), EB (electron beam), X-rays, etc. which are shorter wavelength (high energy) than these excimer laser.

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

As a resist material that satisfies such a requirement, a chemically amplified resist composition containing an acid generator component which generates an acid upon exposure and a base component whose solubility in a developer is changed by the action of an acid has been used. .

Resin (base resin) is generally used as a base material component used in a chemically amplified resist composition.

For example, as a chemically amplified resist composition for forming a positive resist pattern in an alkali developing process using an alkaline developer as a developer, solubility in an alkaline developer is increased by the action of an acid generator component and an acid. It is generally used to contain the resin component. 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 from an acid generator component in an exposure part, and the solubility of the resin component with respect to the alkaline developing solution by the action of the acid will be. This increases and the exposure part becomes soluble to the alkaline developer. Therefore, by alkali development, the positive pattern in which an unexposed part remains as a pattern is formed.

In general, as the resin component, one in which the polarity of the resin is increased by the action of an acid is used. When the polarity is increased, the solubility in the alkaline developer is increased while the solubility in the organic solvent is decreased. Therefore, if the solvent developing process using the developing solution (organic developing solution) containing the organic solvent instead of the alkaline developing process is applied, since the solubility with respect to an organic developing solution will fall comparatively in the exposure part, in the solvent developing process, 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 remains as a pattern is formed. Thus, the solvent developing process which forms a negative resist pattern may be called a negative developing process (for example, refer patent document 1).

Currently, as a base resin of a chemically amplified resist composition used in ArF excimer laser lithography or the like, the resin having a structural unit derived from (meth) acrylic acid ester in the main chain in terms of excellent transparency at around 193 nm ( Acrylic resin) etc. are generally used (for example, refer patent document 2).

The base resin has a plurality of structural units in order to improve lithography characteristics and the like. For example, in the case of a resin component in which the polarity of the resin is increased by the action of the acid, the resin component usually has a structural unit having an acid-decomposable group which is decomposed by the action of an acid generated from the acid generator component to increase the polarity. And those having a structural unit having a polar group such as a hydroxyl group, a structural unit having a lactone structure, and the like are used.

Here, "(meth) acrylic acid ester" means the one or both of the acrylate 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.

As the acid generator used in the chemically amplified resist composition, various kinds have been proposed so far, for example, onium salt-based acid generators, oxime sulfonate-based acid generators, diazomethane-based acid generators, nitro Benzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators and the like are known.

Moreover, as a resist material, resin which has a structural unit which has an acid-decomposable group, and General formula (i): R ¹⁰¹ -R ¹⁰² -N ^-- S (= O) ₂ -R ¹⁰³ Z ⁺ [wherein, R ¹⁰¹ Is a hydrogen atom, a part or all of the hydrogen atoms are fluorine atoms, hydroxyl groups, -OR ¹⁰⁰ groups, -OCOR ¹⁰⁰ groups, or -COOR ¹⁰⁰ groups (wherein R ¹⁰⁰ is a linear or branched C1-C10 group; C1-10 linear or branched monovalent hydrocarbon group, which may be substituted with a monovalent hydrocarbon group having 1 to 10 carbon atoms or a cyclic or cyclic partial structure having 3 to 20 carbon atoms. Or a monovalent hydrocarbon group having a cyclic or cyclic substructure having 3 to 20 carbon atoms, R ¹⁰² represents a single bond or a -O- (C = O)-group, and R ¹⁰³ represents a part or all of the hydrogen atoms C1-C10 linear or branched monovalent hydrocarbons which may be substituted with fluorine atoms Sense containing (hereinafter referred to as "compound (i)") group, or represents a monovalent hydrocarbon group having a ring or part of a cyclic structure with a carbon number of 3 ~ 20, Z ⁺ represents an onium cation; a compound represented by The radiation resin composition is disclosed (refer patent document 3).

Compound (i) in the unexposed portion of the resist film performs an ion exchange reaction with an acid generated from an acid generator or the like to suppress the diffusion phenomenon of acid, and compound (i) in the exposed portion, By decomposition, the basicity with respect to the acid generated from an acid generator or the like is lost. Thereby, according to the radiation sensitive resin composition of patent document 3, it is thought that the improvement of a lithography characteristic, a resist pattern shape, etc. can be aimed at.

Japanese Unexamined Patent Publication No. 2008-292975 Japanese Patent Application Laid-Open No. 2003-241385 International Publication No. 2010/147079 Pamphlet

However, in the radiation sensitive resin composition of patent document 3, when the said resin composition is prepared and preserve | saved for a fixed period, there exists a problem that the dimension of the resist pattern formed before and after storage differs.

On the other hand, the miniaturization of the resist pattern is further progressed, and the resist material is required to have a good lithography characteristic and a resist pattern shape so far.

This invention is made | formed in view of the said situation, Comprising: It is an object to provide the resist composition and the resist pattern formation method which are excellent in the lithographic characteristic and the resist pattern shape, while suppressing the dimensional fluctuation by the influence of time.

In order to solve the above problems, the present invention employs the following configuration.

That is, the 1st aspect of this invention is a compound (G) which has monovalent group represented by the following general formula (g1) or monovalent group represented by general formula (g2), and monovalent group represented by the following general formula (h1). Or compound (H) which has monovalent group represented by general formula (h2) is contained, It is a resist composition characterized by the above-mentioned.

[Formula 1]

[In formula (g1), R <^2> is a single bond or -C (= O) -O- group. However, when R <^2> is a single bond, what N <^-> in a formula couple | bonds with -C (= O)-group shall not be included in (G) component. R ³ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group which has a partial structure. M ⁺ is each independently an organic cation]

[Formula 2]

[In formula (h1), R <^6> is a single bond or -C (= O) -O- group. R ⁷ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. Monovalent hydrocarbon group having a partial structure]

A second aspect of the present invention includes a step of forming a resist film on the support using the resist composition of the first aspect, a step of exposing the resist film, and a step of developing the resist film to form a resist pattern. It is a resist pattern formation method.

In this specification and a claim, "exposure" is taken as the concept containing the irradiation of radiation in general.

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

An "aliphatic" is a relative concept with respect to aromatic, and is defined as meaning a group, a compound, etc. which do not have aromaticity.

"Alkyl group" shall contain a linear, branched, and cyclic monovalent saturated hydrocarbon group unless otherwise specified.

"Alkylene group" shall contain a bivalent, saturated, cyclic, divalent hydrocarbon group unless otherwise indicated. The alkyl group in the alkoxy group is also the same.

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 the "halogenated alkylene group" is a group in which part or all of the hydrogen atoms of the alkylene group are replaced by halogen atoms, and as the halogen atom, fluorine Atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

The "fluorinated alkyl group" is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and the "fluorinated alkylene group" is a group in which part or all of the hydrogen atoms of the alkylene group are replaced by fluorine atoms.

According to the present invention, it is possible to provide a resist composition and a method of forming a resist pattern excellent in lithography properties and resist pattern shape while suppressing dimensional fluctuations due to the influence of time.

&Quot; Resist composition &

The resist composition of the present invention comprises a compound (G) having a monovalent group represented by the general formula (g1) or a monovalent group represented by the general formula (g2) (hereinafter also referred to as "(G) component"), and the general formula ( The compound (H) (henceforth "(H) component") which has a monovalent group represented by h1) or a monovalent group represented by general formula (h2) is contained.

(G) component and (H) component in this invention can be used as a base material component, or as an additive mix | blended with a base material component, respectively.

As used herein, the "base component" is an organic compound having a film-forming ability, which is a main component constituting the resist film, and preferably an organic compound having a molecular weight of 500 or more. When the molecular weight of this organic compound is 500 or more, film forming ability improves and it is easy to form a resist pattern of a nano level.

Organic compounds used as base components are roughly divided into nonpolymers and polymers.

As a nonpolymer, the thing of molecular weight 500-4000 is normally used. In this specification, when it says "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. In this specification and a claim, when it says "resin", the polymer whose molecular weight is 1000 or more is shown. As a molecular weight of a polymer, the mass average molecular weight of polystyrene conversion by GPC (gel permeation chromatography) shall be used.

When using (G) component and (H) component as an additive mix | blended with a base material component, as a resist composition of this invention, in addition to (G) component and (H) component, it adds to a developing solution by the action of an acid. It contains the base component (A) (hereinafter also referred to as "(A) component") to which the solubility changes, and the acid generator component (B) (henceforth "(B) component") which generate | occur | produces an acid by exposure. (Hereinafter, this resist composition is called "1st Embodiment.").

When using one or both of (G) component and (H) component as a base material component ((A) component), As the resist composition of this invention, (G) component as a base material component ((A) component), (H) component as an additive, and (B) component containing (hereinafter this resist composition is called "2nd Embodiment"); (H) component as base component ((A) component), and as an additive ( Containing G) component and (B) component (hereinafter, this resist composition is called "third embodiment"); (G) component as base component ((A) component) and base component ((A) (H) component as a component) and what contains (B) component (Hereinafter, this resist composition is called "fourth embodiment") are mentioned.

When resist films are formed using the resist compositions of the first to fourth embodiments, and selective exposure is performed on the resist films, an acid is generated from the component (B) in the exposed portion, and the action of the acid ( While the solubility of the component A) in the developer is changed, while the solubility of the component (A) in the developer is not changed, a difference in solubility in the developer is caused between the exposed portion and the unexposed portion. Therefore, when the resist film is developed, when the resist composition is positive, the exposed portion is dissolved and removed to form a positive resist pattern. When the resist composition is negative, the unexposed portion is dissolved and removed to form a negative resist pattern. Is formed.

In that case, the (G) component in the unexposed part of a resist film performs the ion exchange reaction with the acid generate | occur | produced from (B) component, and shows the effect | action which suppresses the diffusion phenomenon of an acid, and (G) in an exposure part The component is decomposed by exposure, thereby losing basicity to the acid generated from the component (B). Thereby, lithographic characteristics, a resist pattern shape, etc. can be improved.

(H) component mainly contributes to the improvement of the storage stability over time of a resist composition.

The resist composition of this invention is not limited to the 1st-4th embodiment mentioned above,

A copolymer having a structural unit derived from the component (G) and a structural unit derived from the component (H) as the base component (component (A)), and containing the component (B) (hereinafter resist) The composition is referred to as a "fifth embodiment"; containing the component (G) as an additive, the component (H) as an additive, and the component (A) capable of generating an acid by exposure (hereinafter referred to as a resist composition "6th Embodiment", etc. are mentioned.

In this specification, the resist composition which melt | dissolves and removes an exposure part and forms a positive resist pattern is called a positive resist composition, and the resist composition which forms a negative resist pattern in which an unexposed part is dissolved and removed is called a negative resist composition.

The resist composition of the present invention may be a positive resist composition or a negative resist composition. Moreover, the resist composition of this invention may be for the alkali developing process which uses an alkaline developing solution for the developing process at the time of resist pattern formation, or for the solvent developing process which uses the developing solution (organic developing solution) containing an organic solvent for this developing process. do.

When the resist composition of this invention is a resist composition which forms a negative resist pattern in an alkali developing process (or forms a positive resist pattern in a solvent developing process), As (A) component, Preferably it is alkali A soluble base component (hereinafter referred to as an "alkali soluble base component") is used in the developer, and a crosslinking agent component is further blended. As an alkali-soluble base material component, resin (alkali-soluble resin) is used normally.

Alkali-soluble base material components have alkali-soluble groups, such as a hydroxyl group, a carboxyl group, and an amino group, normally, As a crosslinking agent component, it has a reactive group which can react with the alkali-soluble group by action of an acid, such as a methylol group and an alkoxy methyl group. Is used. Therefore, when a resist film is formed using such a resist composition, and selective exposure is performed to the resist film, an acid is generated in the exposed portion, for example, from component (B), and the alkali-soluble base component is caused by the action of the acid. Crosslinking occurs between the crosslinking agent component and the crosslinking agent component, resulting in a decrease in the alkali-soluble group of the alkali-soluble substrate component, a decrease in the polarity thereof, an increase in the molecular weight, and the like, and as a result, the solubility in the alkaline developer is decreased. Solubility is increased). Therefore, in forming a resist pattern, when the resist film obtained by apply | coating the said resist composition on a support body is selectively exposed, an exposure part will change to poor solubility (soluble to an organic developing solution) with respect to an alkaline developing solution, while an unexposed part is alkali Since it does not change while being soluble (hardly soluble to organic developer) with respect to the developer, the negative resist pattern can be formed by developing with an alkaline developer. In this case, when the organic developer is used as the developer, a positive resist pattern can be formed.

As a crosslinking agent component, for example, when an amino crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group, a melamine crosslinking agent or the like is used, a good resist pattern with less swelling can be formed, which is preferable. It is preferable that the compounding quantity of a crosslinking agent component is 1-50 mass parts with respect to 100 mass parts of alkali-soluble resin.

In addition, when an alkali-soluble base material component has self-crosslinking property (for example, when an alkali-soluble base material component has group which can react with an alkali-soluble group by the action of an acid), a crosslinking agent component does not necessarily need to be mix | blended.

When the resist composition of the present invention is a resist composition which forms a positive resist pattern in an alkali developing process and forms a negative resist pattern in a solvent developing process, as the component (A), preferably, the action of an acid The base component (henceforth "(A0) component") whose polarity increases by using is used. Since the polarity of the (A0) component changes before and after exposure, by using the (A0) component, 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 (A0) is poorly soluble to the alkaline developer before exposure, and when acid is generated from the component (B) by exposure, for example, the polarity is increased by the action of the acid. Solubility in an alkaline developer increases. 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 exposed portion is changed from poorly soluble to soluble to the alkaline developer, while the unexposed portion is alkali poorly soluble. Since it does not remain unchanged, a positive resist pattern can be formed by alkali development. On the other hand, in the case of applying the solvent developing process, the component (A0) has high solubility with respect to the organic developer before exposure, and when an acid is generated from the component (B) by exposure, for example, the polarity becomes high due to the action of the acid, resulting in an organic system. Solubility in the developer is reduced. Therefore, in forming the resist pattern, when the resist composition is selectively exposed to the resist film obtained by applying the resist composition on the support, the exposed portion is changed from soluble to poorly soluble to the organic developer, while the unexposed portion remains soluble. Since it does not change, by developing with an organic developer, contrast can be formed between the exposed portion and the unexposed portion, and a negative resist pattern can be formed.

<(G) component>

(G) A component is a compound which has monovalent group represented by the following general formula (g1), or monovalent group represented by general formula (g2).

(3)

[In formula (g1), R <^2> is a single bond or -C (= O) -O- group. However, when R <^2> is a single bond, what N <^-> in a formula couple | bonds with -C (= O)-group shall not be included in (G) component. R ³ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group which has a partial structure. M ⁺ is each independently an organic cation]

In said formula (g1), R <^2> is a single bond or -C (= O) -O- group, and it is preferable that it is a single bond. However, when R <^2> is a single bond, (G) component does not include that which N <^-> in the formula couple | bonds with -C (= O)-group (having -N ^-- C (= O)-group). Do not.

With respect to a linear or branched monovalent hydrocarbon group in R ³ , carbon number is 1 to 10, 1 to 5 are preferable, and 1 to 3 are more preferable. Examples of the linear or branched monovalent hydrocarbon group for R ³ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group and tert -Butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. are mentioned.

With respect to the cyclic monovalent hydrocarbon group in R ³ , carbon number is 3-20, and it is preferable that it is 3-12. Examples of the cyclic monovalent hydrocarbon group for R ³ include a group obtained by removing one or more hydrogen atoms from a monocycloalkane; one or more hydrogen atoms from polycycloalkanes such as bicycloalkane, tricycloalkane, and tetracycloalkane. And the like from which the product was removed. Specifically, group which removed 1 or more hydrogen atoms from monocycloalkane, such as cyclopentane, cyclohexane, cyclooctane; Poly, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclo dodecane The group etc. which removed 1 or more hydrogen atoms from cycloalkane are mentioned.

As the monovalent hydrocarbon group having a cyclic partial structure in R ³ , a group in which a cyclic hydrocarbon is bonded to a terminal of a linear or branched hydrocarbon group, or a cyclic hydrocarbon is linear or branched. The group etc. which are interposed in the middle of a linear hydrocarbon group are mentioned. The cyclic partial structure has 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, in which one or more hydrogen atoms are removed from the monocycloalkane described above, and one or more hydrogen atoms are removed from the polycycloalkane. And the like can be mentioned.

The linear or branched monovalent hydrocarbon group, the cyclic monovalent hydrocarbon group, or the monovalent hydrocarbon group having a cyclic partial structure in R ³ may each be part of a hydrogen atom in the hydrocarbon group or All may or may not be substituted by the fluorine atom. Moreover, you may substitute by substituents other than a fluorine atom, As a substituent, a C1-C5 alkyl group, a C1-C5 fluorinated alkyl group, an oxygen atom (= O), etc. are mentioned.

In said formula (g1), (g2), M <^+> is organic cation each independently.

The organic cation of M ⁺ is not particularly limited, and among them, an organic cation known as a cation portion of the onium salt-based acid generator blended in a conventional resist composition may be mentioned as a preferable one.

As such cation moiety, sulfonium ions or iodonium ions are preferable, and sulfonium ions are particularly preferable.

As an organic cation of M <^+>, the organic cation represented by the following general formula (g-c1) or general formula (g-c2) is mentioned.

[Formula 4]

[In formula (g-c1), R < ^{1 >} -R < ^{3 >} represents the aryl group, alkyl group, or alkenyl group which may respectively independently have a substituent. Any two of R ^{1 "} to R ^{3 " may} be bonded to each other to form a ring together with a sulfur atom in the formula. In formula (g-c2), each of R ^{5 "} to R ^{6 "} independently represents an aryl group, alkyl group or alkenyl group which may have a substituent]

In said formula (g-c1), R < ^{1 >} -R < ^{3 >} represents the aryl group, alkyl group, or alkenyl group which may respectively independently have a substituent. Any two of R ^{1 "} to R ^{3 " may} be bonded to each other to form a ring together with a sulfur atom in the formula.

Moreover, since a lithographic characteristic and a resist pattern shape improve more, it is preferable that at least 1 is an aryl group among R < ^{1 >} -R < ^{3 >} , and it is preferable that 2 or more of R < ^{1 >} -R < ^{3 >} is an aryl group. More preferably, it is especially preferable that all of R < ^{1 >} -R <^3> are an aryl group.

As an aryl group of R < ^{1 >} -R <^3> , a C6-C20 unsubstituted aryl group; one part or all part of the hydrogen atom of the unsubstituted aryl group is an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, an oxo group (= O ), Aryl group, alkoxyalkyloxy group, alkoxycarbonylalkyloxy group, substituted aryl group substituted with -C (= O) -OR ^{6 '} , -OC (= O) -R ^{7 '} , -OR ^{8 '} Etc. can be mentioned. R ^{6 ＇} , R ^{7 ＇} and R ^{8 ＇} each represent a linear, branched or cyclic saturated hydrocarbon group having 1 to 25 carbon atoms, or a linear hydrocarbon having 2 to 5 carbon atoms. Or a branched aliphatic unsaturated hydrocarbon group.

In R < ^{1 >} -R < ^{3 >} , as an unsubstituted aryl group, a C6-C10 aryl group is preferable at the point which can be synthesize | combined cheaply. Specific examples thereof include a phenyl group and a naphthyl group.

As an alkyl group as a substituent in the substituted aryl group of R < ^{1 >} -R <^3> , 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 as a substituent in a substituted aryl group, a C1-C5 alkoxy group is preferable, and it is a methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, and tert-butoxy group. Most preferred.

As a halogen atom as a substituent in a substituted aryl group, a fluorine atom is preferable.

As an aryl group as a substituent in a substituted aryl group, the same thing as the said aryl group of R < ^{1 >} -R <^3> is mentioned, A C6-C20 aryl group is preferable, A C6-C10 aryl group is more preferable, A phenyl group , Naphthyl group is more preferable.

As an alkoxyalkyloxy group in a substituted aryl group, it is, for example,

General formula: -OC (R ⁴⁷ ) (R ⁴⁸ ) -OR ⁴⁹

In the formula, groups represented by R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom or a linear or branched alkyl group, and R ⁴⁹ is an alkyl group.

In R ⁴⁷ and R ⁴⁸ , the number of carbon atoms of the alkyl group is preferably 1 to 5, which may be either a linear or branched chain, preferably an ethyl group or a methyl group, and most preferably a methyl group.

It is preferable that at least one of R ⁴⁷ and R ⁴⁸ be a hydrogen atom. In particular, it is more preferable that one is a hydrogen atom and the other is a hydrogen atom or a methyl group.

As an alkyl group of R <^49> , Preferably, it is C1-C15, Any of a linear type, a branched chain type, and a cyclic type may be sufficient.

As a linear and branched alkyl group in R <^49> , it is preferable that carbon number is 1-5, For example, a methyl group, an ethyl group, a propyl group, n-butyl group, tert- butyl group etc. are mentioned. have.

The cyclic alkyl group for R ⁴⁹ is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, one or more hydrogens from polycycloalkanes such as monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, etc. which may or may not be substituted with an alkyl group, a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms The group which removed the atom etc. are mentioned. Cyclopentane, cyclohexane, etc. are mentioned as monocycloalkane. Examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like. Especially, the group remove | excluding one or more hydrogen atoms from adamantane is preferable.

As an alkoxycarbonylalkyloxy group in a substituted aryl group, it is, for example,

General formula: -OR ⁵⁵ -C (= O) -OR ⁵⁶

In the formula, a group represented by R ⁵⁵ is a linear or branched alkylene group and R ⁵⁶ is a tertiary alkyl group.

As a linear and branched alkylene group in R <^55> , it is preferable that carbon number is 1-5, For example, a methylene group, ethylene group, trimethylene group, tetramethylene group, 1,1- A dimethyl ethylene group etc. are mentioned.

As the tertiary alkyl group for R ⁵⁶ , 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclophene Tyl group, 1-methyl-1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, 1- (1-adamantyl) -1-methylethyl group, 1- (1-adamantyl) -1-methyl Propyl group, 1- (1-adamantyl) -1-methylbutyl group, 1- (1-adamantyl) -1-methylpentyl group; 1- (1-cyclopentyl) -1-methylethyl group, 1 -(1-cyclopentyl) -1-methylpropyl group, 1- (1-cyclopentyl) -1-methylbutyl group, 1- (1-cyclopentyl) -1-methylpentyl group; 1- (1-cyclo Hexyl) -1-methylethyl group, 1- (1-cyclohexyl) -1-methylpropyl group, 1- (1-cyclohexyl) -1-methylbutyl group, 1- (1-cyclohexyl) -1-methyl Pentyl group, tert-butyl group, tert-pentyl group, tert-hexyl group, etc. are mentioned.

In addition, the formula: the R ⁵⁶ in ^{-OR 55 -C (= O) -OR} 56, can be given a prayer substituted with R ^{56 '.} R ^{56 '} is an aliphatic cyclic group which may contain a hydrogen atom, an alkyl group, a fluorinated alkyl group, or a hetero atom.

The alkyl group in R <^{56> 'B} is the same as the alkyl group of said R <^49> . Examples of the fluorinated alkyl group in R ^{56 ′} include a group in which part or all of the hydrogen atoms in the alkyl group of R ⁴⁹ are substituted with fluorine atoms.

Examples of the aliphatic cyclic group which may contain a hetero atom in R ^{56 ′} include an aliphatic cyclic group not containing a hetero atom, an aliphatic cyclic group containing a hetero atom in a ring structure, and a hydrogen atom in the aliphatic cyclic group as a hetero atom. Substituted thing etc. are mentioned.

With respect to R ^{56 ',} in the aliphatic cyclic group does not contain a heteroatom, mono cycloalkane, bicyclo alkane, tricyclo alkane, tetracyclo alkane such as poly-cycloalkyl group removing one or more hydrogen atoms from an alkane, such as Can be. Cyclopentane, cyclohexane, etc. are mentioned as monocycloalkane. Examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like. Especially, the group remove | excluding one or more hydrogen atoms from adamantane is preferable.

As an aliphatic cyclic group containing a hetero atom in a ring structure with respect to R ^{56 '} , specifically, the formulas (L1) to (L6), (S1) to (S4) exemplified in the description of component (B) described later. The group represented by) is mentioned.

With respect to R ^{56 ',} as being a hydrogen atom it is substituted with a hetero atom in the aliphatic cyclic group and specifically there may be such that the substituted hydrogen atom is an oxygen atom (= O) of the aliphatic cyclic group.

^{-C (= O) -OR 6 '} , -OC (= O) -R 7', -OR 8, R 7 ', R 8''R 6 ^in', respectively, non-woven having a carbon number of 1 to 25 It is a linear, branched or C3-C20 cyclic saturated hydrocarbon group, or a C2-C5 linear or branched aliphatic unsaturated hydrocarbon group.

The linear or branched saturated hydrocarbon group has 1 to 25 carbon atoms, preferably 1 to 15 carbon atoms, and more preferably 4 to 10 carbon atoms.

Examples of the linear saturated hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group.

As the branched saturated hydrocarbon group, except for the tertiary alkyl group, 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.

The linear or branched saturated hydrocarbon group may have a substituent. As this substituent, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (= O), a cyano group, a carboxyl group etc. are mentioned, for example.

As an alkoxy group as a substituent of the said linear or branched saturated hydrocarbon group, a C1-C5 alkoxy group is preferable, and a methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy Timing and tert-butoxy group are preferable, and a methoxy group and an ethoxy group are the most preferable.

As a halogen atom as a substituent of the said linear or branched saturated hydrocarbon group, 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 of the said linear or branched saturated hydrocarbon group, the group by which one part or all the hydrogen atoms of the said linear or branched saturated hydrocarbon group were substituted by the said halogen atom is mentioned.

R ^{6 ',} R ^7', a saturated hydrocarbon group of cyclic having 3 to 20 carbon atoms in the R ^{8 'is,} it may be any of the cyclic group, monocyclic sentence, for example, one hydrogen from mono cycloalkane The group which removed the atom; The group remove | excluding one hydrogen atom from polycyclo alkanes, such as a bicyclo alkan, tricyclo alkan, and tetracyclo alkan, etc. are mentioned. More specifically, it is 1 from monocyclo alkanes, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, and polycyclo alkanes, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclo dodecane. The group remove | excluding two hydrogen atoms is mentioned.

The cyclic saturated hydrocarbon group may have a substituent. For example, a part of the carbon atoms which comprise the ring which the said cyclic alkyl group has may be substituted by the hetero atom, and the hydrogen atom couple | bonded with the ring which the said cyclic alkyl group has may be substituted by the substituent.

Examples of the former include groups in which at least one hydrogen atom is removed from a heterocycloalkane in which a part of the carbon atoms constituting the monocycloalkane or polycycloalkane ring is substituted with a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Can be. Moreover, you may have ester bond (-C (= O) -O-) in the structure of the said ring. Specifically, lactone-containing monocyclic groups such as groups in which one hydrogen atom is removed from γ-butyrolactone, and groups in which one hydrogen atom is removed from bicycloalkane, tricycloalkane, and tetracycloalkane having a lactone ring And lactone-containing polycyclic groups.

As a substituent in the latter example, the thing similar to what was illustrated as a substituent which the above-mentioned linear or branched alkyl group may have, a lower alkyl group, etc. are mentioned.

Moreover, the combination of a linear or branched alkyl group and a cyclic alkyl group may be sufficient as R <^{6> '} , R <^{7> '} , and R <^{8> '} .

As a combination of a linear or branched alkyl group and a cyclic alkyl group, a group in which a cyclic alkyl group is bonded as a substituent to a linear or branched alkyl group, or a linear or branched substituent as a substituent in a cyclic alkyl group The group etc. which the linear alkyl group couple | bonded are mentioned.

As a linear aliphatic unsaturated hydrocarbon group in R <^{6> '} , R <^{7> '} , and R <^{8> '} , a vinyl group, a propenyl group (allyl group), butynyl group, etc. are mentioned, for example.

As a branched aliphatic unsaturated hydrocarbon group in R <^{6> '} , R <^{7> '} , and R <^{8> '} , 1-methylpropenyl group, 2-methylpropenyl group, etc. are mentioned, for example.

The linear or branched aliphatic unsaturated hydrocarbon group may have a substituent. As this substituent, the thing similar to what was illustrated as a substituent which the said linear or branched alkyl group may have is mentioned.

In the R ^{7 ',} R ^8', wherein among the lithographic properties, the resist pattern is in a preferred point-like, cyclic C 1 -C 15 linear or branched saturated hydrocarbon group, or a 3 to 20 carbon atoms in the Saturated hydrocarbon groups are preferred.

As an aryl group of R < ^{1 >} -R <^3> , it is preferable that it is a phenyl group or a naphthyl group, respectively.

As an alkyl group of R < ^{1 >} -R <^3> , a C1-C10 linear, branched or cyclic alkyl group etc. are mentioned, for example. Especially, it is preferable that it is C1-C5 from the point which is excellent in resolution. Specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, decyl group, etc. are mentioned. A methyl group can be mentioned as a point which is excellent in the resolution, and can be synthesize | combined inexpensively.

As an alkenyl group of R < ^{1 >} -R <^3> , it is preferable that it is C2-C10, for example, 2-5 are more preferable, and 2-4 are more preferable. Specifically, a vinyl group, a propenyl group (allyl group), butynyl group, 1-methylpropenyl group, 2-methylpropenyl group, etc. are mentioned.

When any two of R ^{1 "} to R ^{3 "} are bonded to each other to form a ring together with a sulfur atom in the formula, it is preferable to contain a sulfur atom to form a 3 to 10 membered ring, and a 5 to 7 membered ring It is especially preferable to form a.

When any two of R ^{1 "} to R ^{3 "} are bonded to each other to form a ring together with a sulfur atom in the formula, the other one is preferably an aryl group. The said aryl group is the same as the aryl group of said R < ^{1 >} -R <^3> .

As a specific example of the cation part in the compound represented by said formula (g-c1), it is a triphenylsulfonium, (3,5- dimethylphenyl) diphenylsulfonium, (4- (2-Adaman), for example. Methoxymethyloxy) -3,5-dimethylphenyl) diphenylsulfonium, (4- (2-adamantoxymethyloxy) phenyl) diphenylsulfonium, (4- (tert-butoxycarbonylmethyloxy) phenyl ) Diphenylsulfonium, (4- (tert-butoxycarbonylmethyloxy) -3,5-dimethylphenyl) diphenylsulfonium, (4- (2-methyl-2-adamantyloxycarbonylmethyloxy ) Phenyl) diphenylsulfonium, (4- (2-methyl-2-adamantyloxycarbonylmethyloxy) -3,5-dimethylphenyl) diphenylsulfonium, tri (4-methylphenyl) sulfonium, dimethyl (4-hydroxynaphthyl) sulfonium, monophenyldimethylsulfonium, diphenylmonomethylsulfonium, (4-methylphenyl) diphenylsulfonium, (4-methoxyphenyl) diphenylsulfonium, tri (4- tert-butyl) phenylsulfonium, diphenyl (1- (4-methoxy) naphthyl) sulfonium, di (1-naphthyl) phenylsulfonium, 1-phenyltetra Hydrothiophenium, 1- (4-methylphenyl) tetrahydrothiophenium, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium, 1- (4-methoxynaphthalene-1- 1) tetrahydrothiophenium, 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium, 1- Phenyltetrahydrothiopyranium, 1- (4-hydroxyphenyl) tetrahydrothiopyranium, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiopyranium, 1- (4-methylphenyl) Tetrahydrothiopyranium and the like.

Moreover, what is shown below is specifically mentioned as a preferable thing in the cation part in the compound represented by said formula (g-c1).

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Wherein, g1 represents a repeating number and is an integer of 1 to 5]

[Chemical Formula 9]

[Formula 10]

[In formula, g2 and g3 represent a repeating number, g2 is an integer of 0-20, g3 is an integer of 0-20.]

[Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

In said formula (g-c2), R < ^{5 >} -R < ^{6 >} respectively independently represents the aryl group, alkyl group, or alkenyl group which may have a substituent.

It is preferable that at least 1 is an aryl group among R < ^{5 >} -R <^{6> "} , and it is especially preferable that all of R < ^{5 >} -R <^{6> "} are aryl groups.

Examples of the aryl group for R ^{5 "} to R ^{6" include the same as} the aryl group for R ^{1 "} to R ^3" .

Examples of the alkyl group of R ^{5 "} to R ^{6" include} the same alkyl groups as those of R ^{1 "} to R ^3" .

Examples of the alkenyl group of R ^{5 "} to R ^{6" include} the same alkenyl groups as R ^{1 "} to R ^3" .

Among these, it is most preferable that all of R < ^{5 >} -R <^{6> "} are phenyl groups.

As a specific example of the cation part represented by said formula (g-c2), diphenyl iodonium, bis (4-tert- butylphenyl) iodonium, etc. are mentioned.

Moreover, as a preferable thing of the organic cation of M <^+> , the cationic temperature represented by the following general formula (g-c3) or general formula (g-c4) is mentioned, for example.

[Formula 14]

[Wherein, R ⁸¹ to R ⁸⁶ are each independently an alkyl group, an acetyl group, an alkoxy group, a carboxyl group, a hydroxyl group or a hydroxyalkyl group; n ₁ to n ₅ are each independently an integer of 0 to 3, and n ₆ is 0 Is an integer of ~ 2]

In R ⁸¹ to R ⁸⁶ , the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and in particular, a linear or branched alkyl group is more preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group Or a tert-butyl group is particularly preferable.

The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, among them, a linear or branched alkoxy group is more preferable, and a methoxy group and an ethoxy group are particularly preferable.

The hydroxyalkyl group is preferably a group in which one or a plurality of hydrogen atoms in the alkyl group is substituted with a hydroxy group, and examples thereof include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

When the codes n ₁ to n ₆ assigned to R ⁸¹ to R ⁸⁶ are integers of 2 or more, a plurality of R ⁸¹ to R ⁸⁶ may be the same or different.

n ₁ is preferably 0 to 2, more preferably 0 or 1, still more preferably 0.

n ₂ and n ₃ are preferably each independently 0 or 1, and more preferably 0.

n ₄ becomes like this. Preferably it is 0-2, More preferably, it is 0 or 1.

n ₅ is preferably 0 or 1, and more preferably 0.

n ₆ is preferably 0 or 1, more preferably 1.

As a preferable thing of the cation represented by said Formula (g-c3) or Formula (g-c4), what is shown below is mentioned, for example.

[Formula 15]

Moreover, as a preferable thing of the organic cation of M <^+> , the cationic temperature represented by the following general formula (g-c5) or general formula (g-c6) is mentioned, for example.

[Chemical Formula 16]

In formulas (g-c5) and (g-c6), R ⁹ and R ¹⁰ each independently represent a phenyl group, naphthyl group, or an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a hydroxyl group which may have a substituent. Examples of the substituent include substituents (alkyl group, alkoxy group, alkoxyalkyloxy group, alkoxycarbonylalkyloxy group, halogen atom, hydroxyl group, etc.) in the substituted aryl group exemplified in the description of the aryl groups of R ^{1 "} to R ^3" . Oxo group (= O), an aryl group, -C (= O) -OR ^{6 '} , -OC (= O) -R ^{7 '} , -OR ^{8 '} , the said general formula: -OR ⁵⁵ -C (= O) -OR ⁵⁶ is the same as one group and the like) of the substituted R ⁵⁶ to R ^{56 '.}

R <^{4> '} is a C1-C5 alkylene group.

u is an integer of 1-3 and 1 or 2 is the most preferable.

As a preferable thing of the cation represented by said Formula (b-7) or Formula (b-8), what is shown below is mentioned, for example. In the formula, R ^C is a substituent (alkyl group, alkoxy group, alkoxyalkyloxy group, alkoxycarbonylalkyloxy group, halogen atom, hydroxyl group, oxo group (= O), aryl group, exemplified in the description of the substituted aryl group)- C (= O) is a ^{-OR 6 ', -OC (= O} ) -R 7', -OR 8 ').

[Chemical Formula 17]

[Chemical Formula 18]

Among the above, as the organic cation of M ^+, an organic cation represented by the general formula (g-c1) is most preferable in view of better lithography characteristics and a resist pattern shape when blended with a resist composition. Do.

Specifically as a component (G), the compound (Gm-1) represented by the following general formula (g1-1), the compound (Gm-2) represented by the general formula (g2-1), and general formula (g1-2) Low molecular compound components, such as the compound (Gm-3) shown and the compound (Gm-4) represented by general formula (g2-2), are mentioned.

Moreover, as (G) component, the resin component etc. which have a structural unit (g ') derived from at least 1 sort (s) of compound chosen from the group which consists of said compound (Gm-1) and a compound (Gm-2) are mentioned. have.

[Formula 19]

[In formula (g1-1), R <^P1> is monovalent group represented by either of following general formula (I) or general formula (II). R ² is a single bond or a —C (═O) —O— group. However, when R <^2> is a single bond, what N <^-> in a formula couple | bonds with -C (= O)-group shall not be included in (G) component. R ³ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group which has a partial structure. In formula (g2-1), R ^P2 is a monovalent group represented by any of the following General Formulas (I) to (III). X each independently represents a single bond or a divalent linking group. M ⁺ is each independently an organic cation]

[Chemical Formula 20]

[In formula (I)-(III), R ^a is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group, R ⁿ is a hydrogen atom or a C1-C5 alkyl group.]

[Chemical Formula 21]

Equation (g1-2) of, R ¹ is a fluorine atom, a hydroxyl group, -OR ¹⁰ group, -NH-C (= O) -R 10 group, -OC (= O) -R ¹⁰ group, or a - C (= O) -OR ¹⁰ group, provided that R ¹⁰ is a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or 3 to 20 carbon atoms C1-C20 linear or branched monovalent hydrocarbon group, C3-C20 cyclic monovalent hydrocarbon group which may be substituted by the C1-C20 monovalent hydrocarbon group which has a cyclic partial structure of , A monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom. R ² is a single bond or a —C (═O) —O— group. However, when R <^2> is a single bond, what N <^-> in a formula couple | bonds with -C (= O)-group shall not be included in (G) component. R ³ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group which has a partial structure. In formula (g2-2), R <^4> is a fluorine atom, a hydroxyl group, -OR <^10> group, -OC (= O) -R <^10> group, or -C (= O) -OR <^10> group (R <^10>). Represents a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms) 1 having a linear or branched monovalent alkyl group of 1 to 20 carbon atoms, a cyclic monovalent hydrocarbon group of 3 to 20 carbon atoms, or a cyclic partial structure of 3 to 20 carbon atoms which may be substituted with It is a noble hydrocarbon group. M ⁺ is each independently an organic cation]

[Compound (Gm-1)]

Compound (Gm-1) is a compound represented by the general formula (g1-1).

In formula (g1-1), R ^P1 is a monovalent group represented by any of the above general formula (I) or general formula (II).

R ^<a> is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group in Formula (I), (II). The alkyl group of 1 to 5 carbon atoms in R ^a is preferably a linear or branched alkyl group, and specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, or tert. -Butyl group, pentyl group, isopentyl group, neopentyl group, etc. are mentioned. Halogenated alkyl group having a carbon number of 1-5 in the R ^a may include groups some or all of the hydrogen atoms of the "alkyl group having 1 to 5 carbon atoms in R ^a", the one substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable. As R ^a , a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms is more preferable, and a hydrogen atom or a methyl group is particularly preferable from industrial availability.

In formula (II), ^Rn is a hydrogen atom or a C1-C5 alkyl group.

In formula (g1-1), X represents a single bond or a bivalent coupling group.

The divalent linking group in X is not specifically limited, The bivalent hydrocarbon group which may have a substituent, the bivalent coupling group containing a hetero atom, etc. are mentioned as a preferable thing.

A hydrocarbon group "has a substituent" means that part or all of the hydrogen atoms in the hydrocarbon group are substituted with a substituent (group or atom other than a hydrogen atom).

The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.

The aliphatic hydrocarbon group as the divalent hydrocarbon group in X may be saturated or unsaturated, and is preferably saturated.

More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, still more preferably 1 to 4, 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.

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- ; 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 ) Alkyl ethylene groups such as ₂ -CH _2- ; alkyltrimethylene groups such as -CH (CH ₃ ) CH ₂ CH _2- , -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.

The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O), and the like.

Examples of the aliphatic hydrocarbon group containing a ring in the above structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms are removed from an aliphatic hydrocarbon ring) and an alicyclic hydrocarbon group bonded to a terminal of a linear or branched aliphatic hydrocarbon group. And group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same ones as described above.

It is preferable that carbon number is 3-20, and, as for the said alicyclic hydrocarbon group, it is more preferable that it is 3-12.

The alicyclic hydrocarbon group may be polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon group, a group in which two hydrogen atoms are removed from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group in which two hydrogen atoms have been removed from a polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically, adamantane, norbornane and iso Bornan, tricyclodecane, tetracyclo dodecane, etc. are mentioned.

The alicyclic hydrocarbon group may or may not have a substituent. As a substituent, a C1-C5 alkyl group, a fluorine atom, a C1-C5 fluorinated alkyl group substituted by the fluorine atom, an oxygen atom (= O), etc. are mentioned.

The aromatic hydrocarbon group as the divalent hydrocarbon group in X is a hydrocarbon group having an aromatic ring.

It is preferable that carbon number of this aromatic hydrocarbon group is 3-30, It is more preferable that it is 5-30, 5-20 are still more preferable, 6-15 are especially preferable, 6-10 are the most preferable. However, the carbon number does not include the carbon number in the substituent.

As an aromatic ring which an aromatic hydrocarbon group has, Specifically, aromatic hydrocarbon ring, such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene; The aromatic heterocyclic ring in which some carbon atoms which comprise the said aromatic hydrocarbon ring were substituted by the hetero atom. Etc. can be mentioned. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom and a nitrogen atom.

Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms are removed from the aromatic hydrocarbon ring (arylene group); one of the hydrogen atoms in the group (aryl group) in which one hydrogen atom is removed from the aromatic hydrocarbon ring is alkylene. A hydrogen atom from an aryl group in an arylalkyl group such as a group substituted with a group (for example, a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.) And group removed one more). 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.

The aromatic hydrocarbon group may or may not have a substituent. For example, the hydrogen atom couple | bonded with the aromatic hydrocarbon ring which the said aromatic hydrocarbon group has 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, an oxygen atom (= O), 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 tert- butyl group.

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

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

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

The hetero atom in the "bivalent coupling group containing a hetero atom" of said X is atoms other than a carbon atom and a hydrogen atom, For example, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, etc. are mentioned.

As a bivalent coupling group containing a hetero atom, -O-, -C (= O) -O-, -C (= O)-, -OC (= O) -O-, -C (= O)- NH-, -NH- (H may be substituted with substituents such as alkyl groups, acyl groups), -S-, -S (= O) _2- , -S (= O) ₂ -O-, -NH- C (= O)-, = N-, general formula -Y ²¹ -OY ²² -,-[Y ²¹ -C (= O) -O] _{m ＇} -Y ²² -or -Y ²¹ -OC (= O) A group represented by -Y ^22- [wherein, Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m ＇is an integer of 0 to 3; Can be.

When X is -NH-, H may be substituted by substituents, such as an alkyl group and an aryl group (aromatic group). The substituent (alkyl group, aryl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms.

In the formulas -Y ²¹ -OY ²² -,-[Y ²¹ -C (= O) -O] _m -Y ²² -or -Y ²¹ -OC (= O) -Y ^22- , Y ²¹ and Y ²² are Each is a divalent hydrocarbon group which may have a substituent independently. Examples of the divalent hydrocarbon group include those similar to those exemplified above as "the divalent hydrocarbon group which may have a substituent" in X.

As Y <^21> , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a C1-C5 linear alkylene group is more preferable, and a methylene group or an ethylene group is especially preferable.

Y ²² is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is most preferred.

Formula ^{- [Y 21 -C (= O} ) -O] m '-Y 22 - in groups represented by, m' is an integer from 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, 1 is particularly preferable. In short, the formula ^{- [Y 21 -C (= O} ) -O] m '-Y 22 - group represented by the formula ^{-Y 21 -C (= O) -OY} 22 - group represented by is particularly preferred. In particular, expression is preferred group represented by _{- (CH 2) a '-C} (= O) -O- (CH 2) b'. In formula, a 'is an integer of 1-10, the integer of 1-8 is preferable, the integer of 1-5 is more preferable, 1 or 2 is still more preferable, and 1 is the most preferable. b 'is an integer of 1-10, the integer of 1-8 is preferable, the integer of 1-5 is more preferable, 1 or 2 is more preferable, and 1 is the most preferable.

As the divalent linking group containing a hetero atom, a group containing a linear group having an oxygen atom as a hetero atom, for example, an ether bond or an ester bond is preferable, and the above formula -Y ²¹ -OY ²² -,- ^{[Y 21 -C (= O)} -O] m '-Y 22 - is more preferably a group represented by - or ^{-Y 21 -OC (= O) -Y} 22.

Especially as said bivalent coupling group of X, a linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, or the bivalent coupling group containing a hetero atom is preferable. Among these, a linear or branched alkylene group and a divalent alicyclic hydrocarbon group are preferable, and a linear alkylene group and a divalent alicyclic hydrocarbon group are more preferable.

Equation (g1-1) of, R ^2, R ³ and M ⁺ are the same and each R ^2, R ³ and M ⁺ in the formula (g1).

Below, the specific example of a compound (Gm-1) is illustrated.

[Formula 22]

[Compound (Gm-2)]

Compound (Gm-2) is a compound represented by the general formula (g2-1).

In formula (g2-1), R ^P2 is a monovalent group represented by any of the above general formulas (I) to (III). R ^a and R ⁿ are the same as above.

Equation (g2-1) of, X and M ⁺ are the same as each of the X and M ⁺ in the above formula (g1-1). In the case where R ^P2 is a monovalent group represented by the general formula (III), as the divalent linking group for X, a divalent aromatic hydrocarbon group which may have a substituent is preferable, and an arylene group is more preferable.

Below, the specific example of a compound (Gm-2) is illustrated.

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[Compound (Gm-3)]

Compound (Gm-3) is a compound represented by the general formula (g1-2).

In formula (g1-2), R <^1> is a fluorine atom, a hydroxyl group, -OR <^10> group, -NH-C (= O) -R <^10> group, -OC (= O) -R <^10> group, or -C (= O) -OR ¹⁰ groups, provided that R ¹⁰ is a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or 3 to 20 carbon atoms C1-C20 linear or branched monovalent hydrocarbon group, C3-C20 cyclic monovalent hydrocarbon group, which may be substituted by the cyclic partial structure), It is a monovalent hydrocarbon group or hydrogen atom which has a C3-C20 cyclic partial structure.

With respect to a linear or branched monovalent alkyl group in R ¹⁰ , carbon number is 1 to 10, 1 to 5 are preferable, and 1 to 3 are more preferable. Examples of the linear or branched monovalent alkyl group for R ¹⁰ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert -Butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. are mentioned.

The cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms and the monovalent hydrocarbon group having cyclic partial structure having 3 to 20 carbon atoms in R ¹⁰ have 3 carbon atoms in R ³ in the formula (g1). It is the same as the monovalent hydrocarbon group which has a cyclic monovalent hydrocarbon group of -20, and a C3-C20 cyclic partial structure, respectively.

With respect to a linear or branched monovalent hydrocarbon group in R ¹ , carbon number is 1 to 20, 1 to 15 are preferable, 1 to 10 are more preferable, and 1 to 5 are more preferable. However, the carbon number does not include the carbon number in the substituent.

Examples of the linear or branched monovalent hydrocarbon group for R ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group and tert -Butyl group, n-pentyl group, i-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, undecyl group, dodecyl group, tridecyl group, i -Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, i-hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, an isosil group, etc. are mentioned.

Of the R ^1, groups are a monovalent hydrocarbon group having a partial structure of the cyclic having 3 to 20 carbon atoms cyclic monovalent hydrocarbon group, having 3 to 20 carbon atoms of, in R ³ in the formula (g1), having up to 3 carbon atoms And the same ones as the monovalent hydrocarbon groups having a cyclic monovalent hydrocarbon group of ˜20 and a cyclic partial structure having 3 to 20 carbon atoms. In addition, the cyclic hydrocarbon group may be an aromatic hydrocarbon group. An aromatic hydrocarbon group is a hydrocarbon group which has an aromatic ring. It is preferable that carbon number of this aromatic hydrocarbon group is 5-20, 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 hydrocarbon group include one hydrogen atom from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, or a phenanthryl group. Aryl group removed; arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group; corresponding aryl group or one or more hydrogen from the arylalkyl group The group which removed the atom etc. are mentioned. It is preferable that carbon number of the alkyl chain in the said arylalkyl group is 1-4, It is more preferable that it is 1-2, It is especially preferable that it is 1.

The aromatic hydrocarbon group is a fluorine atom, a hydroxyl group, a -OR ¹⁰ group, a -NH-C (= O) -R ¹⁰ group, a -OC (= O) -R ¹⁰ group, or -C (= O) -OR ¹⁰ In addition to the group, you may have a substituent. For example, a part of the carbon atoms which comprise the aromatic ring which the said aromatic hydrocarbon group has may be substituted by the hetero atom, and the hydrogen atom couple | bonded with the aromatic ring which the said aromatic hydrocarbon group has may be substituted by the substituent.

Examples of the former include a heteroaryl group in which a part of the carbon atoms constituting the ring of the aryl group is substituted with a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, and a part of the carbon atoms constituting the aromatic hydrocarbon ring in the arylalkyl group. The heteroaryl alkyl group in which the substituent was substituted by the said hetero atom is mentioned.

As a substituent of the aromatic hydrocarbon group in the latter example, an alkyl group, a halogen atom other than a fluorine atom, a halogenated alkyl group, an oxygen atom (= O), etc. are mentioned, for example.

As an alkyl group as a substituent of the said aromatic hydrocarbon group, 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 a halogen atom as a substituent of the said aromatic hydrocarbon group, a chlorine atom, a bromine atom, and an iodine atom are mentioned. As a halogenated alkyl group as a substituent of the said aromatic hydrocarbon group, the group by which one part or all part of the hydrogen atom of the said alkyl group was substituted by the chlorine atom, bromine atom, or iodine atom is mentioned.

Equation (g1-2) of, R ^2, R ³ and M ⁺ are the same and each R ^2, R ³ and M ⁺ in the formula (g1).

Below, the specific example of a compound (Gm-3) is illustrated.

&Lt; EMI ID =

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[Compound (Gm-4)]

Compound (Gm-4) is a compound represented by the general formula (g2-2).

In formula (g2-2), R <^4> is a fluorine atom, a hydroxyl group, -OR <^10> group, -OC (= O) -R <^10> group, or -C (= O) -OR <^10> group (R <^10>). Represents a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms) 1 having a linear or branched monovalent alkyl group of 1 to 20 carbon atoms, a cyclic monovalent hydrocarbon group of 3 to 20 carbon atoms, or a cyclic partial structure of 3 to 20 carbon atoms which may be substituted with It is a hydrocarbon group, and is the same as R <^1> in said formula (g1-2).

In the formula (g2-2), M ⁺ is the same as M ⁺ in the formula (g1).

Below, the specific example of a compound (Gm-4) is illustrated.

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Low molecular compound components, such as the compound (Gm-1), the compound (Gm-2), the compound (Gm-3), and the compound (Gm-4) mentioned above, are an additive mix | blended with a base component in a resist composition. Can be used.

In the resist composition, (G) component as such an additive may be used individually by 1 type, and may be used in combination of 2 or more type.

The component (G) as an additive preferably contains at least one compound selected from the group consisting of compound (Gm-1), compound (Gm-2), compound (Gm-3) and compound (Gm-4). Do.

In a resist composition, 0.5-20 mass parts is preferable with respect to 100 mass parts of base materials of a resist composition, as for content of (G) component as an additive, 1.0-15 mass parts is more preferable, 1.5-10 mass parts is especially preferable. .

When the content of the component (G) is in the above range, the effect of acid diffusion control becomes higher, and the contrast in the unexposed portion and the exposed portion becomes good, so that the lithographic characteristics or the resist pattern shape become better. .

[Resin component having a structural unit (g ')]

The structural unit (g ') is a structural unit derived from at least one compound selected from the group consisting of the compound (Gm-1) and the compound (Gm-2).

Hereinafter, in the structural unit (g '), the structural unit derived from the compound (Gm-1) is also called the structural unit (g'1) and the structural unit derived from the compound (Gm-2) is also called the structural unit (g'2). do.

The term "structural unit derived from compound (Gm-1)" and "structural unit derived from compound (Gm-2)" as used herein mean a structural unit formed by cleavage of the ethylenic double bond of each compound.

Construction unit (g 단위 1)

Structural unit (g # 1) is a structural unit represented by the following general formula (Gm-1-I) or general formula (Gm-1-II).

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[Wherein, R ^a , R ⁿ , R ² , R ³ , X and M ⁺ are the same as above, respectively]

In the formula (Gm-1-I), R ^a is preferably ^a hydrogen atom or a methyl group.

It is preferable that X is a linear, branched or cyclic alkylene group, and it is more preferable that it is a linear or cyclic alkylene group.

R ² is preferably a single bond.

It is preferable that R <^3> is a C1-C10 linear or branched monovalent hydrocarbon group which may be substituted by the fluorine atom, and it is a C1-C10 linear or branched monovalent fluorinated alkyl group. More preferred.

M ⁺ is preferably an organic cation represented by General Formula (g-c1).

In the formula (Gm-1-II), R ^a is preferably ^a hydrogen atom or a methyl group.

R ⁿ is preferably a hydrogen atom or a methyl group.

It is preferable that X is a linear, branched or cyclic alkylene group, and it is more preferable that it is a linear or cyclic alkylene group. R ² is preferably a single bond.

It is preferable that R <^3> is a C1-C10 linear or branched monovalent hydrocarbon group which may be substituted by the fluorine atom, and it is a C1-C10 linear or branched monovalent fluorinated alkyl group. More preferred.

M ⁺ is preferably an organic cation represented by General Formula (g-c1).

Below, the specific example of structural unit (g # 1) is illustrated. In the following formulae, R ^{a '} represents a hydrogen atom, a methyl group or a trifluoromethyl group.

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Constituent unit (g) 2)

Structural unit (g'2) is a structural unit represented by the following general formula (Gm-2-I), general formula (Gm-2-II), or general formula (Gm-2-III).

[Formula 29]

[Wherein, R ^a , R ⁿ , X and M ⁺ are the same as described above]

In the formula (Gm-2-I), R ^a is preferably ^a hydrogen atom or a methyl group.

It is preferable that X is a linear, branched or cyclic alkylene group, and it is more preferable that it is a linear or cyclic alkylene group.

M ⁺ is preferably an organic cation represented by General Formula (g-c1).

In the formula (Gm-2-II), R ^a is preferably ^a hydrogen atom or a methyl group.

R ⁿ is preferably a hydrogen atom or a methyl group.

It is preferable that X is a linear, branched or cyclic alkylene group, and it is more preferable that it is a linear or cyclic alkylene group.

M ⁺ is preferably an organic cation represented by General Formula (g-c1).

In the formula (Gm-2-III), R ^a is preferably ^a hydrogen atom or a methyl group. It is preferable that it is an arylene group which may have a single bond or a substituent, and it is more preferable that X is a single bond.

M ⁺ is preferably an organic cation represented by General Formula (g-c1).

Below, the specific example of structural unit (g'2) is illustrated. In the following formulae, R ^{a '} represents a hydrogen atom, a methyl group or a trifluoromethyl group. m "is 0 or 1;

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The structural unit (g ') which a resin component contains may be used individually by 1 type, and may use 2 or more types together.

In the resin component which has a structural unit (g '), 0.5-30 mol% is preferable with respect to the all the structural units which comprise the said resin component, and, as for the ratio of a structural unit (g'), 1-15 mol% is more preferable. Preferably, 1-10 mol% is more preferable.

By carrying out the ratio of a structural unit (g ') in the said range, the effect of acid diffusion control becomes high, and the contrast in an unexposed part and an exposure part becomes favorable, and a lithographic characteristic or a resist pattern shape is more favorable. Become.

Other structural units

The resin component having a structural unit (g ') may have other structural units other than the structural unit (g').

Such other structural units are not particularly limited as long as they are structural units not classified in the above-described structural units (g '), and for resists such as for ArF excimer lasers and KrF excimer lasers (preferably for ArF excimer lasers). As what is used for resin, many conventionally known things can be used.

As such another structural unit, 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, and the structural unit containing the acid-decomposable group whose polarity increases by the action of an acid (to be described later) It is preferable to have a structural unit (a1)). In particular, the copolymer which has this structural unit (a1) and the structural unit (g ') mentioned above can be used as a base material component ((A) component) of a resist composition.

In the resist composition of the present invention, the resin component having the structural unit (g ') is a copolymer having the structural unit (g') and the structural unit (a1), that is, (G) as the base component (component (A)). It is preferable that it is a component.

In addition to the structural unit (g ') and the structural unit (a1), the resin component which has a structural unit (g') as a base material component ((A) component) further has the hydrogen atom couple | bonded with the carbon atom of the (alpha) position substituent. As a structural unit derived from the acrylate ester which may be substituted by the structural unit (a0) containing a -SO2- containing cyclic group, and the hydrogen atom _{couple |} bonded with the carbon atom of the (alpha) position is derived from the acrylate ester which may be substituted by the substituent. It is preferable to have at least 1 type of structural unit chosen from the group which consists of a structural unit (a2) containing a lactone containing cyclic group as a structural unit.

Moreover, the resin component which has a structural unit (g ') as a base material component ((A) component) adds to a structural unit (g') and a structural unit (a1), or a structural unit (a0) and a structural unit ( In addition to at least one of a2) and the structural unit (a1) and the structural unit (g '), a polar group-containing aliphatic hydrocarbon as a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α position may be substituted with a substituent. It is preferable to have a structural unit (a3) containing a group.

Details of the structural units (a1) to (a3) and (a0) will be described later.

In a resist composition, the resin component which has a structural unit (g ') may be used individually by 1 type, and may be used in combination of 2 or more type.

<(H) component>

(H) A component is a compound which has monovalent group represented by the following general formula (h1), or monovalent group represented by general formula (h2).

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[In formula (h1), R <^6> is a single bond or -C (= O) -O- group. R ⁷ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. Monovalent hydrocarbon group having a partial structure]

In said formula (h1), R <^6> is a single bond or -C (= O) -O- group, and it is preferable that it is a single bond.

In R ^7, one having a partial structure of the cyclic group having 1 to 10 carbon atoms in a linear or branched monovalent hydrocarbon group of chain-like, having 3 to 20 carbon atoms cyclic monovalent hydrocarbon group, having 3 to 20 carbon atoms in the A valent hydrocarbon group is a C1-C10 linear or branched monovalent hydrocarbon group, a C3-C20 cyclic monovalent hydrocarbon group, and C3-C3 in R <^3> in said Formula (g1). It is the same as each monovalent hydrocarbon group which has 20 cyclic partial structure.

Specifically as the (H) component, the compound (Hm-1) represented by the following general formula (h1-1), the compound (Hm-2) represented by the general formula (h2-1), and the general formula (h1-2) Low molecular compound components, such as a compound (Hm-3) and a compound (Hm-4) represented by general formula (h2-2), are mentioned.

Moreover, as (H) component, the resin component etc. which have a structural unit (h ') derived from the at least 1 sort (s) of compound chosen from the group which consists of said compound (Hm-1) and a compound (Hm-2) are mentioned. have.

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[In formula (h1-1), R <^P1> is monovalent group represented by either of said general formula (I) or general formula (II). R ⁶ is a single bond or a —C (═O) —O— group. R ⁷ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group which has a partial structure. In formula (h2-1), R ^P2 is a monovalent group represented by any of the above general formulas (I) to (III). Each X independently represents a single bond or a divalent linking group]

(33)

Equation (h1-2) of, R ⁵ is a fluorine atom, a hydroxyl group, -OR ¹⁰ group, -NH-C (= O) -R 10 group, -OC (= O) -R ¹⁰ group, or a - C (= O) -OR ¹⁰ group, provided that R ¹⁰ is a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or 3 to 20 carbon atoms C1-C20 linear or branched monovalent hydrocarbon group, C3-C20 cyclic monovalent hydrocarbon group which may be substituted by the C1-C20 monovalent hydrocarbon group which has a cyclic partial structure of , A monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom. R ⁶ is a single bond or a —C (═O) —O— group. R ⁷ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group which has a partial structure. In formula (h2-2), R <^8> is a fluorine atom, a hydroxyl group, -OR <^10> group, -OC (= O) -R <^10> group, or -C (= O) -OR <^10> group (R <^10>). Represents a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms) 1 having a linear or branched monovalent alkyl group of 1 to 20 carbon atoms, a cyclic monovalent hydrocarbon group of 3 to 20 carbon atoms, or a cyclic partial structure of 3 to 20 carbon atoms which may be substituted with Is a hydrocarbon group]

[Compound (Hm-1)]

A compound (Hm-1) is a compound represented with the said general formula (h1-1).

In formula (h1-1), R ^P1 is a monovalent group represented by any of the above general formula (I) or general formula (II).

In formula (h1-1), R <^6> , R <^7> and X are the same as R <^2> , R <^3> and X in said formula (g1-1), respectively.

Compound (Hm-1) as a specific example, as shown below as an example, "-N ^- -" in the exemplified compound No. moiety in the compound (Gm-1) of the "-NH-" The compound substituted by the above is mentioned.

[Formula 34]

[Compound (Hm-2)]

A compound (Hm-2) is a compound represented with the said general formula (h2-1).

In formula (h2-1), R ^P2 is a monovalent group represented by any of the above general formulas (I) to (III).

In formula (h2-1), X is the same as X in said formula (g2-1).

Specific examples of the below compound (Hm-2) is "-COO ^-" in no moiety of the compound exemplified in the above compound (Gm-2) there may be mentioned a compound substituted with a "-COOH" .

[Compound (Hm-3)]

Compound (Hm-3) is a compound represented by the general formula (h1-2).

Equation (h1-2) of, R ⁵ is a fluorine atom, a hydroxyl group, -OR ¹⁰ group, -NH-C (= O) -R 10 group, -OC (= O) -R ¹⁰ group, or a -C (= O) -OR ¹⁰ groups, provided that R ¹⁰ is a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or 3 to 20 carbon atoms C1-C20 linear or branched monovalent hydrocarbon group, C3-C20 cyclic monovalent hydrocarbon group, which may be substituted by the cyclic partial structure), It is a monovalent hydrocarbon group or hydrogen atom which has a C3-C20 cyclic partial structure, and is the same as R <^1> in said formula (g1-2).

In the formula (h1-2), R ⁶ and R ⁷ are the same and each of R ⁶ and R ⁷ in the formula (h1-1).

Specific examples of the below compound (Hm-3) is "-N - ^-" in as shown below as an example, no moiety of the compound exemplified in the above compound (Gm-3) a "- The compound substituted by "NH-", etc. are mentioned.

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[Compound (Hm-4)]

Compound (Hm-4) is a compound represented by the general formula (h2-2).

In formula (h2-2), R <^8> is a fluorine atom, a hydroxyl group, -OR <^10> group, -OC (= O) -R <^10> group, or -C (= O) -OR <^10> group (R <^10>). Represents a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms) 1 having a linear or branched monovalent alkyl group of 1 to 20 carbon atoms, a cyclic monovalent hydrocarbon group of 3 to 20 carbon atoms, or a cyclic partial structure of 3 to 20 carbon atoms which may be substituted with It is a hydrocarbon group, and is the same as R <^5> in said Formula (h1-2).

In the following, compound (Hm-4) as a specific example, as shown below as an example, the compound (Gm-4) "-COO ^-" in no moiety of the exemplified compound in the "-COOH The compound substituted with ", etc. are mentioned.

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The low molecular weight compound components, such as the compound (Hm-1), a compound (Hm-2), a compound (Hm-3), and a compound (Hm-4) mentioned above, are an additive mix | blended with a base component in a resist composition. Can be used.

In the resist composition, (H) component as such an additive may be used individually by 1 type, and may be used in combination of 2 or more type.

The component (H) as an additive preferably contains at least one compound selected from the group consisting of compound (Hm-1), compound (Hm-2), compound (Hm-3) and compound (Hm-4). Do.

In a resist composition, 0.1-15 mass parts is preferable with respect to 100 mass parts of base materials of a resist composition, as for content of (H) component as an additive, 0.3-7 mass parts is more preferable, 0.5-5 mass parts is especially preferable. .

When content of (H) component exists in the said range, the dimensional fluctuation of the resist pattern by the influence of time progress is suppressed more.

[Resin component having structural unit (h ')]

The structural unit (h ') is a structural unit derived from at least one compound selected from the group consisting of the compound (Hm-1) and the compound (Hm-2).

Hereinafter, in the structural unit (h '), the structural unit derived from the compound (Hm-1) is also called the structural unit (h'1) and the structural unit derived from the compound (Hm-2) is also called the structural unit (h'2). do.

The term "structural unit derived from compound (Hm-1)" and "structural unit derived from compound (Hm-2)" as used herein mean a structural unit formed by cleavage of the ethylenic double bond of each compound.

Construction unit (h＇1)

The structural unit (h (1) is a structural unit represented by the following general formula (Hm-1-I) or general formula (Hm-1-II).

[Formula 37]

[Wherein R ^a , R ⁿ , R ⁶ , R ⁷ and X are the same as above]

In the formula (Hm-1-I), R ^a is preferably ^a hydrogen atom or a methyl group.

It is preferable that X is a linear, branched or cyclic alkylene group, and it is more preferable that it is a linear or cyclic alkylene group.

R ⁶ is preferably a single bond.

R ⁷ is preferably a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and is a linear or branched monovalent fluorinated alkyl group having 1 to 10 carbon atoms. More preferred.

In the formula (Hm-1-II), R ^a is preferably ^a hydrogen atom or a methyl group.

R ⁿ is preferably a hydrogen atom or a methyl group.

It is preferable that X is a linear, branched or cyclic alkylene group, and it is more preferable that it is a linear or cyclic alkylene group.

R ⁶ is preferably a single bond.

R ⁷ is preferably a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, and is a linear or branched monovalent fluorinated alkyl group having 1 to 10 carbon atoms. More preferred.

Below, the specific example of structural unit (h'1) is illustrated. In the following formulae, R ^{a '} represents a hydrogen atom, a methyl group or a trifluoromethyl group.

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Construction unit (h＇2)

The structural unit (h (2) is a structural unit represented by the following general formula (Hm-2-I), general formula (Hm-2-II) or general formula (Hm-2-III).

[Chemical Formula 39]

[Wherein R ^a , R ⁿ and X are the same as above]

In the formula (Hm-2-I), R ^a is preferably ^a hydrogen atom or a methyl group.

It is preferable that X is a linear, branched or cyclic alkylene group, and it is more preferable that it is a linear or cyclic alkylene group.

In the formula (Hm-2-II), R ^a is preferably ^a hydrogen atom or a methyl group.

R ⁿ is preferably a hydrogen atom or a methyl group.

It is preferable that X is a linear, branched or cyclic alkylene group, and it is more preferable that it is a linear or cyclic alkylene group.

In the formula (Hm-2-III), R ^a is preferably ^a hydrogen atom or a methyl group. It is preferable that it is an arylene group which may have a single bond or a substituent, and it is more preferable that X is a single bond.

Below, the specific example of structural unit (h'2) is illustrated. In the following formulae, R ^{a '} represents a hydrogen atom, a methyl group or a trifluoromethyl group. m "is 0 or 1;

[Formula 40]

The structural unit (h ') which a resin component contains may be used individually by 1 type, and may use 2 or more types together.

In the resin component which has a structural unit (h '), 0.5-30 mol% is preferable and, as for the ratio of a structural unit (h') with respect to all the structural units which comprise the said resin component, 1-15 mol% is more Preferably, 1.5-10 mol% is more preferable.

By making ratio of a structural unit (h ') more than a lower limit, the dimensional fluctuation of a resist pattern by the influence of time progress is suppressed more. On the other hand, when the ratio of the structural unit (h ') is below an upper limit, the dissolution contrast of a developing solution (especially alkaline developing solution) becomes favorable, and lithographic characteristics, such as resolution and pattern shape, become favorable.

Other structural units

The resin component which has a structural unit (h ') may have other structural units other than a structural unit (h').

Such other structural units are not particularly limited as long as they are structural units not classified in the above-described structural unit (h '), and are used for resists such as for ArF excimer laser and KrF excimer laser (preferably for ArF excimer laser). As what is used for resin, many conventionally known things can be used.

It is preferable to have a structural unit (a1) mentioned later as such another structural unit. In particular, the copolymer which has this structural unit (a1) and the structural unit (h ') mentioned above can be used as a base component ((A) component) of a resist composition.

In the resist composition of the present invention, the resin component having the structural unit (h ') is a copolymer having the structural unit (h') and the structural unit (a1), that is, (H) as the base component (component (A)). It is preferable that it is a component.

The resin component having a structural unit (h ') is at least one kind selected from the group consisting of the structural unit (a0) and the structural unit (a2) in addition to the structural unit (h') and the structural unit (a1). It is preferable to have a structural unit of.

Moreover, the resin component which has a structural unit (h ') is in addition to a structural unit (h') and a structural unit (a1), or at least one of a structural unit (a0) and a structural unit (a2), and a structural unit (a1). ) And in addition to the structural unit (h '), it is preferable to further have the structural unit (a3).

In a resist composition, the resin component which has a structural unit (h ') may be used individually by 1 type, and may be used in combination of 2 or more type.

In addition, as above-mentioned "resin component which has a structural unit (g '), and" resin component which has a structural unit (h') ", the structural unit guide | induced from (G) component in the same copolymer (structural unit The copolymer which has a structural unit (structural unit (h ')) derived from (g') and (H) component is also mentioned.

In the copolymer which has such a structural unit (g ') and a structural unit (h'), as for the ratio of a structural unit (g '), 0.5-30 mol% is preferable with respect to all the structural units which comprise the said copolymer. , 1-15 mol% is more preferable, 1-10 mol% is further more preferable, The ratio of a structural unit (h ') is 0.5-30 mol% with respect to the all structural units which comprise the said copolymer. 1-15 mol% is more preferable, and 1-10 mol% is further more preferable.

By carrying out the ratio of a structural unit (g ') in the said range, the effect of acid diffusion control becomes high and a lithographic characteristic or a resist pattern shape becomes more favorable.

By making ratio of a structural unit (h ') more than a lower limit, the dimensional fluctuation of a resist pattern by the influence of time progress is suppressed more. On the other hand, when the ratio of the structural unit (h ') is below an upper limit, the dissolution contrast of a developing solution (especially alkaline developing solution) becomes favorable, and lithographic characteristics, such as resolution and pattern shape, become favorable.

In the resist composition of this invention, it is preferable that the content mass of the said compound (H) is more than the mass of content of the said compound (G). Thereby, the dimensional fluctuation with the influence of time progresses when a resist composition is prepared and preserve | saved for a fixed period is suppressed.

In the present invention, the "content mass" when the compound (H) or the compound (G) is a low molecular weight compound component means the number of moles (mol) of the compound to be blended into the resist composition based on 100 parts by mass of the base component. it means.

The "content mass" in the case where the compound (H) or the compound (G) is a resin component as the base component is defined as the number of moles (mol) calculated by the following procedures (1) to (3).

Procedure (1): About the resin used for a resist composition, the copolymer composition ratio (ratio of each structural unit in a structural formula (molar ratio) in the structural formula) is calculated | required by carbon 13 nuclear magnetic resonance spectrum (600 MHz # ¹³ C-NMR). . Thereby, the ratio (molar ratio) of a structural unit (h ') or a structural unit (g') is calculated | required.

Procedure (2): From the molar ratio calculated | required in procedure (1), the mass ratio of a structural unit (h ') or a structural unit (g') is calculated | required, and from this, when setting the whole resin component to 100 (mass part), respectively Find the ratio (mass ratio) of the structural units of.

Procedure (3): Consider the ratio (mass ratio) of the structural unit calculated | required in procedure (2) as the mass of a compound (H) or a compound (G), and from this, the mole of a compound (H) or a compound (G) ( Mole) number is calculated.

<(A) component>

In the resist composition of the present invention, as the component (A), it is preferable to use a base component (component (A0)) whose polarity is increased by the action of an acid. That is, the resist composition of the present invention is preferably a chemically amplified resist composition that becomes positive in the alkali developing process and becomes negative in the solvent developing process.

The component (A0) may be a resin component whose polarity is increased by the action of an acid, a low molecular compound component whose polarity is increased by the action of an acid, or a mixture thereof.

The component (A0) is preferably a resin component whose polarity is increased by the action of an acid, and in particular, a hydrogen unit bonded to a carbon atom at the α-position is a structural unit derived from an acrylate ester which may be substituted with a substituent. It is preferable to contain the polymer (A1) (henceforth "the (A1) component") which has a structural unit (a1) containing the acid-decomposable group which increases polarity by effect | action.

In addition to the structural unit (a1), the component (A1) further contains a -SO ₂ -containing cyclic group as a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α position may be substituted with a substituent. At least 1 selected from the group consisting of a structural unit (a0) and a structural unit (a2) containing a lactone-containing cyclic group as a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent. It is preferable to have a structural unit of a species.

In addition, the component (A1) is a carbon atom in the α position in addition to the structural unit (a1), or in addition to at least one of the structural unit (a0) and the structural unit (a2) and the structural unit (a1). It is preferable to have a structural unit (a3) containing a polar group containing aliphatic hydrocarbon group as a structural unit derived from the acrylate ester which the hydrogen atom couple | bonded with the substituent may be substituted by the substituent.

Moreover, as (A1) component, the copolymer (component (G) as a base material component) which has a structural unit (g ') mentioned above further in addition to the said structural unit (a1) is mentioned as a preferable thing.

Moreover, as (A1) component, the copolymer ((H) component as a base material component) which has a structural unit (h ') mentioned above further in addition to the said structural unit (a1) is mentioned as a preferable thing.

Here, in this specification and a claim, a "structural unit derived from an acrylate ester" means the structural unit which the ethylenic double bond of an acrylate ester is cleaved and comprised.

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

As for the acrylate ester, the hydrogen atom couple | bonded with the carbon atom of the (alpha) position may be substituted by the substituent. Substituents for substituting a hydrogen atom bonded to the carbon atom at the α-position are atoms or groups other than hydrogen atoms, and examples thereof include an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a hydroxyalkyl group. . In addition, the carbon atom of the (alpha) position of an acrylate ester is a carbon atom to which the carbonyl group couple | bonded 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. Moreover, acrylic ester and alpha substituted acrylate ester may be encompassed and may be called "(alpha substituted) acrylic acid ester."

In the α-substituted acrylic acid ester, the alkyl group as the substituent at the α-position is preferably a linear or branched alkyl group, and specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group, pentyl group, isopentyl group and neopentyl group.

Moreover, the halogenated alkyl group as a substituent of the (alpha) position specifically, mention | raise | lifted the group which substituted part or all of the hydrogen atom of the said "alkyl group as a substituent of the (alpha) position" by the halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

The thing bonded to the α position of the α-substituted acrylic acid ester is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms. More preferably, a hydrogen atom or a methyl group is most preferable from industrial availability.

[Structural unit (a1)]

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

An "acid-decomposable group" is an acid-decomposable group which can cleave at least one bond in the structure of the acid-decomposable group by the action of an acid generated, for example, from component (B).

As an acid-decomposable group 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 a carboxyl group, there may be mentioned hydroxyl group, an amino group, a sulfo group (-SO ₃ H) or the like. Among these, a polar group (hereinafter sometimes referred to as an "OH-containing polar group") in the structure is preferable, a carboxyl group or a hydroxyl group is preferable, and a carboxyl group is particularly preferable.

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

An "acid dissociable group" has an acid dissociation property which the bond between the said acid dissociable group and the atom adjacent to this acid dissociable group can cleave at least by the action | action of the acid generate | occur | produced from (B) component by exposure, for example. Qi. 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. Thus, when the acid dissociable group is dissociated by the action of acid, the polar group having a higher polarity than the acid dissociable group Is generated to increase the polarity. As a result, the polarity of the whole (A1) component increases. By increasing the polarity, the solubility in the developer is relatively changed, when the developer is an alkaline developer, the solubility is increased, while when the developer is a developer (organic developer) containing an organic solvent, the solubility is decreased.

It does not specifically limit as an acid dissociable group, The thing proposed as an acid dissociable group of the base resin for chemically amplified resist can be used so far. Generally, the group which forms a cyclic group or a linear tertiary alkyl ester with a carboxyl group in (meth) acrylic acid; Acetal-type acid dissociable groups, such as an alkoxyalkyl group, etc. are widely known.

As used herein, "tertiary alkyl ester" is a hydrogen atom of a carboxyl group is substituted with a chain or cyclic alkyl group to form an ester, and oxygen at the terminal of the carbonyloxy group (-C (= O) -O-) The structure which the tertiary carbon atom of the said linear or cyclic alkyl group couple | bonds with the atom is shown. In this tertiary alkyl ester, when an acid acts, the bond is cleaved between an oxygen atom and a tertiary carbon atom to form a carboxyl group.

The chain or cyclic alkyl group may have a substituent.

Hereinafter, the group which becomes acid dissociable by forming a carboxyl group and a tertiary alkyl ester is called "tertiary alkyl ester type acid dissociable group" for convenience.

Examples of the tertiary alkyl ester type acid dissociable group include an acid dissociable group containing an aliphatic branched acid dissociable group and an aliphatic cyclic group.

Here, an "aliphatic branched chain type" means having a branched chain structure having no aromaticity. Although the structure of an "aliphatic branched-type acid dissociable group" is not limited to being a group (carbon group) which consists of carbon and hydrogen, It is preferable that it is a hydrocarbon group. The hydrocarbon group may be either saturated or unsaturated, but is usually saturated.

As an aliphatic branched-type acid dissociable group, group represented by -C (R ⁷¹ ) (R ⁷² ) (R ⁷³ ) is mentioned, for example. In formula, R <^71> -R <^73> is a C1-C5 linear alkyl group each independently. The group represented by -C (R ⁷¹ ) (R ⁷² ) (R ⁷³ ) preferably has 4 to 8 carbon atoms, and specifically, tert-butyl group, 2-methyl-2-butyl group, 2-methyl-2- A pentyl group, 3-methyl-3- pentyl group, etc. are mentioned. Especially tert- butyl group is preferable.

An "aliphatic cyclic group" shows that it is a monocyclic group or polycyclic group which does not have aromaticity.

The aliphatic cyclic group in the "acid dissociable group containing an aliphatic cyclic group" may or may not have a substituent. As a substituent, a C1-C5 alkyl group, a C1-C5 alkoxy group, a fluorine atom, a C1-C5 fluorinated alkyl group substituted with the fluorine atom, an oxygen atom (= O), etc. are mentioned.

The basic ring structure excluding the substituent of the aliphatic cyclic group is not limited to being a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. Moreover, although the hydrocarbon group may be either saturated or unsaturated, it is preferable that it is normally saturated. 3-30 are preferable, as for carbon number which comprises the basic ring, 3-20 are more preferable, 5-15 are more preferable, and 5-12 are especially preferable.

The aliphatic cyclic group may be monocyclic or polycyclic.

As an aliphatic cyclic group, group which removed 1 or more hydrogen atoms from the monocycloalkane which may or may not be substituted by the C1-C5 alkyl group, a fluorine atom, or a fluorinated alkyl group, for example; bicycloalkane, tri The group remove | excluding one or more hydrogen atoms from polycycloalkane, such as cycloalkane and tetracycloalkane, etc. are mentioned. More specifically, group which removed 1 or more hydrogen atoms from monocyclo alkanes, such as cyclopentane and cyclohexane; Polycyclo alkanes, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclo dodecane Alicyclic hydrocarbon groups, such as group which removed 1 or more hydrogen atoms from the, are mentioned. In addition, a part of the carbon atoms constituting the ring of these alicyclic hydrocarbon groups may be substituted with an ether group (-O-).

As the acid dissociable group containing an aliphatic cyclic group, for example,

(Iii) a substituent (a hydrogen atom) on a ring skeleton of a monovalent aliphatic cyclic group bonded to an atom adjacent to the acid dissociable group (for example, -O- in -C (= O) -O-) Or other atoms or groups) to which a tertiary carbon atom is formed;

And (ii) a group having a monovalent aliphatic cyclic group and a branched alkylene having a tertiary carbon atom bonded thereto.

In the group of (i) above, an alkyl group is mentioned as a substituent couple | bonded with the carbon atom couple | bonded with the atom adjacent to the said acid dissociable group on the ring skeleton of an aliphatic cyclic group. As this alkyl group, the same thing as R <^14> in Formula (1-1)-(1-9) mentioned later is mentioned, for example.

As a specific example of group of said (i), group etc. which are represented by following General formula (1-1) (1-9)-are mentioned, for example.

As a specific example of group of said (ii), group etc. which are represented by following General formula (2-1)-(2-6) are mentioned, for example.

(41)

[Wherein, R ¹⁴ is an alkyl group and g is an integer of 0 to 8]

(42)

[Wherein, R ¹⁵ and R ¹⁶ are each independently an alkyl group]

In formulas (1-1) to (1-9), any of a linear, branched, and cyclic alkyl group of R ¹⁴ may be preferable, and a linear or branched chain type is preferable.

It is preferable that carbon number of this linear alkyl group is 1-5, 1-4 are more preferable, and 1 or 2 is still more preferable. Specifically, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. are mentioned. Among them, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

It is preferable that carbon number is 3-10, and, as for this branched alkyl group, 3-5 are more preferable. Specifically, isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, etc. are mentioned, It is most preferable that it is an isopropyl group.

The integer of 0-3 is preferable, as for g, the integer of 1-3 is more preferable, and 1 or 2 is further more preferable.

In Formulas (2-1) to (2-6), examples of the alkyl group represented by R ¹⁵ to R ^{16 include} the same alkyl groups as those described above for R ¹⁴ .

In the formulas (1-1) to (1-9) and (2-1) to (2-6), a part of the carbon atoms constituting the ring may be substituted with an ethereal oxygen atom (-O-). .

In addition, in the formulas (1-1) to (1-9) and (2-1) to (2-6), the hydrogen atom bonded to the carbon atom constituting the ring may be substituted with a substituent. As this substituent, a C1-C5 alkyl group, a fluorine atom, and a fluorinated alkyl group are mentioned.

The "acetal acid dissociable group" is generally substituted with a hydrogen atom at the terminal of an OH-containing polar group such as a carboxyl group or a hydroxyl group and bonded to an oxygen atom. And when an acid generate | occur | produces by exposure, this acid will act | work and a bond will be cleaved between the acetal type acid dissociable group and the oxygen atom which the said acetal type acid dissociable group couple | bonded, and OH containing polar groups, such as a carboxyl group and a hydroxyl group, are formed.

As an acetal type acid dissociable group, group represented by the following general formula (p1) is mentioned, for example.

(43)

[Wherein, R ^{1 ＇} and R ^{2 ＇} each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n represents an integer of 0 to 3, and Y represents an alkyl group having 1 to 5 carbon atoms or an aliphatic cyclic group Shows]

In formula (p1), it is preferable that n is an integer of 0-2, 0 or 1 is more preferable and 0 is the most preferable.

As an alkyl group of R <^{1> '} , R <^2>' , the thing similar to the alkyl group illustrated as a substituent which may be couple | bonded with the carbon atom of the (alpha) position in the description about said (alpha) substituted acrylate ester is mentioned, A methyl group or an ethyl group is preferable, Methyl groups are most preferred.

In this invention, it is preferable that at least 1 of R <^{1> '} and R <^{2> '} is a hydrogen atom. That is, it is preferable that acid dissociable group (p1) is group represented by the following general formula (p1-1).

(44)

[Wherein, R ^{1 ′} , n, Y are the same as above]

As an alkyl group of Y, the thing similar to the alkyl group quoted as a substituent which may be couple | bonded with the carbon atom of the (alpha) position in description about said (alpha) substituted acrylic ester is mentioned.

As the aliphatic cyclic group of Y, any of monocyclic or polycyclic aliphatic cyclic groups that have been conventionally proposed in ArF resists or the like can be appropriately selected and used, for example. The same thing as an aliphatic cyclic group can be illustrated.

As an acetal type acid dissociable group, the air represented by the following general formula (p2) is mentioned.

[Chemical Formula 45]

[In formula, R <^17> , R <^18> is a linear or branched alkyl group or a hydrogen atom each independently; R <^19> is a linear, branched or cyclic alkyl group. Or R ¹⁷ and R ¹⁹ are each independently a linear or branched alkylene group, and R ¹⁷ and R ¹⁹ may be bonded to each other to form a ring]

In R <^17> , R <^18> , carbon number of an alkyl group becomes like this. Preferably it is 1-15, any of a linear type and a branched chain type may be sufficient, an ethyl group and a methyl group are preferable, and a methyl group is the most preferable. It is preferable that especially one of R <^17> , R <^18> is a hydrogen atom, and the other is a methyl group.

R ¹⁹ is a linear, branched or cyclic alkyl group, and preferably has 1 to 15 carbon atoms, and may be any of linear, branched or cyclic.

When R <^19> is linear and branched, it is preferable that it is C1-C5, an ethyl group and a methyl group are more preferable, and an ethyl group is the most preferable.

In the case where R ¹⁹ is cyclic, it is preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, the group etc. which removed one or more hydrogen atoms from polycycloalkane, such as monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, may be used. It can be illustrated. Specific examples thereof include a monocycloalkane such as cyclopentane and cyclohexane, a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane And the like. Especially, the group remove | excluding one or more hydrogen atoms from adamantane is preferable.

In the formula (p2), R ¹⁷ and R ¹⁹ are each independently a linear or branched alkylene group (preferably an alkylene group having 1 to 5 carbon atoms), and R ¹⁹ and R ¹⁷ are bonded to each other. You may do it.

In this case, a cyclic group is formed by R ¹⁷ and, R ^19, and an oxygen atom, a carbon atom to the oxygen atom and R ¹⁷ is R ¹⁹ combined are combined. As this cyclic group, a 4-7 membered ring is preferable and a 4-6 membered ring is more preferable. Specific examples of the cyclic group include a tetrahydropyranyl group, a tetrahydrofuranyl group, and the like.

As a structural unit (a1), the structural unit represented by the following general formula (a1-0-1), the structural unit represented by the following general formula (a1-0-2), etc. are mentioned specifically ,.

(46)

[Wherein R is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; X ¹ is an acid dissociable group; Y ² is a divalent linking group; X ² is an acid dissociable group]

In general formula (a1-0-1), the alkyl group and halogenated alkyl group of R are respectively the alkyl group and halogenated alkyl group which were illustrated as a substituent which may be couple | bonded with the carbon atom of the (alpha) position in the description about said (alpha) substituted acrylate ester. The same thing is mentioned. 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.

If X ¹ is an acid dissociable group, it will not specifically limit, For example, the above-mentioned tertiary alkyl ester type acid dissociable group, an acetal type acid dissociable group, etc. are mentioned, A tertiary alkyl ester type acid dissociable group is preferable.

In general formula (a1-0-2), R is the same as the above.

X ² is the same as X ¹ in Formula (a1-0-1).

Although it does not specifically limit as a bivalent coupling group of Y <^2> , The bivalent hydrocarbon group which may have a substituent, the bivalent coupling group containing a hetero atom, etc. are mentioned as a preferable thing.

A hydrocarbon group "has a substituent" means that part or all of the hydrogen atoms in the hydrocarbon group are substituted with a substituent (group or atom other than a hydrogen atom).

The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.

The aliphatic hydrocarbon group as the divalent hydrocarbon group in Y ² may be saturated or unsaturated, and is preferably saturated.

More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, still more preferably 1 to 4, 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.

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- ; 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 ) Alkyl ethylene groups such as ₂ -CH _2- ; alkyltrimethylene groups such as -CH (CH ₃ ) CH ₂ CH _2- , -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.

The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O), and the like.

Examples of the aliphatic hydrocarbon group containing a ring in the above structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms are removed from an aliphatic hydrocarbon ring) and an alicyclic hydrocarbon group bonded to a terminal of a linear or branched aliphatic hydrocarbon group. And group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include the same ones as described above.

It is preferable that carbon number is 3-20, and, as for the said alicyclic hydrocarbon group, it is more preferable that it is 3-12.

The alicyclic hydrocarbon group may be polycyclic or monocyclic. As the monocyclic alicyclic hydrocarbon group, a group in which two hydrogen atoms are removed from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. As the polycyclic alicyclic hydrocarbon group, a group in which two hydrogen atoms have been removed from a polycycloalkane is preferable, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically, adamantane, norbornane and iso Bornan, tricyclodecane, tetracyclo dodecane, etc. are mentioned.

The alicyclic hydrocarbon group may or may not have a substituent. As a substituent, a C1-C5 alkyl group, a fluorine atom, a C1-C5 fluorinated alkyl group substituted by the fluorine atom, an oxygen atom (= O), etc. are mentioned.

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

Group is an aromatic hydrocarbon as a hydrocarbon divalent group in said Y ² preferably a carbon number of 3-30, more preferably 5-30, and 5-20 is more preferred, and 6 to 15 are particularly preferred, and 6 ~ 10 is most preferred. However, the carbon number does not include the carbon number in the substituent.

As an aromatic ring which an aromatic hydrocarbon group has, Specifically, aromatic hydrocarbon ring, such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene; The aromatic heterocyclic ring in which some carbon atoms which comprise the said aromatic hydrocarbon ring were substituted by the hetero atom. Etc. can be mentioned. Examples of the heteroatom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom and a nitrogen atom.

Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms are removed from the aromatic hydrocarbon ring (arylene group); one of the hydrogen atoms in the group (aryl group) in which one hydrogen atom is removed from the aromatic hydrocarbon ring is alkylene. A hydrogen atom from an aryl group in an arylalkyl group such as a group substituted with a group (for example, a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.) And group removed one more). 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.

The aromatic hydrocarbon group may or may not have a substituent. For example, the hydrogen atom couple | bonded with the aromatic hydrocarbon ring which the said aromatic hydrocarbon group has 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, an oxygen atom (= O), 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 tert- butyl group.

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

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

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

The hetero atom in the "divalent linking group containing a hetero atom" of Y ² is an atom other than a carbon atom and a hydrogen atom, and an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, etc. are mentioned, for example. .

As a bivalent coupling group containing a hetero atom, -O-, -C (= O) -O-, -C (= O)-, -OC (= O) -O-, -C (= O)- NH-, -NH- (H may be substituted with substituents such as alkyl groups, acyl groups), -S-, -S (= O) _2- , -S (= O) ₂ -O-, -NH- C (= O)-, = N-, general formula -Y ²¹ -OY ²² -,-[Y ²¹ -C (= O) -O] _{m ＇} -Y ²² -or -Y ²¹ -OC (= O) A group represented by -Y ^22- [wherein, Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m ＇is an integer of 0 to 3; Can be.

When Y <^2> is -NH-, that H may be substituted by substituents, such as an alkyl group and an aryl group (aromatic group). The substituent (alkyl group, aryl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms.

In the formulas -Y ²¹ -OY ²² -,-[Y ²¹ -C (= O) -O] _m -Y ²² -or -Y ²¹ -OC (= O) -Y ^22- , Y ²¹ and Y ²² are Each is a divalent hydrocarbon group which may have a substituent independently. Examples of the divalent hydrocarbon group include those similar to those exemplified above as "the divalent hydrocarbon group which may have a substituent" in Y ² .

As Y <^21> , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a C1-C5 linear alkylene group is more preferable, and a methylene group or an ethylene group is especially preferable.

Y ²² is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is most preferred.

Formula ^{- [Y 21 -C (= O} ) -O] m '-Y 22 - in groups represented by, m' is an integer from 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, 1 is particularly preferable. In short, the formula ^{- [Y 21 -C (= O} ) -O] m '-Y 22 - group represented by the formula ^{-Y 21 -C (= O) -OY} 22 - group represented by is particularly preferred. In particular, expression is preferred group represented by _{- (CH 2) a '-C} (= O) -O- (CH 2) b'. In formula, a 'is an integer of 1-10, the integer of 1-8 is preferable, the integer of 1-5 is more preferable, 1 or 2 is still more preferable, and 1 is the most preferable. b 'is an integer of 1-10, the integer of 1-8 is preferable, the integer of 1-5 is more preferable, 1 or 2 is more preferable, and 1 is the most preferable.

As the divalent linking group containing a hetero atom, a group containing a linear group having an oxygen atom as a hetero atom, for example, an ether bond or an ester bond is preferable, and the above formula -Y ²¹ -OY ²² -,- ^{[Y 21 -C (= O)} -O] m '-Y 22 - is more preferably a group represented by - or ^{-Y 21 -OC (= O) -Y} 22.

Among the above, as the divalent linking group for Y ² , a linear or branched alkylene group, a divalent alicyclic hydrocarbon group, or a divalent linking group containing a hetero atom is particularly preferable. Among these, a linear or branched alkylene group or a divalent linking group containing a hetero atom is preferable.

Specific examples of the structural unit (a1) include structural units represented by general formulas (a1-1) to (a1-4) shown below.

[Formula 47]

[Wherein, R, R ^{1 '} , R ^{2 '} , n, Y and Y ² are the same as above, and X 'represents a tertiary alkyl ester type acid dissociable group]

In formula, X 'is the same as the said tertiary alkyl ester type acid dissociable group.

^{R 1 ', R 2',} n, roneun Y, respectively, R ^{1 ',} R ^2' in the general formula (p1) illustrated in the description of the above-mentioned "acetal-type acid-dissociable group", n, Y and The same thing can be mentioned.

As Y <^2> , the same thing as Y <^2> in general formula (a1-0-2) mentioned above is mentioned.

Specific examples of the structural units represented by general formulas (a1-1) to (a1-4) are shown below.

In the following formulas, R ^{? Represents} a hydrogen atom, a methyl group or a trifluoromethyl group.

(48)

(49)

(50)

(51)

(52)

(53)

[Formula 54]

(55)

In this invention, as a structural unit (a1), the structural unit represented by the following general formula (a1-0-11), the structural unit represented by the following general formula (a1-0-12), and the following general formula (a1-0-) Represented by the structural unit represented by 13), the structural unit represented by the following general formula (a1-0-14), the structural unit represented by the following general formula (a1-0-15), and the following general formula (a1-0-2) It is preferable to have at least 1 sort (s) chosen from the group which consists of a structural unit.

Especially, the structural unit represented by the following general formula (a1-0-11), the structural unit represented by the following general formula (a1-0-12), the structural unit represented by the following general formula (a1-0-13), and the following general formula It is more preferable to have at least 1 sort (s) chosen from the group which consists of a structural unit represented by a formula (a1-0-14) and a structural unit represented with the following general formula (a1-0-15).

(56)

[Wherein R is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, R ²¹ is an alkyl group; R ²² is a group which forms an aliphatic monocyclic group together with the carbon atom to which R ²² is bonded; R ²³ is a branched alkyl group; R ²⁴ is a group forming an aliphatic polycyclic group together with the carbon atom to which R ²⁴ is bonded; R ²⁵ is a linear alkyl group having 1 to 5 carbon atoms. R ¹⁵ and R ¹⁶ are each independently an alkyl group. Y ² is a divalent linking group, X ² is an acid dissociable group]

Description of each of the formulas, R, Y ^2, X ² is as defined above.

Examples of the alkyl group represented by R ^{21 in} the formula (a1-0-11) include the same alkyl groups as those described for R ¹⁴ in the formulas (1-1) to (1-9), and a methyl group, an ethyl group, or an isopropyl group is preferable. Do.

The aliphatic monocyclic sentence to R ²² form together with the carbon atom to which R ²² is bonded is the art, the first may be of the aliphatic cyclic group exemplified in the tertiary alkyl ester-type acid-dissociable group, the same as the single ring sentence. Specifically, the group etc. which removed 1 or more hydrogen atoms from monocycloalkane are mentioned. The monocycloalkane is preferably a 3 to 11 membered ring, more preferably a 3 to 8 membered ring, still more preferably a 4 to 6 membered ring, and particularly preferably a 5 or 6 membered ring.

In the monocycloalkane, a part of the carbon atoms constituting the ring may or may not be substituted with an ether group (-O-).

Moreover, the monocycloalkane may have a C1-C5 alkyl group, a fluorine atom, or a C1-C5 fluorinated alkyl group as a substituent.

As R <^{22> which} comprises such an aliphatic monocyclic group, the linear alkylene group by which the ether group (-O-) may be interposed between carbon atoms is mentioned, for example.

As a specific example of the structural unit represented by a formula (a1-0-11), said formula (a1-1-16)-(a1-1-23), (a1-1-27), (a1-1-31) The structural unit represented by) is mentioned. Among these, formulas (a1-1-16) to (a1-1-17), (a1-1-20) to (a1-1-23), (a1-1-27), and (a1-1-31) The structural unit represented by the following (a1-1-02) which covers the structural unit represented by (a1-1-32) and (a1-1-33) is preferable. Moreover, the structural unit represented by following (a1-1-02 ') is also preferable.

In each formula, h is an integer of 1-4, and 1 or 2 is preferable.

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[Wherein R and R ²¹ are the same as described above and h is an integer of 1 to 4]

In the formula (a1-0-12), the branched alkyl group of R ²³ is the same as the branched alkyl group exemplified in the alkyl group of R ¹⁴ in the formulas (1-1) to (1-9). And isopropyl group is the most preferable.

That R ²⁴ is an aliphatic forming art with R ²⁴ is a carbon atom bound polycyclic group is the first example can be mentioned that one of the aliphatic cyclic group, in the tertiary alkyl ester-type acid-cleavable group to the same as polycyclic group.

As a specific example of the structural unit represented by a formula (a1-0-12), the structural unit represented by said formula (a1-1-26), (a1-1-28)-(a1-1-30) is mentioned. have.

A structural unit represented by the formula (a1-0-12) is, R ²⁴ is R ²⁴ is the art that with the combination of the carbon atom forming the aliphatic polycyclic group is 2-adamantyl group is preferred, and particularly, the above formula (a1- The structural unit represented by 1-26) is preferable.

In formula (a1-0-13), R and R ²⁴ are the same as above.

As a linear alkyl group of R <^25> , the thing similar to the linear alkyl group illustrated by the alkyl group of R <^14> in said Formula (1-1)-(1-9) is mentioned, A methyl group or an ethyl group is the most preferable. Do.

Specific examples of the structural unit represented by formula (a1-0-13) include formulas (a1-1-1) to (a1-1-2) and (exemplified as specific examples of the general formula (a1-1). The structural unit represented by a1-1-7) (a1-1-15) is mentioned.

A structural unit represented by the following formula (a1-0-13) is, R ²⁴ is R ²⁴ is the art that with the combination of the carbon atom forming the aliphatic polycyclic group is 2-adamantyl group is preferred, and particularly, the above formula (a1- The structural unit represented by 1-1) or (a1-1-2) is preferable.

In formula (a1-0-14), R and R ²² are the same as above. R ¹⁵ and R ¹⁶ are the same as R ¹⁵ and R ¹⁶ in the general formula (2-1) to (2-6), respectively.

As a structural unit represented by a formula (a1-0-14), specifically, it represents with the formula (a1-1-35) and (a1-1-36) illustrated as a specific example of the said general formula (a1-1). The structural unit is mentioned.

In formula (a1-0-15), R and R ²⁴ are the same as above. R ¹⁵ and R ¹⁶ are the same as R ¹⁵ and R ¹⁶ in the general formula (2-1) to (2-6), respectively.

Specific examples of the structural unit represented by formula (a1-0-15) include formulas (a1-1-4) to (a1-1-6) and (exemplified as specific examples of the general formula (a1-1). The structural unit represented by a1-1-34) is mentioned.

As a structural unit represented by a formula (a1-0-2), the structural unit represented by said formula (a1-3) or (a1-4) is mentioned, Especially the structural unit represented by a formula (a1-3) is preferable. Do.

As a structural unit represented by a formula (a1-0-2), it is especially preferable that Y <^2> in a formula is group represented by said -Y ²¹ -OY ²² -or -Y ²¹ -C (= O) -OY ^22- . .

Preferable examples of such structural units include structural units represented by the following general formula (a1-3-01); structural units represented by the following general formula (a1-3-02); represented by the following general formula (a1-3-03). Structural unit etc. are mentioned.

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[Wherein R is the same as above, R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is an alkyl group, e is an integer of 1 to 10, and n is an integer of 0 to 3]

[Chemical Formula 59]

[Wherein R is the same as above, Y ^{2 ′} and Y ^{2 ″} each independently represent a divalent linking group, X ′ is an acid dissociable group, and w is an integer of 0 to 3]

In Formulas (a1-3-01) to (a1-3-02), R ¹³ is preferably a hydrogen atom.

R ¹⁴ is the same as R ¹⁴ in the formula (1-1) to (1-9).

The integer of 1-8 is preferable, as for e, the integer of 1-5 is more preferable, and 1 or 2 is the most preferable.

1 or 2 is preferable and 2 is most preferable for n '.

Specific examples of the structural unit represented by the formula (a1-3-01) include structural units represented by the above formulas (a1-3-25) to (a1-3-26).

As a specific example of the structural unit represented by a formula (a1-3-02), the structural unit represented by said formula (a1-3-27)-(a1-3-28), etc. are mentioned.

Formula (a1-3-03) of, Y ^{2 ',} Y ^{2 "2-valent} connecting group in the are, are the same as Y ² in the general formula (a1-3).

As Y <^2>' , the bivalent hydrocarbon group which may have a substituent is preferable, A linear aliphatic hydrocarbon group is more preferable, A linear alkylene group is still more preferable. Especially, a C1-C5 linear alkylene group is preferable and a methylene group and ethylene group are the most preferable.

As Y ^{2 ″} , a divalent hydrocarbon group which may have a substituent is preferable, a linear aliphatic hydrocarbon group is more preferable, and a linear alkylene group is more preferable. Among them, a linear C 1-5 group The alkylene group of is preferable, and a methylene group and ethylene group are the most preferable.

The acid dissociable group in X 'may be the same as the above, It is preferable that it is a tertiary alkyl ester type acid dissociable group, and is adjacent to the said acid dissociable group on the ring skeleton of the above-mentioned monovalent aliphatic cyclic group. The group which the substituent bonds to the carbon atom couple | bonded with the atom to which it is couple | bonded, and the tertiary carbon atom is formed is more preferable, and the group represented by the said General formula (1-1) is especially preferable.

It is preferable that w is an integer of 0-3, w is an integer of 0-2, 0 or 1 is more preferable, and 1 is the most preferable.

As a structural unit represented by a formula (a1-3-03), the structural unit represented by the following general formula (a1-3-03-1) or (a1-3-03-2) is preferable, Especially, a formula ( The structural unit represented by a1-3-03-1) is preferable.

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[Wherein R and R ¹⁴ are the same as described above, a 'is an integer of 1 to 10, b' is an integer of 1 to 10, and t is an integer of 0 to 3]

In formula (a1-3-03-1)-(a1-3-03-2), a 'is the same as the above, the integer of 1-8 is preferable, the integer of 1-5 is more preferable, 1 Or 2 is particularly preferred.

b 'is the same as above, the integer of 1-8 is preferable, the integer of 1-5 is preferable, and 1 or 2 is especially preferable.

The integer of 1-3 is preferable, and 1 or 2 of t is especially preferable.

As a specific example of the structural unit represented by a formula (a1-3-03-1) or (a1-3-03-2), the structure represented by said formula (a1-3-29)-(a1-3-32) A unit is mentioned.

The structural unit (a1) contained in the component (A1) may be one type or two or more types.

15-70 mol% is preferable with respect to all the structural units which comprise (A1) component, and, as for the ratio of a structural unit (a1), in a (A1) component, 15-60 mol% is more preferable, 20-55 Mol% is more preferable.

By making the ratio of a structural unit (a1) more than a lower limit, when it is set as a resist composition, a pattern can be obtained easily and lithography characteristics, such as a sensitivity, a resolution, and LWR, also improve. Moreover, it becomes easy to balance with the other structural unit by using below an upper limit.

[Construction unit (a0)]

Structural unit (a0) is a 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, and is a structural unit containing a -SO2- containing cyclic group.

A structural unit (a0) is a, -SO ₂ - by containing a cyclic group containing, increases the adhesion to the resist film to the substrate is formed using a resist composition containing the component (A1). It also contributes to the improvement of lithography characteristics such as sensitivity, resolution, exposure margin (EL margin), LWR (line with roughness), LER (line edge roughness) and mask reproducibility.

The "-SO ₂ - containing cyclic group" means, -SO ₂ during the ring backbone - represents a cyclic group containing a ring containing, specifically, -SO ₂ - sulfur atom (S) is in the ring It is a cyclic group which forms part of the ring skeleton of a mold group.

In a -SO ₂ -containing cyclic group, a ring containing -SO ₂ -is counted as the first ring in the ring skeleton thereof, and in the case of only the ring, a monocyclic group and in addition to the other ring structure, Regardless, it is called a polycyclic mold.

The -SO ₂ -containing cyclic group may be monocyclic or polycyclic.

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

-SO ₂ - containing cyclic group is particularly preferably a carbon number of 3-30 is preferable, and 4 to 20 is preferable, and more preferably from 4 to 15, 4-12. However, the carbon number is the number of carbon atoms constituting the ring skeleton and does not include the carbon number in the substituent.

The -SO ₂ -containing cyclic group may be a -SO ₂ -containing aliphatic cyclic group or a -SO ₂ -containing aromatic cyclic group. Preferably an —SO ₂ — containing aliphatic cyclic group.

Examples of the -SO ₂ -containing aliphatic cyclic group include groups in which at least one hydrogen atom is removed from an aliphatic hydrocarbon ring in which part of the carbon atoms constituting the ring skeleton is substituted with -SO ₂ -or -O-SO _2- . have. More specifically, -CH ₂ constituting the ring skeleton - is -SO ₂ - -CH ₂ constituting the group, the ring at least one of removing the hydrogen atom from the aliphatic hydrocarbon ring is substituted by -CH ₂ - is - O-SO ₂ - group and at least one removing a hydrogen atom from an aliphatic hydrocarbon ring substituted with, and the like.

It is preferable that carbon number is 3-20, and, as for this alicyclic hydrocarbon group, it is more preferable that it is 3-12.

The alicyclic hydrocarbon group may be polycyclic or monocyclic. As a monocyclic alicyclic hydrocarbon group, the group remove | excluding two hydrogen atoms from the C3-C6 monocycloalkane is preferable, Cyclopentane, cyclohexane, etc. can be illustrated as this monocycloalkane. As the polycyclic alicyclic hydrocarbon group, a group in which two hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms is preferable, and specifically, as the polycycloalkane, adamantane, norbornane, isobornane or tri Cyclodecane, tetracyclo dodecane, etc. are mentioned.

The -SO ₂ -containing cyclic group may have a substituent. As the substituent, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (= O), -COOR ", -OC (= O) R" (R "is a hydrogen atom or an alkyl group) , Hydroxyalkyl group, cyano group and the like.

As an alkyl group as this substituent, a C1-C6 alkyl group is preferable. The alkyl group is preferably a linear or branched chain. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl and hexyl. Among them, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

As an alkoxy group as this substituent, a C1-C6 alkoxy group is preferable. The alkoxy group is preferably a linear or branched chain. Specifically, there can be mentioned a group in which an oxygen atom (-O-) is bonded to an alkyl group exemplified as an alkyl group as the above substituent.

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

The halogenated alkyl group of the substituent includes a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom.

As a halogenated alkyl group as this substituent, the group by which one part or all hydrogen atoms of the alkyl group illustrated as the alkyl group as said substituent were substituted by the said halogen atom is mentioned. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

It is preferable that all R "in the said -COOR" and -OC (= O) R "are a hydrogen atom or a C1-C15 linear, branched or cyclic alkyl group.

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 preferably 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, the substituent is substituted with a fluorine atom or a fluorinated alkyl group. The group which removed 1 or more hydrogen atoms from polycycloalkane, such as monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane which may or may not be mentioned, etc. can be illustrated. And monocycloalkanes such as pentane and cyclohexane, and groups in which one or more hydrogen atoms are removed from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. .

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

Specific examples of the -SO ₂ -containing cyclic group include groups represented by the following General Formulas (3-1) to (3-4).

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[Wherein, A 'is an oxygen atom or containing a sulfur atom and having 1 to 5 carbon atoms alkylene group, which optionally an oxygen atom or a sulfur atom, z is an integer of 0 ~ 2, R ⁶ is an alkyl group, an alkoxy group, a halogenated Alkyl group, hydroxyl group, -COOR ", -OC (= O) R", a hydroxyalkyl group or a cyano group, and R "is a hydrogen atom or an alkyl group]

In the general formulas (3-1) to (3-4), A 'represents an alkyl atom having 1 to 5 carbon atoms, an oxygen atom or an oxygen atom (-O-) or a sulfur atom (-S-); Sulfur atom.

As a C1-C5 alkylene group in A ', a linear or branched alkylene group is preferable, and a methylene group, ethylene group, n-propylene group, isopropylene group, etc. are mentioned.

When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include a group in which -O- or -S- is interposed between the terminal or carbon atom of the alkylene group, for example -O -CH _2- , -CH ₂ -O-CH _2- , -S-CH _2- , -CH ₂ -S-CH ₂ -and the like.

As A ', a C1-C5 alkylene group or -O- is preferable, A C1-C5 alkylene group is more preferable, and a methylene group is the most preferable.

z may be any of 0-2, and 0 is the most preferable.

When z is 2, some R <^6> may be the same respectively and may differ.

The alkyl group, alkoxy group, halogenated alkyl group, -COOR ", -OC (= O ) R", hydroxy alkyl group in R ⁶ are, respectively, -SO ₂ In the above-exemplified as the substituent-containing cyclic group which may have The same thing as an alkyl group, an alkoxy group, a halogenated alkyl group, -COOR ", -OC (= O) R", and a hydroxyalkyl group is mentioned.

Below, the specific cyclic group represented by the said General Formula (3-1)-(3-4) is illustrated. In addition, "Ac" in a formula represents an acetyl group.

[Formula 62]

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&Lt; EMI ID =

(65)

[Formula 66]

-SO ₂ - containing cyclic group include, among the above, preferably a group represented by the general formula (3-1), and the above formula (3-1-1), (3-1-18), (3-3- It is more preferable to use at least 1 sort (s) chosen from the group which consists of groups represented by either 1) and (3-4-1), and the group represented by the said General formula (3-1-1) is the most preferable.

More specifically, examples of the structural unit (a0) include structural units represented by the following general formula (a0-0).

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[Wherein R is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, R ³⁰ is a -SO ₂ -containing cyclic group, and R ^{29 '} is a single bond or a divalent linking group]

In formula (a0-0), R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group.

The alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, 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.

The halogenated alkyl group in R is a group in which part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

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 the most preferable from industrial availability.

In formula (a0-0), R ³⁰ is the same as the -SO ₂ -containing cyclic group exemplified above.

R ^{29 '} may be either a single bond or a divalent linking group. It is preferable that it is a bivalent coupling group from the point which is excellent in the effect of this invention.

Examples of the divalent linking group for R ^{29 ′} include those similar to those exemplified as the divalent linking group for Y ² in General Formula (a1-0-2) exemplified in the description of the structural unit (a1) described above. Can be.

As the divalent linking group for R ^{29 ′} , an alkylene group, a divalent alicyclic hydrocarbon group or a divalent linking group containing a hetero atom is preferable. Among these, it is preferable that an alkylene group and ester bond (-C (= O) -O-) are included.

The alkylene group is preferably a linear or branched alkylene group. Specifically, the Y ² aliphatic hydrocarbon group which alkylene group of linear as illustrated in, there may be mentioned the same alkylene group of branched.

Preferred is represented by ^{-R 20 -C (= O) -O-} [ wherein, R ²⁰ is 2-valent connecting group]: a bivalent connecting group containing an ester bond, in particular, the general formula. That is, it is preferable that a structural unit (a0) is a structural unit represented with the following general formula (a0-0-1).

(68)

[Wherein R is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, R ²⁰ is a divalent linking group, and R ³⁰ is a -SO ₂ -containing cyclic group]

It does not specifically limit as R <^20> , For example, the same thing as what was illustrated as a bivalent coupling group in R <^{29> '} in said general formula (a0-0) is mentioned.

As the divalent linking group for R ²⁰ , a linear or branched alkylene group, a divalent alicyclic hydrocarbon group, or a divalent linking group containing a hetero atom is preferable.

As the linear or branched alkylene group, the divalent alicyclic hydrocarbon group, and the divalent linking group containing a hetero atom, each of the linear or branched chains exemplified as the above-mentioned R ^{29 '} is preferable. The same thing as an alkylene group, a bivalent alicyclic hydrocarbon group, and a bivalent coupling group containing a hetero atom is mentioned.

Among the above, a linear or branched alkylene group or a divalent linking group containing an oxygen atom as a hetero atom is preferable.

As a linear alkylene group, a methylene group or an ethylene group is preferable and a methylene group is especially preferable.

As the branched alkylene group, an alkylmethylene group or an alkylethylene group is preferable, and -CH (CH ₃ )-, -C (CH ₃ ) ₂ -or -C (CH ₃ ) ₂ CH ₂ -is particularly preferable. .

As the divalent linking group containing an oxygen atom, a divalent linking group containing an ether bond or an ester bond is preferable, and the above formula -Y ²¹ -OY ^22- , formula-[Y ²¹ -C (= O) -O] _{The group} represented by m'-Y ²² -or the formula -Y ²¹ -OC (= O) -Y ²² -is more preferable. Y ²¹ , Y ²² , and m, are the same as above.

Of these, formula ^{-Y 21 -OC (= O) -Y} 22 - group is preferably represented by the formula _{- (CH 2) c -OC (} = O) - group is particularly preferably represented by - (CH _{2) d.} c is an integer of 1-5, the integer of 1-3 is preferable, and 1 or 2 is more preferable. d is an integer of 1-5, the integer of 1-3 is preferable, and 1 or 2 is more preferable.

Especially as a structural unit (a0), the structural unit represented by the following general formula (a0-0-11) or (a0-0-12) is preferable, and the structural unit represented by a formula (a0-0-12) is more preferable. desirable.

[Formula 69]

[Wherein R, A ', R ⁶ , z and R ²⁰ are the same as above]

In Formula (a0-0-11), A 'is preferably a methylene group, an ethylene group, an oxygen atom (-O-), or a sulfur atom (-S-).

As R ²⁰ , a linear or branched alkylene group or a divalent linking group containing an oxygen atom is preferable. As a divalent coupling group containing a linear or branched alkylene group and an oxygen atom in R <^20> , each containing the linear or branched alkylene group and oxygen atom which were illustrated above is respectively. The same thing as a coupler is mentioned.

As a structural unit represented by a formula (a0-0-12), the structural unit represented by the following general formula (a0-0-12a) or (a0-0-12b) is especially preferable.

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[Wherein R and A 'are the same as above, c and d are the same as above, and f is an integer of 1 to 5 (preferably an integer of 1 to 3)]

The structural unit (a0) contained in the component (A1) may be one type or two or more types.

The ratio of the structural unit (a0) in the component (A1) has a good shape of the resist pattern formed by using the resist composition containing the component (A1), and is also excellent in lithography characteristics such as EL margin, LWR, and mask reproducibility. It is preferable that it is 1-60 mol% with respect to the sum total of all the structural units which comprise (A1) component, 5-55 mol% is more preferable, 10-50 mol% is still more preferable, 15-45 Mol% is most preferred.

[Structural unit (a2)]

Structural unit (a2) is a structural unit containing a lactone containing cyclic group as a 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.

Here, a lactone containing cyclic group represents the cyclic group containing one ring (lactone ring) containing a -O-C (= O)-structure. The lactone ring is counted as the first ring, and in the case of only the lactone ring, it is called a polycyclic group irrespective of the structure when the lactone ring has only another ring structure.

When the (A1) component is used for formation of a resist film, the lactone cyclic group of a structural unit (a2) improves adhesiveness with respect to the board | substrate of a resist film, or has a close relationship with the developing solution (especially in the case of an alkaline developing process) containing water. It is useful for raising Mars.

The structural unit (a2) is not particularly limited, and any one can be used.

Specifically, as a lactone containing monocyclic group, group which removed one hydrogen atom from 4-6 membered ring lactone, for example, group which removed one hydrogen atom from (beta) -propionolactone, hydrogen from (gamma) -butyrolactone The group which removed one hydrogen atom from group which removed one atom, and (delta) -valerolactone is mentioned. Moreover, as a lactone containing polycyclic type group, the group remove | excluding one hydrogen atom from bicycloalkane, tricycloalkane, and tetracycloalkane which has a lactone ring is mentioned.

More specifically, examples of the structural unit (a2) include structural units represented by general formulas (a2-1) to (a2-5) shown below.

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[Wherein R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; R 'is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -COOR ", and R" is hydrogen An atom or an alkyl group; R ²⁹ is a single bond or a divalent linking group, s "is an integer of 0 or 1 to 2; A" is an alkyl group of 1 to 5 carbon atoms or oxygen containing an oxygen atom or a sulfur atom; An atom or a sulfur atom; m is an integer of 0 or 1;

R in general formula (a2-1) (a2-5) is the same as R in the said structural unit (a1).

As a C1-C5 alkyl group of R ', a methyl group, an ethyl group, a propyl group, n-butyl group, tert- butyl group is mentioned, for example.

As a C1-C5 alkoxy group of R ', a methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group is mentioned, for example.

In consideration of the fact that R 'is readily available industrially, a hydrogen atom is preferable.

R "is preferably a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms.

When R "is a linear or branched alkyl group, it is preferable that it is C1-C10, and it is more preferable that it is C1-C5.

When R ″ is a cyclic alkyl group, it is preferably 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, the substituent is substituted with a fluorine atom or a fluorinated alkyl group. Monocycloalkane which may or may not be used; groups in which one or more hydrogen atoms have been removed from polycycloalkane such as bicycloalkane, tricycloalkane, tetracycloalkane, etc. may be exemplified. And monocycloalkanes such as cyclohexane, and groups in which one or more hydrogen atoms have been removed from polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

As A ", a C1-C5 alkylene group or -O- is preferable, A C1-C5 alkylene group is more preferable, and a methylene group is the most preferable.

R ²⁹ is a single bond or a divalent linking group. The divalent linking group is the same as the divalent linking group described for Y ² in General Formula (a1-0-2), and among them, an alkylene group, an ester bond (-C (= O) -O-), or those It is preferable that it is a combination. The alkylene group as the divalent linking group for R ²⁹ is more preferably a linear or branched alkylene group. Specifically, the Y ² aliphatic hydrocarbon group which alkylene group of linear exemplified in, those similar to the alkylene groups of the branched.

s "is preferably an integer of 1 to 2.

Specific examples of the structural units represented by general formulas (a2-1) to (a2-5) are shown below.

In the following formulas, R ^{? Represents} a hydrogen atom, a methyl group or a trifluoromethyl group.

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(73)

&Lt; EMI ID =

(75)

[Formula 76]

The structural unit (a2) contained in the component (A1) may be one type or two or more types.

As the structural unit (a2), at least one member selected from the group consisting of structural units represented by general formulas (a2-1) to (a2-5) is preferable, and general formulas (a2-1) to (a2-3) It is more preferable than at least 1 sort (s) chosen from the group which consists of structural units represented by the following. Among them, the formulas (a2-1-1), (a2-1-2), (a2-2-1), (a2-2-7), (a2-3-1) and (a2-3-5) It is preferable to use at least 1 sort (s) chosen from the group which consists of structural units represented by ().

As for the ratio of the structural unit (a2) in (A1) component, 5-60 mol% is preferable with respect to the total of all the structural units which comprise (A1) component, 10-50 mol% is more preferable, 10- 45 mol% is more preferable.

By making ratio of a structural unit (a2) more than a lower limit, the effect by containing a structural unit (a2) is fully acquired, and it becomes easy to balance with another structural unit by setting it below an upper limit.

[Structural unit (a3)]

The structural unit (a3) is a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α position may be substituted with a substituent, and a structural unit containing a polar group-containing aliphatic hydrocarbon group (however, the structural unit (a1) described above, (a0), (a2); structural unit (g ') and the structural unit (h') are excluded).

When (A1) component has a structural unit (a3), the hydrophilicity of (A) component becomes high and contributes to the improvement of resolution.

As a polar group, a hydroxyl group, a cyano group, a carboxyl group, the hydroxyalkyl group in which some hydrogen atoms of the alkyl group were substituted by the fluorine atom, etc. are mentioned, Especially a hydroxyl group is preferable.

As an aliphatic hydrocarbon group, a C1-C10 linear or branched hydrocarbon group (preferably alkylene group) and cyclic aliphatic hydrocarbon group (cyclic group) are mentioned. As the cyclic group, a monocyclic group or a polycyclic group may be used. For example, in the resin for the resist composition for ArF excimer laser, it can select suitably from a lot of what is proposed, and can use. It is preferable that it is a polycyclic group as this cyclic group, and it is more preferable that carbon number is 7-30.

Especially, the structural unit derived from the acrylate ester containing the aliphatic polycyclic group containing the hydroxyalkyl group in which one part of the hydrogen atoms of a hydroxyl group, a cyano group, a carboxyl group, or an alkyl group substituted by a fluorine atom is more preferable. Examples of the polycyclic group include groups in which two or more hydrogen atoms have been removed from bicycloalkane, tricycloalkane, tetracycloalkane, and the like. Specifically, the group remove | excluding two or more hydrogen atoms from polycycloalkane, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclo dodecane, etc. are mentioned. Among these polycyclic groups, a group in which two or more hydrogen atoms are removed from adamantane, a group in which two or more hydrogen atoms are removed from norbornane, and a group in which two or more hydrogen atoms are removed from tetracyclododecane are industrially preferable.

As the structural unit (a3), when the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a structural unit derived from hydroxyethyl ester of acrylic acid is preferable. When a hydrocarbon group is a polycyclic group, the structural unit represented by a following formula (a3-1), the structural unit represented by a formula (a3-2), and the structural unit represented by a formula (a3-3) are mentioned as a preferable thing.

[Formula 77]

(Wherein R is the same as above, j is an integer of 1 to 3, k is an integer of 1 to 3, t ＇is an integer of 1 to 3, l is an integer of 1 to 5, and s is Is an integer from 1 to 3)

In formula (a3-1), j is preferably 1 or 2, more preferably 1. When j is 2, it is preferable that the hydroxyl group couple | bonds with the 3rd and 5th positions of an adamantyl group. When j is 1, it is preferable that the hydroxyl group couple | bonds with the 3-position of an adamantyl group.

It is preferable that j is 1, and it is especially preferable that the hydroxyl group couple | bonds with the 3-position of an adamantyl group.

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

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

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

It is preferable that it is 5-50 mol% with respect to the total of all the structural units which comprise the said (A1) component, and, as for the ratio of a structural unit (a3) in (A1) component, 5-40 mol% is more preferable. , 5-25 mol% is more preferable.

By making ratio of a structural unit (a3) more than a lower limit, the effect by containing a structural unit (a3) is fully acquired, and it becomes easy to balance with another structural unit by setting it below an upper limit.

[Constituent unit (g ＇)]

The structural unit (g ') contained in the component (A1) may be one type or two or more types.

0.1-30 mol% is preferable with respect to the total of all the structural units which comprise the said (A1) component, and, as for the ratio of a structural unit (g '), in a component (A1), 0.5-15 mol% is more preferable. , 1 to 10 mol% is more preferable.

By making ratio of a structural unit (g ') more than a lower limit, the effect of acid diffusion control becomes high, and a lithographic characteristic or a resist pattern shape becomes more favorable. On the other hand, it becomes easy to balance with the other structural unit by using below an upper limit.

[Constituent unit (h ＇)]

The structural unit (h ') contained in the component (A1) may be one type or two or more types.

0.1-30 mol% is preferable with respect to the total of all the structural units which comprise the said (A1) component, and, as for the ratio of a structural unit (h ') in (A1) component, 0.5-15 mol% is more preferable. , 1 to 10 mol% is more preferable.

By making ratio of a structural unit (h ') more than a lower limit, the dimensional fluctuation of a resist pattern by the influence of time progress is suppressed more. On the other hand, it becomes easy to balance with the other structural unit by using below an upper limit.

[Other structural units]

The component (A1) is a structural unit (a1), a structural unit (a0), a structural unit (a2), a structural unit (a3), a structural unit (g ') and a structure within a range that does not impair the effects of the present invention. You may have other structural units other than a unit (h ').

Such other structural units are not particularly limited as long as they are structural units not classified in the above-described structural units, and are used for resist resins such as for ArF excimer lasers and KrF excimer lasers (preferably for ArF excimer lasers). Many known ones can be used as these.

As such other structural units, the structural unit (a4) containing an acid-non-dissociable aliphatic polycyclic group as a 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, and exposure to The structural unit (a5) etc. which can generate | occur | produce acid can be mentioned.

(Constituent unit (a4))

Structural unit (a4) is a 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, and is a structural unit containing an acid non-dissociable aliphatic polycyclic group.

In the structural unit (a4), the polycyclic group can exemplify the same as the polycyclic type group exemplified in the case of the structural unit (a1), for ArF excimer laser, KrF excimer laser ( Preferably, a large number of conventionally known ones can be used as the resin component of a resist composition such as ArF excimer laser).

In particular, at least one surface selected from tricyclodecyl group, adamantyl group, tetracyclododecyl group, isobornyl group and norbornyl group is preferable in view of industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specifically as a structural unit (a4), the thing of the structure represented by the following general formula (a4-1) (a4-5) can be illustrated.

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(Wherein R is the same as above)

When including such a structural unit (a4) in (A1) component, it is preferable to contain 1-30 mol% of structural units (a4) with respect to the total of all the structural units which comprise (A1) component, and it is 10- It is more preferable to make it contain 20 mol%.

(The constituent unit (a5))

Structural unit (a5) is a structural unit which can generate an acid by exposure.

The structural unit (a5) is not particularly limited as long as it generates an acid by exposure, and for example, conventional chemical amplification to a structural unit copolymerizable with the structural units (a1) to (a4), (a0) and the like described above. As the acid generator for the type resist, those which have been proposed can be used.

As a structural unit copolymerizable with a structural unit (a1)-(a4), (a0) etc., 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, and the carbon atom of the (alpha) position The structural unit derived from the hydroxy styrene which the couple | bonded hydrogen atom may be substituted by the substituent is mentioned as a preferable thing.

As what is conventionally proposed as an acid generator for chemically amplified resists, the component (B) mentioned later is mentioned as a preferable thing.

As a structural site which generate | occur | produces an acid by exposure in a structural unit (a5), it is preferable that it is an ionic structural site, and in the sulfonium salt or iodonium salt which are illustrated in description about (B) component mentioned later, The ionic structural site of is preferred. As acid anions generated by exposure, sulfonic acid anions, carboxylic acid anions, sulfonyl imide anions, bis (alkylsulfonyl) imide anions, tris (alkylsulfonyl) methed anions On is preferred. As for these acid anions, it is more preferable to generate | occur | produce from the side chain of resin by exposure.

Especially, the structural unit (a5) of this invention has a group represented by the following general formula (a5-1-1) or (a5-2-1) in terms of acid strength, sensitivity, resolution, and roughness. desirable.

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[And of, A is a single bond or a divalent connecting group formula, R ⁴⁴ is an arylene group which may have a substituent, R ^45, R ⁴⁶ is in each independently an organic group, R ^45, R ⁴⁶ are combined with each other expression It may form a ring with a sulfur atom, X <^-> is a counter anion, R <^f1> , R <^f2> are respectively independently a hydrogen atom, an alkyl group, a fluorine atom, or a fluorinated alkyl group, and at least 1 of R <^f1> , R <^f2> Is a fluorine atom or a fluorinated alkyl group, n "is an integer of 1 to 8, M ^{r +} is a counter cation, and r is an integer of 1 to 3]

In formula (a5-1-1) or (a5-2-1), A is a single bond or a divalent linking group.

As a bivalent coupling group of A, the bivalent hydrocarbon group which may have a substituent, the bivalent coupling group containing a hetero atom, etc. are mentioned as a preferable thing.

The hydrocarbon group "having a substituent" means that part or all of the hydrogen atoms in the hydrocarbon group are substituted with groups or atoms other than hydrogen atoms.

The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.

The aliphatic hydrocarbon group may be saturated or unsaturated, and in general, the aliphatic hydrocarbon group is preferably saturated.

More specifically, as said aliphatic hydrocarbon group, a linear or branched aliphatic hydrocarbon group, the aliphatic hydrocarbon group containing a ring in a structure, etc. are mentioned.

The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, still more preferably 1 to 5, and most preferably 1 to 2 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.

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- ; 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 ) Alkyl ethylene groups such as ₂ -CH _2- ; alkyltrimethylene groups such as -CH (CH ₃ ) CH ₂ CH _2- , -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.

The chain aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O), and the like.

As an aliphatic hydrocarbon group containing a ring in the structure, a cyclic aliphatic hydrocarbon group (a group in which two hydrogen atoms are removed from an aliphatic hydrocarbon ring), and the cyclic aliphatic hydrocarbon group is bonded to the terminal of the chain aliphatic hydrocarbon group described above. Or a group interposed in the middle of the chain aliphatic hydrocarbon group.

It is preferable that it is 3-20, and, as for a cyclic aliphatic hydrocarbon group, it is more preferable that it is 3-12.

The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic group, a group in which two hydrogen atoms have been removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and as the monocycloalkane, cyclopentane, cyclohexane and the like can be exemplified. As the polycyclic group, a group in which two hydrogen atoms are removed from a polycycloalkane having 7 to 12 carbon atoms is preferable, and specifically, as the polycycloalkane, adamantane, norbornane, isobornane, tricyclodecane, tetra Cyclododecane etc. are mentioned.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. As a substituent, a C1-C5 alkyl group, a fluorine atom, a C1-C5 fluorinated alkyl group substituted by the fluorine atom, an oxygen atom (= O), etc. are mentioned.

As said aromatic hydrocarbon group, For example, aromatic of monovalent aromatic hydrocarbon groups, such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, a phenanthryl group, etc. A divalent aromatic hydrocarbon group in which one hydrogen atom is further removed from the hydrocarbon core; an aromatic hydrocarbon in which a part of the carbon atoms constituting the ring of the divalent aromatic hydrocarbon group is substituted with a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom Group; an arylalkyl group such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, and the like, and a hydrogen atom is added from the nucleus of the aromatic hydrocarbon. The aromatic hydrocarbon group etc. which one removed were mentioned.

The aromatic hydrocarbon group may or may not have a substituent. As a substituent, a C1-C5 alkyl group, a fluorine atom, a C1-C5 fluorinated alkyl group substituted by the fluorine atom, an oxygen atom (= O), etc. are mentioned.

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

As a divalent linking group containing a hetero atom, specifically, -O-, -C (= O)-, -C (= O) -O-, a carbonate bond (-OC (= O) -O-),- there may be mentioned, = N-, etc. - NH-, -NR ⁰⁵ (R ⁰⁵ is alkyl) -, -NH-C (= O). Moreover, the combination etc. of these "bivalent coupling groups containing a hetero atom" and a bivalent hydrocarbon group are mentioned. As a divalent hydrocarbon group, the same thing as the hydrocarbon group which may have the substituent mentioned above is mentioned, A linear or branched aliphatic hydrocarbon group is preferable.

A may or may not have an acid dissociable site | part in the structure. An "acid dissociable site | part" means the site | part which the acid generate | occur | produced by exposure in the said organic group acts and dissociates. In the case where A has an acid dissociable moiety, it is preferable to have an acid dissociable moiety having a tertiary carbon atom.

As the divalent linking group for A, a divalent linking group containing an alkylene group, a divalent aliphatic cyclic group or a hetero atom is preferable.

When A is an alkylene group, the alkylene group is preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. Specifically, the same thing as the linear alkylene group and the branched alkylene group which were illustrated above are mentioned.

When A is a divalent aliphatic cyclic group, the aliphatic cyclic group may be the same as the cyclic aliphatic hydrocarbon group exemplified in the above "aliphatic hydrocarbon group containing a ring in structure".

The aliphatic cyclic group is particularly preferably a group in which two or more hydrogen atoms are removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane and tetracyclododecane.

When A 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- (H may be substituted with a substituent such as an alkyl group, acyl group), -S-, -S (= O) _2- , -S (= O) there may be mentioned [A'-C (= O) -O] m ' group represented by -B'-, etc. - ₂ -O-, a group represented by formula -A'-OB'-, expression. Here, A 'and B' are each independently a divalent hydrocarbon group which may have a substituent, and m 'is an integer of 0-3.

When A is -NH-, H may be substituted by 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.

-A'-OB'- or _-, according to -B'-, A '[A'-C (= O) -O] m , and B' is a divalent hydrocarbon group which may have a substituent, each independently.

As a bivalent hydrocarbon group which may have a substituent in A 'and B', the same thing as what was illustrated above as "the divalent hydrocarbon group which may have a substituent" in A is mentioned.

As A ', 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 B ', 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, a linear alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is most preferred.

In addition, expression-a [A'-C (= O) -O] m ' in groups represented by -B'-, m' is an integer from 0 to 3, and an integer of 0 to 2, preferably 0 or 1, More preferably, 1 is the most preferable.

In the present invention, A is preferably a single bond or an ester bond [-C (= O) -O-], an ether bond (-O-), an alkylene group or a combination thereof. Among these, an alkylene group is particularly preferred. desirable.

In formula (a5-1-1), R ⁴⁴ is an arylene group which may have a substituent. One or two substituents may be sufficient.

There is no restriction | limiting in particular as an arylene group of R <^44> , For example, as an C6-C20 arylene group, the arylene group may replace part or all of the hydrogen atoms. For example, it may or may not be substituted with an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, or the like.

As such an arylene group, a C6-C10 arylene group is preferable at the point which can be synthesize | combined cheaply. Specifically, a phenylene group and a naphthylene group are mentioned, for example, A phenylene group is especially preferable.

As an alkyl group which the hydrogen atom of the said arylene group may be substituted, a C1-C5 alkyl group is preferable, It is more preferable that they are a methyl group, an ethyl group, a propyl group, n-butyl group, and a tert- butyl group, and a methyl group is especially preferable. .

As an alkoxy group which the hydrogen atom of the said arylene group may substitute, the C1-C5 alkoxy group is preferable, and a methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butok It is more preferable that it is time.

As a halogen atom in which the hydrogen atom of the said arylene group may be substituted, it is preferable that it is a fluorine atom.

In formula (a5-1-1), R ⁴⁵ and R ⁴⁶ are each independently an organic group.

The organic group of R ⁴⁵ and R ⁴⁶ is a group containing a carbon atom, and atoms other than the carbon atom (for example, hydrogen atom, oxygen atom, nitrogen atom, sulfur atom, halogen atom (fluorine atom, chlorine atom, etc.)) You may have it.

As an organic group of R <^45> , R <^46> , an aryl group or an alkyl group is preferable.

There is no restriction | limiting in particular as an aryl group of R <^45> , R <^46> , For example, as a C6-C20 aryl group, the aryl group may replace part or all of the hydrogen atoms. For example, it may or may not be substituted with an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, or the like.

As such an aryl group, a C6-C10 aryl group is preferable at the point which can be synthesize | combined cheaply. Specifically, a phenyl group and a naphthyl group are mentioned, for example, A phenyl group is especially preferable.

Examples of the alkyl group, alkoxy group and halogen atom in which the hydrogen atom of the aryl group may be substituted include the same ones as the alkyl group, alkoxy group and halogen atom in which the arylene group of R ⁴⁴ may be substituted.

There is no restriction | limiting in particular as an alkyl group of R <^45> , R <^46> , For example, a C1-C10 linear, branched or cyclic alkyl group etc. are mentioned. It is preferable that it is C1-C5 from the point which is excellent in resolution. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, decanyl group, etc. are mentioned. Can be. Especially, a methyl group is mentioned at the point which is excellent in resolution and can be synthesize | combined cheaply.

In formula (a5-1-1), R <^45> , R <^46> may combine with each other and may form the ring with the sulfur atom in a formula.

In such a case, it is preferable to form a 3-10 membered ring by including a sulfur atom, and it is especially preferable to form a 5-7 membered ring.

The ring structure formed with the sulfur atom may contain a hetero atom such as a sulfur atom and an oxygen atom (-O-, = O).

Specific examples of the ring to be formed include, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene Ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolidine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, qui Nolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazolin ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, thian A tren ring, a chromen ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring, a phenazine ring, and the like.

In formula (a5-1-1), X <^-> is a counter anion.

It does not specifically limit as a counter anion of X <^-> , The anion part (R4 ^" of onium salt type acid generator represented by general formula (b-1) or (b-2) in (B) component mentioned later). SO ₃ ^-); in the component (b) to be described later, the general formula (b-3) or (b-4) and the like not shown by-one, in particular R ^{4 "SO} ₃ ^- is preferable, and a carbon number of 1 It is preferable that it is at least 1 sort (s) chosen from -8 fluorinated alkyl sulfonic acid ion (preferably C1-C4) or general formula (b1)-(b8) mentioned later.

In formula (a5-2-1), R ^f1 and R ^f2 are each independently a hydrogen atom, an alkyl group, a fluorine atom, or a fluorinated alkyl group, and at least one of R ^f1 and R ^f2 is a fluorine atom or a fluorinated alkyl group.

As an alkyl group of R <^f1> , R <^f2> , a C1-C5 alkyl group is preferable, Specifically, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, tert- butyl group, a pen Tyl group, isopentyl group, neopentyl group, etc. are mentioned.

A fluorinated alkyl group of R ^f1, R ^f2, the R ^f1, is preferably a part or all of the hydrogen atoms of the alkyl group of R ^f2 fluorine atoms.

In the present invention, R ^f1 and R ^f2 are preferably fluorine atoms.

In formula (a5-2-1), n "is an integer of 1-8, it is preferable that it is an integer of 1-4, and it is more preferable that it is 1 or 2.

In formula (a5-2-1), M ^{r +} is a counter cation, and r is an integer of 1-3.

As a counter cation of M < ^{r +>} , a metal cation or an onium cation is mentioned.

Examples of the metal ions of M ^{r +} include alkali metal ions such as sodium, potassium and lithium, alkaline earth metal ions such as magnesium and calcium, iron ions and aluminum ions. Especially, since ion exchange with respect to a sulfonate is easy, sodium ion, potassium ion, and lithium ion are preferable.

As onium cation of M < ^{r +>} , sulfonium cation, iodonium cation, phosphonium cation, diazonium cation, ammonium cation, pyridinium cation, etc. are mentioned. Especially, it is preferable that it is the same as the cation part of the onium salt type acid generator represented by general formula (b-1) or (b-2) in (B) component mentioned later.

Specific examples of the group represented by the formula (a5-1-1) or (a5-2-1) are shown below.

(80)

[Formula 81]

(82)

(83)

[Formula 84]

(85)

The structural unit (a5) of the present invention is, in particular, a structural unit represented by the following general formula (a5-1) in view of acid strength, sensitivity, resolution, roughness, ease of synthesis, or the following general formula (a5). It is preferable that it is a structural unit represented by -2).

&Lt; EMI ID =

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. A is a single bond or a divalent linking group. R ⁴⁴ is an arylene group which may have a substituent. R ⁴⁵ and R ⁴⁶ are each independently an organic group, and R ⁴⁵ and R ⁴⁶ may be bonded to each other to form a ring together with a sulfur atom in the formula. X ^- is the counter anion. R ^f1 and R ^f2 are each independently a hydrogen atom, an alkyl group, a fluorine atom, or a fluorinated alkyl group, and at least one of R ^f1 and R ^f2 is a fluorine atom or a fluorinated alkyl group. n "is an integer from 1 to 8. M ^{r +} is a counter cation, r is an integer from 1 to 3.]

In formulas (a5-1) and (a5-2), R is the same as above and preferably represents a hydrogen atom or a methyl group.

In formulas (a5-1) and (a5-2), A, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , X ⁻ , R ^f1 , R ^f2 , n ″, M ^{r +} and r are the formulas (a5-), respectively. 1-1) and A, R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , X ⁻ , R ^f1 , R ^f2 , n ″, M ^{r +} and r in (a5-2-1).

When including such a structural unit (a5) in (A1) component, it is preferable to contain 1-40 mol% of structural units (a5) with respect to the sum total of all the structural units which comprise (A1) component, and it is 1- It is more preferable to contain 35 mol%, and it is still more preferable to contain 3-30 mol%. By setting it to more than a lower limit, roughness is reduced more, and lithographic characteristics improve. By using below an upper limit, the balance with another structural unit can be taken.

In the resist composition of the present invention, the component (A) preferably contains a polymer (A1) having a structural unit (a1).

Specifically as a (A1) component, the copolymer (A1-11-1) which consists of a structural unit (a1), a structural unit (a2), and a structural unit (a3); a structural unit (a1), a structural unit (a0), and Copolymer (A1-11-2) which consists of a structural unit (a3); Copolymer (A1-12- consisting of a structural unit (a1), a structural unit (a0), a structural unit (a3), and a structural unit (g '). 1); copolymer (A1-13-1) consisting of a structural unit (a1), a structural unit (a0), a structural unit (a3), and a structural unit (h '); a structural unit (a1) and a structural unit (a0) , Copolymer (A1-11-3) comprising structural unit (a2) and structural unit (a3); structural unit (a1), structural unit (a0), structural unit (a2), structural unit (a3) and structural unit copolymer (A1-12-2) consisting of (g '); a copolymer consisting of a structural unit (a1), a structural unit (a0), a structural unit (a2), a structural unit (a3) and a structural unit (h') (A1-13-2) etc. can be illustrated.

In (A) component, (A1) component may be used individually by 1 type, and may use 2 or more types together.

As (A1) component, for example, only the copolymer which does not have a structural unit (g ') or a structural unit (h') in the said illustration (copolymer (A1-11-1)-(A1-11-3 ), At least one copolymer having a structural unit (g ') (at least one of the copolymers (A1-12-1) and (A1-12-2)) and a structural unit (h') Only copolymers (at least one of copolymers (A1-13-1) and (A1-13-2)), or a combination thereof can be used.

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% is more preferable, 75 mass% is more preferable, 100 mass% It may be. If the ratio is 25 mass% or more, lithography characteristics such as MEF, exposure margin (EL margin), roughness reduction, and resist pattern shape are further improved.

The mass average molecular weight (Mw) (polystyrene conversion basis by gel permeation chromatography (GPC)) of (A1) component is not specifically limited, 1000-50000 are preferable, 1500-30000 are more preferable, 2000- 20000 is most preferred. If it is below the upper limit of the range, there is a solubility in a resist solvent sufficient for use as a resist. If the lower limit of the above range is exceeded, the dry etching resistance and the cross-sectional shape of the resist pattern are favorable.

Dispersion degree (Mw / Mn) is not specifically limited, 1.0-5.0 are preferable, 1.0-3.0 are more preferable, 1.0-2.5 are the most preferable. In addition, Mn represents a number average molecular weight.

(A1) A component can be obtained by superposing | polymerizing the monomer which guide | induces each structural unit by well-known radical polymerization etc. using radical polymerization initiators, such as azobisisobutyronitrile (AIBN), for example.

In the component (A1), a chain transfer agent such as HS-CH ₂ -CH ₂ -CH ₂ -C (CF ₃ ) ₂ -OH is used in combination at the time of the polymerization, and thus, -C ( CF ₃ ) ₂ -OH group may be introduced. Thus, the copolymer into which the hydroxyalkyl group in which one part of the hydrogen atoms of the alkyl group was substituted by the fluorine atom was introduce | transduced is effective in reducing a developing defect and reducing LER (line edge roughness: uneven unevenness of a line side wall).

A commercially available monomer may be used as the monomer for inducing each structural unit, or may be synthesized using a known method.

(A) component may contain the base component (henceforth "(A2) component") whose polarity increases by action of an acid other than (A1) component in the range which does not impair the effect of this invention. .

When the resist composition of this invention is a resist composition which forms a positive resist pattern in an alkali developing process, and forms a negative resist pattern in a solvent developing process, as (A2) component, a molecular weight is 500 or more and less than 2500, You may use the low molecular weight compound which has the acid dissociative group and hydrophilic group as illustrated by description of the above-mentioned (A1) component. Specifically, the thing by which one part or all part of the hydrogen atom of the hydroxyl group of the compound which has a some phenol skeleton was substituted by the said acid dissociable group is mentioned.

As this low molecular weight compound, a part of the hydrogen atom of the hydroxyl group of the low molecular weight phenolic compound which is known as a sensitizer in a non-chemically amplified type g-ray or i-ray resist, and a heat resistance improving agent is substituted, for example with the said acid dissociable group. It is preferable to use it from that.

As the low molecular weight phenolic compound, for example, bis (4-hydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- ( 4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, tris (4-hydroxyphenyl Methane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4 -Hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4 -Hydroxy-3-methylphenyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl- 4-hydroxy-6-methylphenyl) -3,4-dihydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-high Hydroxyphenyl) ethyl] benzene, phenol, m- cresol, p- cresol or xylenol, etc., such as a formalin condensate of phenol nuclei 2-6 water. Of course, it is not limited to these. In particular, the phenolic compound which has 2-6 triphenylmethane skeletons is preferable at the point which is excellent in resolution and line edge roughness (LWR). The acid dissociable group is not particularly limited, and the above-mentioned ones may be mentioned.

What is necessary is just to adjust content of (A) component in the resist composition of this invention according to the resist film thickness to form.

<(B) component>

In the resist composition of the present invention, as the component (B), those which have been proposed as acid generators for chemically amplified resists can be used.

As such acid generators, onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and poly (bissulfonyl) Many kinds of diazomethane acid generators such as diazomethanes, nitrobenzyl sulfonate acid generators, iminosulfonate acid generators, and disulfone acid generators are known.

As an onium salt type acid generator, the compound represented by the following general formula (b-1) or (b-2) can be used, for example.

[Chemical Formula 87]

[In formula, R < ^{1 >} -R < ^{3 >} , R < ^{5 >} -R < ^{6 >>} respectively independently represents the aryl group, alkyl group, or alkenyl group which may have a substituent. In R < ^{1 >} -R <^3> in Formula (b-1), any two may combine with each other and may form a ring with the sulfur atom in a formula. R ^{4 "} represents an alkyl group, a halogenated alkyl group, an aryl group, or an alkenyl group which may have a substituent]

In the formula ^{(b-1), R 1} "~ R 3" are the same and each of R ^{1 "~} R ^3" in the above formula (g-c1).

In said formula (b-1), R < ^{4 >} represents the alkyl group, halogenated alkyl group, aryl group, or alkenyl group which may have a substituent.

The alkyl group for R ^{4 ″} may be any of linear, branched, and cyclic.

The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.

As said cyclic alkyl group, it is preferable that it is C4-C15, It is more preferable that it is C4-C10, It is most preferable that it is C6-C10.

Examples of the halogenated alkyl group for R ^{4 ″} include a group in which part or all of the hydrogen atoms of the linear, branched, or cyclic alkyl group are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom and a chlorine atom. Atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable.

In the halogenated alkyl group, the ratio (halogenation rate (%)) of the number of halogen atoms to the total number of halogen atoms and hydrogen atoms contained in the halogenated alkyl group is preferably from 10 to 100%, preferably from 50 to 100%. Preferably, 100% is the most preferable. The higher the halogenation rate is, the more preferable the acid strength becomes.

It is preferable that the aryl group in said R < ^{4 >>} is a C6-C20 aryl group.

It is preferable that the alkenyl group in said R < ^{4 >>} is a C2-C10 alkenyl group.

In the said R ^{4 "} ," you may have a substituent "means that part or all of the hydrogen atoms in the alkyl group, halogenated alkyl group, aryl group, or alkenyl group are substituted (atom or group other than hydrogen atom) as a substituent. It means that it may be substituted.

The number of substituents in R <^{4> "} may be one, and two or more may be sufficient as it.

Examples of the substituent include a halogen atom, a hetero atom, an alkyl group, and a formula: R ^X -Q ^1- [wherein, Q ¹ is a divalent linking group containing an oxygen atom, and R ^X may have a substituent. And a hydrocarbon group having 3 to 30 carbon atoms.

As said halogen atom and an alkyl group, the thing similar to what was illustrated as a halogen atom and an alkyl group in a halogenated alkyl group in R <^{4> "} is mentioned.

An oxygen atom, a nitrogen atom, a sulfur atom etc. are mentioned as said hetero atom.

In the group represented by R ^X -Q ^1- , Q ¹ is a divalent linking group containing an oxygen atom.

Q ¹ may contain atoms other than an oxygen atom. As atoms other than an oxygen atom, a carbon atom, a hydrogen atom, an oxygen 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 amide bond (-C (= O)- Hydrogen atom-containing oxygen atom-containing linking groups such as NH-), carbonyl bond (-C (= O)-), and carbonate bond (-OC (= O) -O-); And combinations of alkylene groups.

As the combination, for example, -R ⁹¹ -O-, -R ⁹² -OC (= O)-, -C (= O) -OR ⁹³ -OC (= O)-(wherein, R ⁹¹ to R ⁹³ each independently represents an alkylene group).

As an alkylene group in R <^91> -R <^93> , a linear or branched alkylene group is preferable, As for carbon number of this alkylene group, 1-12 are preferable, 1-5 are more preferable, 1 ~ 3 is particularly preferred.

Specifically as the alkylene group, for example, methylene group [-CH _2- ]; -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) _2- , -C ( Alkyl methylene groups such as CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, and -C (CH ₂ CH ₃ ) _2- ; ethylene group [-CH ₂ CH _2- ]; -CH (CH ₃ ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2-, etc. Alkylethylene group; trimethylene group (n-propylene group) [-CH ₂ CH ₂ CH _2- ]; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH _2- Alkyltrimethylene group; tetramethylene group [-CH ₂ CH ₂ CH ₂ CH _2- ]; -CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ CH _2- and the like - pentamethylene group _{[-CH 2 CH 2 CH 2 CH} 2 CH 2]; alkyl tetramethylene group.

As Q ¹ , a divalent linking group containing an ester bond or an ether bond is preferable, and among them, —R ⁹¹ —O—, —R ⁹² —OC (═O) — or —C (═O) —OR ⁹³ — OC (= O)-is preferred.

In the group represented by R ^X -Q ^1- , the hydrocarbon group of R ^X may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring. It is preferable that carbon number of this aromatic hydrocarbon group is 3-30, It is more preferable that it is 5-30, 5-20 are further more preferable, 6-15 are especially preferable, 6-12 are the most preferable. However, the carbon number does not include the carbon number in the substituent.

Specific examples of the aromatic hydrocarbon group include one hydrogen atom from an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, or a phenanthryl group. And arylalkyl groups such as aryl group, 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 alkyl chain in the said arylalkyl group is 1-4, It is more preferable that it is 1-2, It is especially preferable that it is 1.

The aromatic hydrocarbon group may have a substituent. For example, part of the carbon atoms constituting the aromatic ring possessed by the aromatic hydrocarbon group may be substituted with a hetero atom, or the hydrogen atom bonded to the aromatic ring possessed by the aromatic hydrocarbon group may be substituted with a substituent.

Examples of the former include a heteroaryl group in which a part of the carbon atoms constituting the ring of the aryl group is substituted with a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, and a part of the carbon atoms constituting the aromatic hydrocarbon ring in the arylalkyl group. The heteroaryl alkyl group in which the substituent was substituted by the said hetero atom is mentioned.

As a substituent of the aromatic hydrocarbon group in the latter example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (= O) etc. are mentioned, for example.

As an alkyl group as a substituent of the said aromatic hydrocarbon group, 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 as a substituent of the said aromatic hydrocarbon group, the C1-C5 alkoxy group is preferable, and a methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, and tert-butoxy group are preferable. And a methoxy group and an ethoxy group are most preferred.

As a halogen atom as a substituent of the said aromatic hydrocarbon group, 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 of the said aromatic hydrocarbon group, 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.

The aliphatic hydrocarbon group in R ^X may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be any of linear, branched and cyclic groups.

In R ^X , a part of the carbon atoms constituting the aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom in the aliphatic hydrocarbon group, and a part or all of the hydrogen atoms constituting the aliphatic hydrocarbon group contain a hetero atom. May be substituted.

As a "hetero atom" in R <^X> , if it is an atom other than a carbon atom and a hydrogen atom, it will not specifically limit, For example, a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. As a halogen atom, a fluorine atom, a chlorine atom, an iodine atom, a bromine atom, etc. are mentioned.

The substituent containing a hetero atom may consist only of the said hetero atom, and the group containing groups or atoms other than the said hetero atom may be sufficient.

As a substituent which substitutes a part of carbon atom, it is specifically -O-, -C (= O) -O-, -C (= O)-, -OC (= O) -O-, -C (= O) -NH-, -NH- (H may be substituted by substituents such as alkyl groups, acyl groups), -S-, -S (= O) _2- , -S (= O) ₂ -O -Etc. can be mentioned. When an aliphatic hydrocarbon group is cyclic, you may contain these substituents in a ring structure.

As a substituent which substitutes one part or all part of a hydrogen atom, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (= O), a cyano group etc. are mentioned, for example.

As said alkoxy group, 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 preferable, A methoxy group and an ethoxy group are preferable. The timing is most desirable.

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

Examples of the halogenated alkyl group include groups in which part or all of hydrogen atoms of an alkyl group having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group, are substituted with the halogen atom. Can be.

As an aliphatic hydrocarbon group, a linear or branched saturated hydrocarbon group, a linear or branched monovalent unsaturated hydrocarbon group, or a cyclic aliphatic hydrocarbon group (aliphatic cyclic group) is preferable.

The linear saturated hydrocarbon group (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, decyl 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 saturated hydrocarbon group (alkyl group) preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples thereof include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, -Ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

As an unsaturated hydrocarbon group, it is preferable that carbon number is 2-10, 2-5 are preferable, 2-4 are preferable, and 3 is especially preferable. As a linear monovalent unsaturated hydrocarbon group, a vinyl group, a propenyl group (allyl group), butynyl group etc. are mentioned, for example. As a branched monovalent unsaturated hydrocarbon group, a 1-methylpropenyl group, 2-methylpropenyl group, etc. are mentioned, for example.

Especially as said unsaturated hydrocarbon group, a propenyl group is preferable.

The aliphatic cyclic group may be a monocyclic group or a polycyclic group. It is preferable that the carbon number is 3-30, It is more preferable that it is 5-30, 5-20 are still more preferable, 6-15 are especially preferable, and 6-12 are the most preferable.

Specifically, the group remove | excluding one or more hydrogen atoms from monocyclo alkanes; The group remove | excluding one or more hydrogen atoms from polycyclo alkanes, such as bicyclo alkanes, tricyclo alkanes, and tetracyclo alkanes, etc. are mentioned, for example. have. More specifically, group which removed 1 or more hydrogen atoms from monocyclo alkanes, such as cyclopentane and cyclohexane; Polycyclo alkanes, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclo dodecane The group etc. which removed 1 or more hydrogen atoms from are mentioned.

When the aliphatic cyclic group does not contain a substituent containing a hetero atom in its ring structure, as the aliphatic cyclic group, a polycyclic group is preferable, and a group in which one or more hydrogen atoms are removed from a polycycloalkane is preferred. Most preferred is a group from which one or more hydrogen atoms have been removed from the carbon.

When the aliphatic cyclic group contains a substituent containing a hetero atom in its ring structure, examples of the substituent containing the hetero atom include -O-, -C (= O) -O-, -S-,- S (= O) ₂ -and -S (= O) ₂ -O- are preferred. As a specific example of such an aliphatic cyclic group, the group etc. which are represented by following formula (L1)-(L6), (S1)-(S4) are mentioned, for example.

[Formula 88]

[Wherein, Q ″ is an alkylene group having 1 to 5 carbon atoms, —O—, —S—, —OR ⁹⁴ — or —SR ⁹⁵ —, and R ⁹⁴ and R ⁹⁵ each independently represent an alkylene group having 1 to 5 carbon atoms; M is an integer of 0 or 1;

In formula, as an alkylene group in Q ", R <^94> and R <^95> , the thing similar to the alkylene group in said R <^91> -R <^93> is mentioned, respectively.

In these aliphatic cyclic groups, part of the hydrogen atoms bonded to the carbon atoms constituting the ring structure may be substituted with a substituent. As this substituent, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (= O), etc. are mentioned, for example.

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

The alkoxy group and a halogen atom are the same as what was illustrated as a substituent which substitutes one part or all of the said hydrogen atom, respectively.

Among these, as such R <^X> , it is preferable that it is a cyclic group which may have a substituent. The cyclic group may be either an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or an aliphatic cyclic group which may have a substituent.

As said aromatic hydrocarbon group, the naphthyl group which may have a substituent, or the phenyl group which may have a substituent is preferable.

As an aliphatic cyclic group which may have a substituent, the polycyclic aliphatic cyclic group which may have a substituent is preferable. As this polycyclic aliphatic cyclic group, the group remove | excluding one or more hydrogen atoms from the said polycycloalkane, the group represented by said (L2)-(L5), (S3)-(S4), etc. are preferable.

Moreover, it is especially preferable that R <^X> has a polar part from the point which a lithographic characteristic and a resist pattern shape improve more.

As having a polar moiety, for example, a part of the carbon atoms constituting the aliphatic cyclic group of R ^X described above contains a hetero atom, that is, -O-, -C (= O) -O- -C (= O)-, -OC (= O) -O-, -C (= O) -NH-, -NH- (H may be substituted with a substituent such as an alkyl group, acyl group),- And those substituted with S-, -S (= O) _2- , -S (= O) ₂ -O- and the like.

Among the above, R ^{4 "} preferably has R ^X -Q ¹ -as a substituent. In this case, as R ^4" , R ^X -Q ¹ -Y ^1- [wherein, Q ¹ and R ^X are the same as described above. Is the same, and Y <^1> is a C1-C4 alkylene group which may have a substituent, or a C1-C4 fluorinated alkylene group which may have a substituent] is preferable.

In the group represented by R ^X -Q ¹ -Y ^1- , examples of the alkylene group represented by Y ¹ include the same as those having 1 to 4 carbon atoms among the alkylene groups exemplified in Q ¹ .

As a fluorinated alkylene group of Y <^1> , the group by which one part or all part of the hydrogen atom of this alkylene group was substituted by the fluorine atom is mentioned.

Specifically as Y ¹ ,

And the like.

As Y <^1> , a fluorinated alkylene group is preferable, and the fluorinated alkylene group in which the carbon atom couple | bonded with the adjacent sulfur atom is fluorinated is especially preferable. As such a fluorinated alkylene group,

And the like.

Among these, -CF _2- , -CF ₂ CF _2- , -CF ₂ CF ₂ CF _2- , or CH ₂ CF ₂ CF ₂ -is preferable, and -CF _2- , -CF ₂ CF ₂ -or -CF ₂ CF ₂ CF ₂ -is more preferred, and -CF ₂ -is particularly preferred.

The alkylene group or fluorinated alkylene group may have a substituent. An "alkylene group or fluorinated alkylene group has a substituent" means that some or all of the hydrogen atoms or fluorine atoms in the alkylene group or fluorinated alkylene group are substituted with atoms or groups other than hydrogen atoms and fluorine atoms. .

As a substituent which the alkylene group or the fluorinated alkylene group may have, a C1-C4 alkyl group, a C1-C4 alkoxy group, a hydroxyl group, etc. are mentioned.

In the formula ^{(b-2), R 5} "~ R 6" are the same and each R ⁵ in the formula ^{(g-c2) "~ R} 6".

Examples of R ^{4 ″} in the formula (b-2) include the same ones as R ^{4 ″} in the formula (b-1).

As a specific example of the onium salt type acid generator represented by Formula (b-1) and (b-2), the trifluoromethane sulfonate or nonafluoro butane sulfonate of diphenyl iodonium, bis (4-tert- Butylphenyl) trifluoromethanesulfonate or nonafluorobutanesulfonate of iodonium, trifluoromethanesulfonate of triphenylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, tri ( Trifluoromethanesulfonate of 4-methylphenyl) sulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, trifluoromethanesulfonate of dimethyl (4-hydroxynaphthyl) sulfonium, its Heptafluoropropanesulfonate or nonafluorobutanesulfonate, trifluoromethanesulfonate of monophenyldimethylsulfonium, heptafluoropropanesulfonate or nonaflu Robutanesulfonate; trifluoromethanesulfonate of diphenylmonomethylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, and trifluoromethanesulfo of (4-methylphenyl) diphenylsulfonium Nate, Heptafluoropropanesulfonate or Nonafluorobutanesulfonate thereof, Trifluoromethanesulfonate of (4-methoxyphenyl) diphenylsulfonium, Heptafluoropropanesulfonate or Nonafluorobutane thereof Sulfonate, trifluoromethanesulfonate of tri (4-tert-butyl) phenylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate, diphenyl (1- (4-methoxy) naph Trifluoromethanesulfonate of butyl) sulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, and trifluoromethanesulfone of di (1-naphthyl) phenylsulfonium Heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, trifluoromethanesulfonate of 1-phenyltetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-methylphenyl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; 1- (3,5-dimethyl-4-hydroxyphenyl ) Trifluoromethanesulfonate of tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; tri- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium Fluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; tripleru of 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium Oromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; trifluoromethanesulfonate of 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium, its Heptafluoropropanesulfonate or its nonafluorobutanesulfonate; trifluoromethanesulfonate of 1-phenyltetrahydrothiopyranium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 4-hydroxyphenyl) tetrahydrothiopyranium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; 1- (3,5-dimethyl-4-hydroxyphenyl) Trifluoromethanesulfonate of tetrahydrothiopyranium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; 1- (4-methylphenyl) tetrahydro And trifluoromethanesulfonate of thiopyranium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof.

In addition, anion parts of these onium salts are alkyl sulfo such as methanesulfonate, n-propanesulfonate, n-butanesulfonate, n-octanesulfonate, 1-adamantanesulfonate and 2-norbornanesulfonate. Nate; onium salts substituted with sulfonates such as d-camphor-10-sulfonate, benzenesulfonate, perfluorobenzenesulfonate, and p-toluenesulfonate can also be used.

Moreover, the onium salt which substituted the anion part of these onium salts with the anion shown by either of following formula (b1)-(b8) can also be used.

(89)

[Wherein y is an integer of 1 to 3, q1 to q2 are each independently an integer of 1 to 5, q3 is an integer of 1 to 12, t3 is an integer of 1 to 3, and r1 to r2 are each Independently an integer from 0 to 3, i is an integer from 1 to 20, R ⁵⁰ is a substituent, m1 to m5 are each independently 0 or 1, v0 to v5 are each independently an integer from 0 to 3, w1 to w5 are each independently an integer of 0 to 3, and Q "is the same as above.

R ⁵⁰ in the substituent, in the R ^X, are the same as those exemplified as the substituent group which may have a substituent, an aromatic hydrocarbon group which may contain aliphatic hydrocarbon.

When the symbols (r1 to r2, w1 to w5) given to R ⁵⁰ are integers of 2 or more, a plurality of R ⁵⁰ in the compound may be the same or different.

Further, onium salt-based acid generator, said in the general formula (b-1) or (b-2), no moiety (R ^{4 "SO} ₃ ^-) the following formula (b-3) or (b-4 An onium salt-based acid generator substituted with an anion represented by) can also be used (the cation moiety is the same as the cation moiety in the formula (b-1) or (b-2)).

(90)

[Wherein X ″ represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; Y ″ and Z ″ each independently represent an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; Indicates

X "is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms. .

Y ″ and Z ″ are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably 1 to 7, carbon atoms. Is 1 to 3 carbon atoms.

Carbon number of the alkylene group of X "or carbon number of the alkyl group of Y" and Z "is so preferable that it is so small that it is solubility to a resist solvent in the range of the said carbon number.

Moreover, in the alkylene group of X "or the alkyl group of Y", Z ", the more the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, and the transparency to high energy light and electron beam of 200 nm or less It is preferable because it improves.

The proportion of the fluorine atom in the alkylene group or the alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably, a perfluoroalkylene group in which all hydrogen atoms are substituted with fluorine atoms. Or a perfluoroalkyl group.

Also, in the onium salt-based acid generator, the general formula (b-1) or (b-2), no moiety (R ^{4 "SO} ₃ ^-) a, R ^h -COO ^- [wherein, R ^h is Alkyl group or fluorinated alkyl group] may be used (the cation moiety is the same as the cation moiety in the formula (b-1) or (b-2)).

Roneun In the formula, R ^h, are the same as the R ^{4 ".}

The "R ^h -COO ^-" Specific examples of include, for example, there may be mentioned acetate ion, acetate ion, and 1-adamantane carboxylic acid ion trifluoromethyl.

Moreover, the sulfonium salt which has the cation represented by the said general formula (g-c3) or (g-c4) as a onium salt type acid generator can be used.

Moreover, the sulfonium salt which has the cation represented by the said general formula (g-c5) or general formula (g-c6) at the cation part can also be used.

The anion part of the sulfonium salt which has the cation represented by said formula (g-c3)-(g-c6) in a cation part is not specifically limited, What is necessary is just the same as the anion part of the onium salt type acid generator proposed so far. The anionic portion is, for example, the formula (b-1) or (b-2) an onium salt-based no moiety of the acid generator (R ^{4 "SO} ₃ ^-) represents a fluorinated alkyl sulfonic acid ion and the like; the general And anion represented by the formula (b-3) or (b-4), and anion represented by any of the above formulas (b1) to (b8).

In this specification, an oxime sulfonate-type acid generator is a compound which has at least 1 group represented by following General formula (B-1), and has a characteristic which generate | occur | produces an acid by irradiation (exposure) of radiation. Since such an oxime sulfonate-type acid generator is used abundantly for chemical amplification resist compositions, it can select arbitrarily and can use it.

[Formula 91]

(In the formula (B-1), R ³¹ and R ³² each independently represent an organic group)

The organic group of R <^31> , R <^32> is group containing a carbon atom, and atoms other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine atom, a chlorine atom, etc.), etc.) You may have it.

As an organic group of R <^31> , a linear, branched or cyclic alkyl group or an aryl group is preferable. These alkyl groups and aryl groups may have a substituent. There is no restriction | limiting in particular as this substituent, For example, a fluorine atom, a C1-C6 linear, branched or cyclic alkyl group etc. are mentioned. Here, "having a substituent" means that one part or all part of the hydrogen atom of an alkyl group or an aryl group is substituted by the substituent.

As an alkyl group, C1-C20 is preferable, C1-C10 is more preferable, C1-C8 is more preferable, C1-C6 is especially preferable, C1-C4 is the most preferable. As the alkyl group, a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is preferable. In addition, the partially halogenated alkyl group means the alkyl group in which a part of hydrogen atoms were substituted by the halogen atom, and the fully halogenated alkyl group means the alkyl group in which all the hydrogen atoms were substituted by the 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 especially preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.

The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. As the aryl group, a partially or completely halogenated aryl group is particularly preferable. In addition, the partially halogenated aryl group means the aryl group in which a part of hydrogen atoms are substituted by the halogen atom, and the fully halogenated aryl group means the aryl group in which all the hydrogen atoms were substituted by the halogen atom.

Especially as R <^31> , a C1-C4 alkyl group or a C1-C4 fluorinated alkyl group which does not have a substituent is preferable.

As an organic group of R <^32> , a linear, branched or cyclic alkyl group, an aryl group, or a cyano group is preferable. As an alkyl group and an aryl group of R <^32> , the thing similar to the alkyl group and aryl group which were illustrated by said R <^31> is mentioned.

Especially as R <^32> , a cyano group, a C1-C8 alkyl group which does not have a substituent, or a C1-C8 fluorinated alkyl group is preferable.

As a more preferable oxime sulfonate-type acid generator, the compound represented by the following general formula (B-2) or (B-3) is mentioned.

&Lt; EMI ID =

[In formula (B-2), R ³³ is a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁴ is an aryl group. R ³⁵ is an alkyl group or a halogenated alkyl group having no substituent]

&Lt; EMI ID =

[In Formula (B-3), R ³⁶ is a cyano group, an alkyl group having no substituent, or a halogenated alkyl group. R ³⁷ is a divalent or trivalent aromatic hydrocarbon group. R ³⁸ is an alkyl group having no substituent or a halogenated alkyl group. p "is 2 or 3]

In the general formula (B-2), the alkyl group or halogenated alkyl group which does not have a substituent of R ³³ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms. .

As R ³³ , a halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.

The fluorinated alkyl group in R ³³ is preferably 50% or more fluorinated, more preferably 70% or more, and particularly preferably 90% or more fluorinated.

As an aryl group for R ³⁴ , one hydrogen atom is formed from a ring of an aromatic hydrocarbon such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. And a heteroaryl group in which a part of the removed group and the carbon atoms constituting the ring of these groups are substituted with a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Among these, a fluorenyl group is preferable.

The aryl group of R ³⁴ may have substituents such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group and an alkoxy group. The alkyl group or halogenated alkyl group in the substituent preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Moreover, it is preferable that this halogenated alkyl group is a fluorinated alkyl group.

The alkyl group or halogenated alkyl group having no substituent of R ³⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.

As R ³⁵ , a halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.

The fluorinated alkyl group in R ³⁵ is preferably 50% or more fluorinated, and more preferably 70% or more fluorinated, and more preferably 90% or more fluorinated, in order to increase the strength of the generated acid. desirable. Most preferably, it is a fully fluorinated alkyl group in which the hydrogen atom is 100% fluorine substituted.

In said general formula (B-3), the thing similar to the alkyl group or halogenated alkyl group which does not have a substituent of said R <^33> is mentioned as an alkyl group or halogenated alkyl group which does not have a substituent of R <^36> .

As a bivalent or trivalent aromatic hydrocarbon group of R <^37> , the group remove | excluding one or two hydrogen atoms from the said aryl group of R <^34> is mentioned.

As an alkyl group or halogenated alkyl group which does not have a substituent of R <^38> , the same thing as the alkyl group or halogenated alkyl group which does not have a substituent of said R <^35> is mentioned.

p "is preferably 2.

Specific examples of the oxime sulfonate acid generator include α- (p-toluenesulfonyloxyimino) -benzyl cyanide, α- (p-chlorobenzenesulfonyloxyimino) -benzyl cyanide, and α- ( 4-nitrobenzenesulfonyloxyimino) -benzyl cyanide, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -benzyl cyanide, α- (benzenesulfonyloxyimino) -4- Chlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -2,4-dichlorobenzyl cyanide, α- (benzenesulfonyloxyimino) -2,6-dichlorobenzylcyanide, α- (benzenesulfonyloxyi Mino) -4-methoxybenzylcyanide, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxybenzylcyanide, α- (benzenesulfonyloxyimino) -thien-2-ylacetonitrile, α- (4-dodecylbenzenesulfonyloxyimino) -benzyl cyanide, α-[(p-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfonyloxyi Mino) -4-methoxyphenyl] acetonitrile , α- (tosyloxyimino) -4-thienyl cyanide, α- (methylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclohexenylaceto Nitrile, α- (methylsulfonyloxyimino) -1-cycloheptenylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclooctenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -1-cyclopentenyl acetonitrile, α- (trifluoromethylsulfonyloxyimino) -cyclohexylacetonitrile, α- (ethylsulfonyloxyimino) -ethylacetonitrile, α- (propylsulfonyloxyimino) -Propyl acetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclopentylacetonitrile, α- (cyclohexylsulfonyloxyimino) -cyclohexylacetonitrile, α- (cyclohexylsulfonyloxyimino) -1- Cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- Propylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohexenyl Acetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyimino ) -Phenylacetonitrile, α- (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsulfonyl Oxyimino) -p-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -p-methylphenylacetonitrile, α- (methyl Sulfonyloxyimino) -p-bromophenylacetonitrile, etc. are mentioned.

Moreover, the oxime sulfonate-type acid generator currently disclosed by Unexamined-Japanese-Patent No. 9-208554 (Schemes 18-19 of Paragraph [0012]-[0014], International Publication No. 04/074242). The oxime sulfonate acid generators disclosed in the arc brochures (Examples 1 to 40 on pages 65 to 85) can also be preferably used.

Moreover, the following can be illustrated as a preferable thing.

(94)

As a specific example of bisalkyl or bisaryl sulfonyl diazomethanes in a diazomethane-type acid generator, bis (isopropylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, etc. are mentioned.

Moreover, the diazomethane type acid generator disclosed in Unexamined-Japanese-Patent No. 11-035551, Unexamined-Japanese-Patent No. 11-035552, and Unexamined-Japanese-Patent No. 11-035573 can also be used preferably.

Moreover, as poly (bissulfonyl) diazomethanes, 1, 3-bis (phenylsulfonyl diazommethyl sulfonyl) propane disclosed by Unexamined-Japanese-Patent No. 11-322707, for example, 1,4-bis (phenylsulfonyldiazomethylsulfonyl) butane, 1,6-bis (phenylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (phenylsulfonyldiazomethylsulfonyl) decane , 1,2-bis (cyclohexylsulfonyldiazomethylsulfonyl) ethane, 1,3-bis (cyclohexylsulfonyldiazomethylsulfonyl) propane, 1,6-bis (cyclohexylsulfonyldiazomethyl Sulfonyl) hexane, 1, 10-bis (cyclohexylsulfonyl diazommethylsulfonyl) decane, etc. are mentioned.

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

0.5-60 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of (B) component in the resist composition of this invention, 1-50 mass parts is more preferable, 1-40 mass parts is more preferable. In the above range, pattern formation is sufficiently performed. Moreover, when each component of a resist composition is melt | dissolved in the organic solvent, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

&Lt; Other components &gt;

In the resist composition of this invention, you may contain the amine component (D) (henceforth "(D) component") which does not correspond to the component mentioned above further in the range which does not impair the effect of this invention. .

The component (D) is not particularly limited as long as it serves as an acid diffusion control agent, that is, a quencher that traps an acid generated from the component (B) by exposure, for example. What is necessary is just to use arbitrarily from a well-known thing. Specific examples include amines such as aliphatic amines and aromatic amines, and among them, aliphatic amines, particularly secondary aliphatic amines and tertiary aliphatic amines are preferable.

The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 20 carbon atoms.

Aliphatic amines include, for example, at least one of the hydrogen atoms of ammonia NH _3, there may be mentioned amine (alkylamine or alkyl alcohol amines), or a cyclic amine substituted with an alkyl group or hydroxy alkyl group having a carbon number of 20 or less .

The alkyl group in the alkyl group and the hydroxyalkyl group may be any of linear, branched and cyclic groups.

When the alkyl group is linear or branched, the carbon number is more preferably 2 to 20, more preferably 2 to 8.

When the alkyl group is cyclic (in the case of a cycloalkyl group), the carbon number is preferably 3 to 30, more preferably 3 to 20, still more preferably 3 to 15, particularly preferably 4 to 12 carbon atoms, Most preferred is 5 to 10 carbon atoms. The alkyl group may be monocyclic or polycyclic. Specifically, the group remove | excluding one or more hydrogen atoms from monocyclo alkanes, the group remove | excluding one or more hydrogen atoms from polycycloalkanes, such as a bicycloalkane, tricycloalkane, and tetracycloalkane, etc. can be illustrated. Specific examples of the monocycloalkane include cyclopentane, cyclohexane, and the like. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

Specific examples of the alkylamine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, diethylamine, di-n-propylamine, Dialkylamines such as di-n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentyl Trialkylamines such as amines, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, and tri-n-dodecylamine Can be mentioned.

Specific examples of the alkyl alcohol amine include diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, stearyl diethanolamine, and lauryl di. Ethanolamine etc. are mentioned.

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

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

As aliphatic polycyclic amine, it is preferable that carbon number is 6-10, Specifically, 1, 5- diazabicyclo [4.3.0] -5-nonene, 1,8- diazabicyclo [5.4.0] -7-undecene, hexamethylenetetramine, 1, 4- diazabicyclo [2.2.2] octane, etc. are mentioned.

As other aliphatic amines, tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} Amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine and the like.

Examples of the aromatic amines include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, tribenzylamine and the like.

These may be used independently and may be used in combination of 2 or more type.

(D) component is normally used in 0.01-5.0 mass part with respect to 100 mass parts of (A) component. By setting the resistivity to the above range, the resist pattern shape, time-course stability after exposure, and the like are improved.

The resist composition of the present invention is at least one member selected from the group consisting of oxo acids of phosphorus and derivatives thereof as an optional component for the purpose of preventing sensitivity deterioration, improving the resist pattern shape, stability over time after exposure, and the like. You may contain the compound (E) (henceforth "(E) component").

Examples of the phosphoric acid include phosphoric acid, phosphonic acid and phosphinic acid, and phosphonic acid is particularly 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, etc. 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 phosphoric acid derivatives 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 the derivatives of phosphinic acid include phosphinic acid esters such as phenylphosphinic acid.

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

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

In order to provide water repellency to a resist film, the resist composition of this invention can be made to contain a fluorine additive (henceforth "(F) component").

By further containing (F) component, the hydrophobicity of the surface of a resist film becomes high and the defect generation after image development is suppressed more.

As (F) component, the fluorine-containing high molecular compound etc. of Unexamined-Japanese-Patent No. 2010-002870 can be used, for example.

Specifically as a component (F), the copolymer which has a structural unit represented by the following general formula (f1) is mentioned preferably. More specifically, the polymer (homopolymer) which consists only of a structural unit represented by following formula (f1), the copolymer of the structural unit represented by the following formula (f1), the said structural unit (a1), and the structure represented by following formula (f1) Preferred is a copolymer of a unit, a structural unit derived from acrylic acid or methacrylic acid, and the structural unit (a1). Among the structural units (a1), structural units represented by the formula (a1-1-32) are particularly preferable.

[Formula 95]

[Wherein R is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, R ^{7 ″} is an organic group containing a fluorine atom, and R ^{8 ″} may have a substituent; 5 is an alkylene group]

In said formula (f1), R <^{7> "} is an organic group containing a fluorine atom, and it is preferable that it is a hydrocarbon group containing a fluorine atom. As a hydrocarbon group containing a fluorine atom, a fluorinated alkyl group is more preferable, and it is C1-C1 a fluorinated alkyl group of 5 is more preferable among them, R ^{7 "roneun,."} _{- (CH 2) o-CF} 3 "is group is preferably represented by the following formula (in the formula, o indicates the number of repetitions of CH _2, 1 ~ 3 Is an integer).

In formula (f1), the carbon number of the alkylene group of R ^{8 "} is 1-5, it is preferable that it is 1-3, and it is more preferable that it is 1 or 2. The hydrogen atom of the alkylene group of R8 ^" is a fluorine atom, It may be substituted by a C1-C5 alkyl group or a C1-C5 fluorinated alkyl group.

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

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

It is preferable to use content of (F) component in a resist composition in the ratio of 1-10 mass parts per 100 mass parts of (A) component. By making content of (F) component into the said range, hydrophobicity of the resist film surface becomes high and defect generation after image development is suppressed more.

The resist composition of the present invention may further contain, as desired, miscible additives, for example, additional resins for improving the performance of resist films, surfactants for improving applicability, dissolution inhibitors, plasticizers, stabilizers, A coloring agent, an antihalation agent, dye, etc. can be added and contained suitably.

The resist composition of this invention can be manufactured by melt | dissolving a material in the organic solvent (Hereinafter, it may be called "(S) component.").

As (S) component, what is necessary is just to melt | dissolve each component to be used and it can be set as a uniform solution, and conventionally select arbitrary 1 type (s) or 2 or more types from the well-known as the solvent of a chemically amplified resist, Can be used.

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; ethylene glycol, diethylene glycol Polyhydric alcohols such as propylene glycol, dipropylene glycol; compounds having ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the above polyhydric alcohols or the esters Derivatives of polyhydric alcohols such as compounds having ether bonds, such as monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether, etc. of the compounds having a bond. Monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) Preferred]; esters such as cyclic ethers such as dioxane and methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate. Anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phentol, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesh Aromatic organic solvents, such as styrene, etc. are mentioned.

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

Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone and EL are preferable.

Moreover, the mixed solvent which mixed PGMEA and a polar solvent is also preferable. What is necessary is just to determine the compounding ratio (mass ratio) suitably in consideration of compatibility of PGMEA and a polar solvent, etc., Preferably it is 1: 9-9: 1, More preferably, it is within the range of 2: 8-8: 2. Do. For example, when mix | blending EL as a polar solvent, the mass ratio of PGMEA: EL becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2. Moreover, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, More preferably, it is 3: 7-7. ： 3. Moreover, when mix | blending PGME and cyclohexanone as a polar solvent, the mass ratio of PGMEA: (PGME + cyclohexanone) becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, More preferably, it is 3: 7-7: 3.

Moreover, as (S) component, the mixed solvent of PGMEA, EL, or the said PGMEA and a polar solvent, and (gamma) -butyrolactone is also preferable elsewhere. 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.

Although the usage-amount of (S) component is not specifically limited, Although it is a density | concentration which can be apply | coated to a board | substrate etc., it sets suitably according to a coating film thickness, Generally, solid content concentration of a resist composition is 1-20 mass%, Preferably it is 2-15. It is used so that it may be in the range of mass%.

When forming a resist pattern using the resist composition of this invention demonstrated above, (G) component which exists in the unexposed part of a resist film, as mentioned above, the ion-exchange reaction with the acid which arises from (B) component, for example. The action of suppressing acid diffusion phenomenon is shown. On the other hand, the (G) component which exists in the exposure part of a resist film decomposes | disassembles by exposure, and loses basicity with respect to the acid generated from the (B) component, for example. By these actions, according to the resist composition of the present invention, it is possible to improve lithography characteristics, resist pattern shape and the like.

In addition, the resist composition of the present invention also has the effect of being able to suppress the dimensional variation of the resist pattern with the influence of time. The reason is not clear, but it is assumed as follows.

In general, in the resist composition, in addition to the base component (A) and the acid generator component (B), in order to control diffusion of an acid generated from the component (B) by exposure, for example, an amine component or the like is preferable. It is compounded.

In such a resist composition, there exists a problem that the dimension of the resist pattern formed before and after storage fluctuates by preparing a resist composition and storing it for a fixed period.

This problem is presumed to be due to the decomposition of the other compounding components (degradation over time) by the interaction of the amine component with other compounding components in the resist composition.

In the resist composition of the present invention, by combining the specific (G) component and the (H) component, the nucleophilicity with respect to other compounding components of the (G) component is further reduced during the storage period, and the other compounding component Since decomposition (deterioration over time) of the is suppressed, it is estimated that the dimensional change of the resist pattern formed before and after storage is also small.

&Lt; Method of forming resist pattern &

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

The resist pattern formation method of this invention can be performed as follows, for example.

That is, first, the resist composition of the present invention is applied onto a support with a spinner or the like, and the bake (post-applied bake (PAB)) treatment is performed for 40 to 120 seconds, for example, at a temperature of 80 to 150 ° C. Is performed for 60 to 90 seconds to form a resist film.

Next, using the exposure apparatus, such as an ArF exposure apparatus, an electron beam drawing apparatus, an EUV exposure apparatus, about the resist film, exposure through the mask (mask pattern) in which the predetermined | prescribed pattern was formed, or not through a mask pattern is performed, for example. After performing selective exposure by drawing or the like by direct irradiation of an electron beam, the baking (post exposure bake (PEB)) treatment is performed, for example, at a temperature condition of 80 to 150 ° C. for 40 to 120 seconds, preferably 60 to 90 degrees. Do it for a second.

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 developing treatment, rinsing treatment is preferably carried out. In the case of an alkali developing process, the 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, a treatment for removing the developing solution or the rinsing liquid adhering to the pattern by the supercritical fluid may be performed after the developing treatment or the rinsing treatment.

After the development treatment or the rinsing treatment, drying is performed. In some cases, after the developing treatment, a bake treatment (post bake) may be performed. In this way, a resist pattern can be obtained.

It does not specifically limit as a support body, A conventionally well-known thing can be used, For example, the board | substrate for electronic components, the thing in which the predetermined wiring pattern was formed, etc. can be illustrated. 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. As the inorganic film, an inorganic anti-reflection film (inorganic BARC) can be mentioned. Examples of the organic film include an organic antireflection film (organic BARC) and an organic film such as a lower organic film in the multilayer resist method.

Here, the multilayer resist method 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 this is a method of patterning the lower organic film, and that a pattern having a high aspect ratio can be formed. That is, according to the multilayer resist method, since the required thickness can be ensured by the lower organic film, the resist film can be thinned and fine 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 can be divided into the method (three-layer resist method) which makes a multilayer structure more than one three layers.

The wavelength used for exposure is not specifically limited, ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray It can carry out using radiation, such as these. The resist composition is highly useful as KrF excimer laser, ArF excimer laser, EB or EUV.

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

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 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 that the medium used for liquid immersion can be removed by a simple method after the end of exposure.

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. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.

Moreover, specifically, as said perfluoroalkyl ether compound, perfluoro (2-butyl- tetrahydrofuran) (boiling point 102 degreeC) is mentioned, As said perfluoroalkylamine compound, a perfluoro tree Butylamine (boiling point 174 degreeC) is mentioned.

As the immersion medium, water is preferably used from the viewpoints 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.

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

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, an ionic or nonionic fluorine type and / or silicone type surfactant etc. can be used.

When mix | blending surfactant, the compounding quantity is 0.001-5 mass% normally with respect to the total amount 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 predetermined time (dip method), a method of mounting the developer on the surface of the support by surface tension to stop for a certain time. (Paddle method), a method of spraying a developer onto the surface of a support (spray method), a method of continuously deriving a developer while scanning a developer extraction nozzle at a constant speed on a support rotating at a constant speed (dynamic dispensing) Law).

As the organic solvent contained in the rinse liquid used for the rinsing treatment after the developing treatment in the solvent developing process, for example, an organic solvent exemplified as the organic solvent contained in the organic developer is selected as appropriate, Can be used. Usually, at least 1 type 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 kind selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent and an amide solvent is preferable, and at least one kind selected from an alcohol solvent and an ester solvent is more preferable. Alcoholic solvents are particularly preferred.

The rinsing treatment (rinsing treatment) using the rinsing liquid can be carried out by a known rinsing method. As the method, 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 a support in a rinse liquid for a predetermined time (dip method), a rinse liquid on a support surface And spraying method (spray method).

Example

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

In the present Example, the compound represented by General formula (1) is described as "compound (1)", and it describes similarly about the compound represented by another chemical formula.

Polymer Synthesis Example 1 (Synthesis of Copolymer (2))

In a separable flask equipped with a thermometer, reflux tube and nitrogen introduction tube, 12.00 g (70.52 mmol) of compound (1), 12.60 g (39.83 mmol) of compound (2), and 20.77 g (79.15 m Mol) compound (3), 5.85 g (34.75 mmol) compound (4), 6.95 g (29.43 mmol) compound (5), and 1.61 g (3.08 mmol) compound (6) It was dissolved in 76.81 g of methyl ethyl ketone (MEK). In this solution, 4.14 g (17.97 mmol) of dimethyl azobisisobutyrate (V-601) was added and dissolved as a polymerization initiator.

This was dripped at 41.66g MEK over 4 hours at 80 degreeC in nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was stirred for 1 hour while heating to 80 ° C, after which the reaction solution was cooled to room temperature.

The obtained reaction polymerization liquid was dripped at large quantity of n-heptane, the operation of depositing a polymer was performed, the precipitated white powder was separated by filtration and dried, and 27.08 g of copolymer (2) which is a target object was obtained.

The mass average molecular weight (Mw) of the standard polystyrene conversion calculated | required by GPC measurement about this copolymer (2) was 7600, and molecular weight dispersion degree (Mw / Mn) was 1.68. In addition, the copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz_ ¹³ C-NMR) was l / m / n / o / p / q = 34.7 / 23.5 /16.3/14.5 /9.8/1.2.

&Lt; EMI ID =

[Polymer Synthesis Examples 2 to 9 (Synthesis of Copolymers (1) and (3) to (9))]

The copolymers (1) and (3) to (9) are the polymer synthesis examples 1 and 1 except that the following compounds (1) to (10) which induce the structural units constituting the respective copolymers are used at a predetermined molar ratio. Synthesis was carried out in the same manner.

About each copolymer, the compound which guide | induces each structural unit, the copolymer composition ratio calculated | required by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR), the mass mean molecular weight of standard polystyrene conversion calculated by GPC measurement, and molecular weight Dispersion degree (Mw / Mn) is shown in Table 1.

[Formula 97]

<Preparation of a resist composition>

Examples 1 to 52, Comparative Examples 1 to 20

The resist composition was prepared by mixing and dissolving each component shown in Tables 2-6.

In Tables 2-6, the numerical value in [] is a compounding quantity (mass part), and each symbol shows the following, respectively.

(A) -1-(A) -9: the said copolymer (1)-copolymer (9).

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

(98)

(G) -1 to (G) -11: the compound represented by chemical formulas (G) -1 to (G) -11 shown below.

[Formula 99]

(H) -1 to (H) -11: The compound represented by chemical formula (H) -1 to (H) -11 shown below.

(100)

(S) -1: γ-butyrolactone.

(S) -2: The mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 6/4 (mass ratio).

<Formation of Resist Pattern>

Film thickness by apply | coating organic type anti-reflective film composition "ARC-29A" (brand name, Brewer Science Co., Ltd.) using a spinner on an 8-inch silicon wafer by baking at 205 degreeC for 60 second on a hotplate, and drying. An organic antireflection film of 82 nm was formed.

Next, the said resist composition is apply | coated using the spinner, respectively, on the anti-reflective film, and it carries out a 60 second prebaking (PAB) process at the temperature shown in the following table on a hotplate, and it dries, and has a film thickness of 150 nm. A resist film of was formed.

Next, about the resist film, ArF excimer laser was carried out through the mask (6% halftone) by ArF exposure apparatus NSR-S302 (made by Nikon Corporation; NA (number of openings) = 0.60, 2/3 annular illumination). (193 nm) was selectively irradiated.

And the post-exposure heating (PEB) process for 60 second is performed at the temperature shown in the following table, and 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" at 23 degreeC (brand name, Tokyo Oka Co., Ltd.) Production), the alkali development treatment was carried out for 30 seconds, followed by pure water rinsing, and shaking and drying for 30 seconds.

As a result, also in any of the examples, a resist pattern (hereinafter referred to as "SL pattern") of space-and-line in which a space having a width of 120 nm was arranged at equal intervals (pitch 240 nm) was formed in the resist film.

The optimum exposure dose Eop (mJ / cm 2), that is, the sensitivity at which the SL pattern is formed, was determined. The results are shown in the table.

[Evaluation of Line With Roughness (LWR)]

According to the same procedure as the formation of the resist pattern, in the SL pattern having a space width of 120 nm and a pitch of 240 nm formed in the Eop, the measurement SEM (scanning electron microscope, acceleration voltage 800 V, trade name: S-9380, Hitachi High) (Manufactured by Technologies Co., Ltd.), the space width was measured 400 points in the longitudinal direction of the space, and from the results, three times the value (3s) of the standard deviation (s) was obtained, and the value was averaged with respect to 5s of 3s. Was calculated as a measure of LWR. The results are shown in the table as "LWR (nm)".

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

[Evaluation of Mask Error Factor (MEF)]

According to the same procedure as the formation of the resist pattern, in the Eop, a mask pattern that targets a SL pattern having a space width of 120 nm and a pitch of 260 nm, and an SL pattern having a space width of 130 nm and a pitch of 260 nm are targeted. The SL pattern was formed using the mask pattern, respectively, and the value of MEF was calculated | required from the following formula | equation. The results are shown in the table as "MEF".

MEF = ｜ CD ₁₃₀ -CD ₁₂₀ ｜ / ｜ MD ₁₃₀ -MD ₁₂₀ ｜

In the above formula, CD _130, CD _120, respectively, the actual width of the space pattern of SL (㎚) formed by using a mask pattern targeting a 130 ㎚ space width, 120 ㎚. MD ₁₃₀ and MD ₁₂₀ are the space width (nm) which the said mask pattern targets, respectively, and are MD ₁₃₀ = 130 and MD ₁₂₀ = 120.

The closer this MEF value is to 1, the more a resist pattern was formed in the mask pattern.

[Evaluation of exposure margin (EL margin)] [

In the above Eop, the exposure amount when the space of the SL pattern is formed within the range of ± 5% (114 nm to 126 nm) of the target dimension (space width 120 nm) is obtained, and the EL margin (unit:%) is expressed by the following equation. ) Was obtained. The result is shown to a table as "EL (%)."

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

E1: Exposure dose (mJ / cm 2) when an SL pattern having a space width of 114 nm was formed.

E2: Exposure dose (mJ / cm 2) when SL pattern with space width of 126 nm was formed

In addition, EL margin shows that the larger the value, the smaller the amount of change in the pattern size accompanying the variation in the exposure amount.

[Evaluation of resist pattern shape]

The SL pattern of 120 nm in space width and 240 nm in pitch formed by the said Eop was observed using the scanning electron microscope SEM (Product name SU8000, the Hitachi High-Technologies company), and the cross-sectional shape of the said SL pattern was evaluated. The results are shown in the table.

[Proportion (Mole Ratio) of Mass Content in Resist Composition of Component (G) and Component (H)

In the resist composition of each example, the ratio (molar ratio) of the mass of the content in the resist composition of the component (G) and the component (H) was calculated. The result is shown in a table | surface as molar ratio "(G) :( H) molar ratio" of (H) component with respect to (G) component.

About Examples 1-38, 45, 52, and Comparative Examples 1 and 2, the molar ratio in the case where both (G) component and (H) component are low molecular weight compounds (additive) is shown.

About Examples 39-43 and 46-50, the molar ratio when (G) component is resin (base material component) and (H) component is low molecular weight compound (additive).

About Examples 44 and 51, the molar ratio when (G) component is a low molecular weight compound (additive) and (H) component is resin (base component) is shown.

As an example, "(G) :( H) molar ratio" of Example 39 is demonstrated.

In Example 39, the component (G) is a resin (base component), and the component (H) is a low molecular compound (additive).

(G) content of the content of the component

The copolymer (2) is used as the component (G) (base component (A)). From the following procedures (1) to (3), the content mass of the component (G) is determined (see Table 7).

Procedure (1): The ratio of the structural unit guide | induced from the compound (6) corresponding to (G) component in the copolymer (2) is 1.2 mol%.

Procedure (2): From the ratio (molar ratio) of the structural unit calculated | required in the procedure (1), when the whole resin (this copolymer (2)) is set to 100 (mass part), the structural unit guide | induced from the compound (6) The ratio (mass ratio) is obtained by 2.73 [= (523.59 × 1.2 / 100) /229.99 × 100].

Step (3): When the ratio (mass ratio) of the structural units obtained in Step (2) is regarded as the mass of the compound (6), and the content mass of the compound (6) is obtained, 5.21 (mmol) (= 2.73 / 523.59 X 10 ³ ).

(H) component mass

(H) -2 (molecular weight 355.11) is used as (H) component (additive).

Content of (H) -2 in a resist composition is 3.39 mass parts with respect to 100 mass parts of (A) component. From this, the content mass of (H) -2 is calculated as 9.55 (mmol) (= 3.39 / 355.11 × 10 ³ ).

(G): (H) molar ratio

The ratio (molar ratio) of the mass of the content in the resist composition of the component (G) and the component (H) is as follows. (G): (H) Molar ratio = 1: (9.55 / 5.21) ≒ 1: 1.8.

[Evaluation of Dimensional Variation of Resist Pattern with Influence of Time]

Using the same exposure amount as the above-mentioned Eop by the same method as the formation of the resist pattern, using the one-time cryopreservation (frozen preservation) and the one-room preservation (room temperature preservation) for each resist composition. SL patterns with a space width of 120 nm and a pitch of 240 nm were formed, respectively.

And the line width (dimension) of the predetermined position of the SL pattern respectively formed by the cryopreservation article and the room temperature storage article was measured, and the dimension difference of both was calculated | required.

Δ, cryopreservation and room temperature preservation when the difference between these two dimensions is 2% or less, ◎◎, when 2% or more and 5% or less, and when 5% or more and 10% or less, or when 10% or more and 50% or less The case where an SL pattern could not be formed in one or both products was made into x, and the dimensional variation of the resist pattern according to the influence of time was evaluated. The results are shown in the table as "CD change after 1 M".

From the results shown in the table, it can be seen that the resist compositions of Examples 1 to 52 to which the present invention is applied exhibit excellent dimensional lithography characteristics and resist pattern shapes while suppressing dimensional fluctuations due to the influence of time.

From Examples 1-3, it was confirmed that the dimensional fluctuations according to the influence of time are suppressed more effectively if the content mass of the compound (H) is equal to or greater than the content mass of the compound (G).

In addition, the combination of the (G) component with respect to the (H) component is preferably considered in consideration of the pKa value and the like in view of suppression of dimensional variation with the influence of time.

Moreover, when using the compound which has the same structure as (G) component as (H) component (Example 1-12, Example 45, Example 52), the dimensional fluctuation by the influence of time can be suppressed, In addition, it was confirmed that LWR or MEF was further improved (Examples 13 to 16 for Example 4, Examples 17 to 20 for Example 6, Examples 21 to 24 for Example 7, and Example 8 Examples 25-28).

Claims (11)

Compound (G) which has monovalent group represented by the following general formula (g1) or monovalent group represented by general formula (g2), and
A resist composition comprising a compound (H) having a monovalent group represented by the following general formula (h1) or a monovalent group represented by the general formula (h2).
[Formula 1]

[In formula (g1), R <^2> is a single bond or -C (= O) -O- group. However, when R <^2> is a single bond, what N <^-> in a formula couple | bonds with -C (= O)-group shall not be included in (G) component. R ³ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group which has a partial structure. M ⁺ is each independently an organic cation]
(2)

[In formula (h1), R <^6> is a single bond or -C (= O) -O- group. R ⁷ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. Monovalent hydrocarbon group having a partial structure] The method of claim 1,
The resist composition whose content mass of the said compound (H) is more than the content mass of the said compound (G). The method according to claim 1 or 2,
At least one compound selected from the group consisting of compound (Gm-1) represented by general formula (g1-1) shown below and compound (Gm-2) represented by general formula (g2-1) shown below A resist composition containing the resin component which has a structural unit (g ') derived from.
(3)

[In formula (g1-1), R <^P1> is monovalent group represented by either of following general formula (I) or general formula (II). R ² is a single bond or a —C (═O) —O— group. However, when R <^2> is a single bond, what N <^-> in a formula couple | bonds with -C (= O)-group shall not be included in (G) component. R ³ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group which has a partial structure. In formula (g2-1), R ^P2 is a monovalent group represented by any of the following General Formulas (I) to (III). X each independently represents a single bond or a divalent linking group. M ⁺ is each independently an organic cation]
[Chemical Formula 4]

[In formula (I)-(III), R ^a is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group, R ⁿ is a hydrogen atom or a C1-C5 alkyl group.] The method according to any one of claims 1 to 3,
At least one compound selected from the group consisting of compound (Hm-1) represented by general formula (h1-1) shown below and compound (Hm-2) represented by general formula (h2-1) shown below The resist composition containing the resin component which has a structural unit (h ') derived from.
[Chemical Formula 5]

[In formula (h1-1), R <^P1> is monovalent group represented by either of said general formula (I) or general formula (II). R ⁶ is a single bond or a —C (═O) —O— group. R ⁷ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group which has a partial structure. In formula (h2-1), R ^P2 is a monovalent group represented by any of the above general formulas (I) to (III). Each X independently represents a single bond or a divalent linking group] The method according to claim 3 or 4,
The resin component further has a resist having a structural unit containing an acid-decomposable group whose polarity is increased by the action of an acid as a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent. Composition. 6. The method according to any one of claims 1 to 5,
Compound (Gm-3) in which the compound (G) is represented by the compound (Gm-1) according to claim 3, the compound (Gm-2) according to claim 3, or the following general formula (g1-2) And at least one compound selected from the group consisting of compound (Gm-4) represented by general formula (g2-2).
[Chemical Formula 6]

Equation (g1-2) of, R ¹ is a fluorine atom, a hydroxyl group, -OR ¹⁰ group, -NH-C (= O) -R 10 group, -OC (= O) -R ¹⁰ group, or a - C (= O) -OR ¹⁰ group, provided that R ¹⁰ is a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or 3 to 20 carbon atoms C1-C20 linear or branched monovalent hydrocarbon group, C3-C20 cyclic monovalent hydrocarbon group which may be substituted by the C1-C20 monovalent hydrocarbon group which has a cyclic partial structure of , A monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom. R ² is a single bond or a —C (═O) —O— group. However, when R <^2> is a single bond, what N <^-> in a formula couple | bonds with -C (= O)-group shall not be included in (G) component. R ³ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group which has a partial structure. In formula (g2-2), R <^4> is a fluorine atom, a hydroxyl group, -OR <^10> group, -OC (= O) -R <^10> group, or -C (= O) -OR <^10> group (R <^10>). Represents a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms) 1 having a linear or branched monovalent alkyl group of 1 to 20 carbon atoms, a cyclic monovalent hydrocarbon group of 3 to 20 carbon atoms, or a cyclic partial structure of 3 to 20 carbon atoms which may be substituted with It is a noble hydrocarbon group. M ⁺ is each independently an organic cation] 7. The method according to any one of claims 1 to 6,
Compound (Hm-3) in which the compound (H) is represented by the compound (Hm-1) according to claim 4, the compound (Hm-2) according to claim 4, or the following general formula (h1-2) And at least one compound selected from the group consisting of compound (Hm-4) represented by general formula (h2-2).
(7)

Equation (h1-2) of, R ⁵ is a fluorine atom, a hydroxyl group, -OR ¹⁰ group, -NH-C (= O) -R 10 group, -OC (= O) -R ¹⁰ group, or a - C (= O) -OR ¹⁰ group, provided that R ¹⁰ is a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or 3 to 20 carbon atoms C1-C20 linear or branched monovalent hydrocarbon group, C3-C20 cyclic monovalent hydrocarbon group which may be substituted by the C1-C20 monovalent hydrocarbon group which has a cyclic partial structure of , A monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms, or a hydrogen atom. R ⁶ is a single bond or a —C (═O) —O— group. R ⁷ is a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, optionally substituted with a fluorine atom, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. It is a monovalent hydrocarbon group which has a partial structure. In formula (h2-2), R <^8> is a fluorine atom, a hydroxyl group, -OR <^10> group, -OC (= O) -R <^10> group, or -C (= O) -OR <^10> group (R <^10>). Represents a linear or branched monovalent alkyl group having 1 to 10 carbon atoms, a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, or a monovalent hydrocarbon group having a cyclic partial structure having 3 to 20 carbon atoms) 1 having a linear or branched monovalent alkyl group of 1 to 20 carbon atoms, a cyclic monovalent hydrocarbon group of 3 to 20 carbon atoms, or a cyclic partial structure of 3 to 20 carbon atoms which may be substituted with Is a hydrocarbon group] The method according to any one of claims 1 to 7,
The resist composition containing the acid generator component (B) which generate | occur | produces an acid by exposure. The method according to any one of claims 1 to 8,
The resist composition whose said M ⁺ is organic cation represented by the following general formula (g-c1).
[Chemical Formula 8]

[In formula (g-c1), R < ^{1 >} -R < ^{3 >} represents the aryl group, alkyl group, or alkenyl group which may respectively independently have a substituent. Any two of R ^{1 "} to R ^{3 " may be} bonded to each other to form a ring together with a sulfur atom in the formula] 10. The method according to any one of claims 1 to 9,
A resist composition containing a polymer having a structural unit containing an acid-decomposable group whose polarity is increased by the action of an acid as a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α position may be substituted with a substituent. A step of forming a resist film using the resist composition according to any one of claims 1 to 10, a step of exposing the resist film, and a step of developing the resist film to form a resist pattern on the support; Resist Pattern Formation Method.