KR20090009113A - Novel compound, manufacturing method thereof, acid generator, resist composition and method of forming resist pattern - Google Patents

Abstract

A resist composition, a novel compound used as an acid generator in the composition, a method for preparing the compound, and a formation method of resist pattern are provided to improve the safety of handling when the accumulation in the human body is considered. A resist composition comprises a base component whose solubility in an alkali developer is changed by the action of an acid; and an acid generator component which generates an acid by exposure and comprises an acid generator comprising a compound represented by the formula b1-1, wherein R1 is an aryl group or an alkyl group; R3 is H or an alkyl group; n1 is 0 or 1; A is a divalent group forming a 3-7-membered ring together with the combined sulfur atom; R2 is an aromatic group, a C1-C10 linear or branched alkyl group, or a C2-C10 linear or branched alkenyl group; n is 0 or 1; and Y1 is a C1-C4 alkylene group substituted or unsubstituted with F.

Description

Novel compounds and preparation methods thereof, acid generators, resist compositions, and resist pattern formation methods {NOVEL COMPOUND, MANUFACTURING METHOD THEREOF, ACID GENERATOR, RESIST COMPOSITION AND METHOD OF FORMING RESIST PATTERN}

The present invention relates to a novel compound useful as an acid generator for a resist composition, a method for producing the same, a compound useful as a precursor of the compound, a method for producing the same, an acid generator, a resist composition and a method for forming a resist pattern.

This application claims priority based on Japanese Patent Application No. 2007-187593 for which it applied to Japan on July 18, 2007, and Japanese Patent Application 2007-257492 which was filed in Japan on October 1, 2007, and The content is used here.

In the lithography technique, for example, a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed to radiation such as light or electron beam through a mask having a predetermined pattern formed thereon, and then developed. By performing the above step, a step of forming a resist pattern having a predetermined shape in the resist film is performed. The resist material in which the exposed portion is changed to the characteristic of dissolving in the developer is positive type, and the resist material in which the exposed portion is changed to the characteristic of not dissolving in the developer is called negative type.

In recent years, in manufacture of a semiconductor element and a liquid crystal display element, refinement | miniaturization of a pattern is progressing rapidly with the advance of the lithography technique.

As a miniaturization method, shortening of the exposure light source is generally performed. 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. In addition, a review is carried out or the like even these shorter wavelength than an excimer laser F ₂ excimer laser, electron beam, EUV (extreme ultraviolet) and an X-ray.

The resist material is required for lithographic characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern of fine dimensions. As a resist material that satisfies these requirements, a chemically amplified resist containing a base resin whose solubility in an alkaline developer is changed by the action of an acid and an acid generator which generates an acid by exposure is used. For example, the positive chemically amplified resist contains, as a base resin, a resin which increases solubility in an alkaline developer by the action of acid and an acid generator. Is generated, the exposed portion becomes soluble in the alkaline developer.

Conventionally, as a base resin of chemically amplified resists, polyhydroxystyrene (PHS) having high transparency to KrF excimer laser (248 nm) and resin (PHS resin) in which the hydroxyl group is protected by an acid dissociable, dissolution inhibiting agent are Has been used. However, since PHS resin has aromatic rings, such as a benzene ring, transparency with respect to the light of wavelength shorter than 248 nm, for example, 193 nm is not enough. Therefore, the chemically amplified resist containing PHS-based resin as a base resin component has a drawback such as low resolution in a process using 193 nm light, for example. Therefore, as a base resin of a resist currently used in ArF excimer laser lithography etc., since it is excellent in transparency in the vicinity of 193 nm, resin which generally has a structural unit derived from (meth) acrylic acid ester in a main chain (acrylic resin) ) Is used. In the case of the positive type, such a resin is a structural unit derived from a (meth) acrylic acid ester containing a tertiary alkyl ester type acid dissociable, dissolution inhibiting group containing an aliphatic polycyclic group, for example, 2-alkyl-2- Resin which has a structural unit derived from adamantyl (meth) acrylate etc. is mainly used (for example, refer patent document 1).

In addition, "(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 acid generators used in chemically amplified resists, various kinds of acid generators have been proposed so far, and onium salt-based acid generators such as iodonium salts and sulfonium salts are known.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2003-241385

As an anion part of the onium salt type acid generator mentioned above, perfluoroalkyl sulfonate ion is currently used generally. It is considered that such an anion perfluoroalkyl chain is preferably long in order to suppress diffusion of an acid after exposure. By the way, the C6-C10 perfluoroalkyl chain is hardly decomposable, and nonafluorobutanesulfonic acid ion etc. are used for the safety of handling which considered bioaccumulation. Therefore, there is a need for a new compound which is more preferable as an acid generator for a resist composition.

This invention is made | formed in view of the said situation, The novel compound useful as an acid generator for resist compositions, its manufacturing method, the compound useful as a precursor of this compound, its manufacturing method, acid generator, resist composition, and resist pattern formation method The purpose is to provide.

In order to achieve the above object, the present invention adopts the following configuration.

That is, the 1st aspect of this invention is a compound (henceforth a compound (B1)) represented by the following general formula (b1-1).

[Formula 1]

[Wherein, R ¹ is an aryl group or alkyl group which may have a substituent, R ³ is a hydrogen atom or an alkyl group, n1 is 0 or 1 and when n1 is 1, R ¹ And R ³ may be bonded to each other to form a ring having a 3 to 7 membered ring structure together with a carbon atom having R ¹ bonded thereto and a carbon atom having R ³ bonded thereto, and A is a sulfur atom having the A bonded thereto; It is a bivalent group which forms the ring of a 3-7 membered ring structure together, The said ring may have a substituent and R <^2> may be a C1-C10 linear group which may have an aromatic group and a substituent. Or a linear or branched alkenyl group having 2 to 10 carbon atoms which may have a branched alkyl group or a substituent, n is 0 or 1, and Y ¹ is an alkylene group having 1 to 4 carbon atoms which may be substituted with fluorine;

In a second aspect of the present invention, a compound represented by the following General Formula (I), a compound represented by the following General Formula (II), and a copper catalyst are reacted to obtain a compound represented by the following General Formula (b1-1-1). It is a manufacturing method (henceforth a manufacturing method of a compound (B1-1)) of a compound represented by general formula (b1-1-1) containing a process.

[Formula 2]

[In formula, A is a divalent group which forms the ring of a 3-7 membered ring structure with the sulfur atom which said A couple | bonded, The said ring may have a substituent and R <^2> may have a substituent. group, carbon atoms which may have a substituent of 1 to 10 for a linear or branched alkyl group, or a straight chain having 2 to 10 carbon atoms which may have a substituent-type or branched alkenyl group, n is 0 or 1, Y ¹ Is an alkylene group having 1 to 4 carbon atoms which may be fluorine-substituted, and R ¹ is each independently an aryl group or alkyl group which may have a substituent]

A third aspect of the present invention is a compound represented by the following general formula (I) (hereinafter referred to as compound (I)).

[Formula 3]

[In formula, R <^2> is a C1-C10 linear or branched alkyl group which may have the aromatic group which may have a substituent, a C1-C10 linear or branched alkyl group which may have a substituent, or a substituent. Is an alkenyl group, n is 0 or 1, Y ¹ is an alkylene group having 1 to 4 carbon atoms which may be fluorine-substituted, and R ¹ is each independently an aryl group or alkyl group which may have a substituent]

The 4th aspect of this invention includes the process of reacting the compound represented by the following general formula (I-1), and the compound represented by the following general formula (I-2), and obtaining the compound represented by the following general formula (I). And a method for producing a compound represented by General Formula (I) (hereinafter referred to as a method for producing Compound (I)).

[Formula 4]

[In formula, R <^2> is a C1-C10 linear or branched alkyl group which may have the aromatic group which may have a substituent, a C1-C10 linear or branched alkyl group which may have a substituent, or a substituent. An alkenyl group, n is 0 or 1, Y ¹ is an alkylene group having 1 to 4 carbon atoms which may be fluorine-substituted, M ⁺ is an alkali metal ion, and R ¹ is an aryl group which may each independently have a substituent; Or an alkyl group, R ⁷ is an alkyl group or a fluorinated alkyl group]

5th aspect of this invention is an acid generator which consists of a compound (B1) of said 1st aspect.

A sixth aspect of the present invention is a resist composition containing a base component (A) whose solubility in an alkaline developer is changed by the action of an acid, and an acid generator component (B) which generates an acid by exposure,

Said acid generator component (B) contains the acid generator (B1) which consists of a compound represented by following General formula (b1-1), It is a resist composition characterized by the above-mentioned.

[Formula 5]

[Wherein, R ¹ is an aryl group or alkyl group which may have a substituent, R ³ is a hydrogen atom or an alkyl group, n1 is 0 or 1 and when n1 is 1, R ¹ and R ³ are bonded to each other, You may form the ring of a 3-7 membered ring structure with the carbon atom which the said R <^1> couple | bonded, and the carbon atom which R <^3> couple | bonded, and A is a 3-7 membered ring structure with the sulfur atom which the said A couple | bonded. It is a bivalent group which forms a ring, The said ring may have a substituent, R <^2> may be the aromatic group which may have a substituent, the C1-C10 linear or branched alkyl group which may have a substituent, or a substituent Is a linear or branched alkenyl group having 2 to 10 carbon atoms, n is 0 or 1, and Y ¹ is an alkylene group having 1 to 4 carbon atoms which may be substituted with fluorine;

A seventh aspect of the present invention includes a step of forming a resist film on a support using the resist composition of the sixth aspect, a step of exposing the resist film, and an alkali development of the resist film to form a resist pattern. It is a resist pattern formation method.

In the specification and claims,

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.

An "aliphatic cyclic group" refers to a monocyclic group or a polycyclic group having no aromatics.

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

"Alkylene group" shall contain a bivalent saturated hydrocarbon group of linear, branched, and cyclic unless otherwise indicated.

A "lower alkyl group" is a C1-C5 alkyl group.

A "structural unit" means the monomeric unit (monomer unit) which comprises a resin component (polymer).

"Exposure" is taken as the concept containing the radiation irradiation generally.

According to the present invention, a novel compound useful as an acid generator for a resist composition, a method for producing the same, a compound useful as a precursor of the compound, a method for producing the acid generator, a resist composition, and a method for forming a resist pattern can be provided.

Compound (B1)

The compound (B1) of the first aspect of the present invention is represented by general formula (b1-1).

In formula (b1-1), n1 is 0 or 1. When n1 is 0, a compound (B1) is represented by the following general formula (b1-1-1). When n1 is 1, a compound (B1) is represented by the following general formula (b1-1-2).

[Formula 6]

^{[Wherein, R 1, R 3, A} , R 2, n, Y 1 is ^{R 1, R 3, A,} R 2, n, Y 1 in each of formula (b1-1) Is the same as

There is no restriction | limiting in particular as an aryl group of R <^1> , For example, a C6-C20 aryl group is mentioned. As this aryl group, a C6-C10 aryl group is preferable at the point which can be synthesize | combined at low cost, and a phenyl group, a naphthyl group, etc. are mentioned specifically ,.

The aryl group may have a substituent. Here, that an aryl group has a substituent means that one part or all part of the hydrogen atom of an unsubstituted aryl group is substituted by the substituent (group or atom other than a hydrogen atom).

As a substituent which the aryl group may have, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group etc. are mentioned, for example.

As an alkyl group as a substituent of the said aryl 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 aryl group, a C1-C5 alkoxy group is preferable, and a methoxy group, an ethoxy group, a propoxy group, n-butoxy group, tert-butoxy group, etc. are mentioned.

As an alkoxy group as a substituent of the said aryl 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 is preferable. , Methoxy group and ethoxy group are most preferred.

As a halogen atom as a substituent of the said aryl 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 aryl 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.

There is no restriction | limiting in particular as an alkyl group of R <^1> , 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. A methyl group is mentioned at the point which is excellent in resolution and can be synthesize | combined at low cost.

The alkyl group may have a substituent. Here, that an alkyl group has a substituent means that one part or all part of the hydrogen atom of an unsubstituted alkyl group is substituted by the substituent (group or atom other than a hydrogen atom).

As a substituent which the alkyl group may have, an alkoxy group, a halogen atom, a hydroxyl group, etc. are mentioned, for example. As this alkoxy group and a halogen atom, the thing similar to the alkoxy group and halogen atom which were illustrated as the substituent which the said aryl group may have, respectively is mentioned.

In the present invention, R ¹ is preferably an aryl group which may have a substituent, more preferably a phenyl group or naphthyl group which may have a substituent, and most preferably a phenyl group which may have a substituent.

There is no restriction | limiting in particular as an alkyl group of R <^3> , The same thing as the alkyl group of said R <^1> is mentioned.

In the present invention, R ³ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

When n1 is 1, R <^1> and R <^3> in a formula may combine with each other, and may form the ring of a 3-7 membered ring structure with the carbon atom which the said R <^1> couple | bonded, and the carbon atom which R <^3> couple | bonded. It is preferable that it is a 5-7 membered ring structure, and, as for the ring, it is more preferable that it is a 5 or 6 membered ring structure.

A is a bivalent group which forms the ring of a 3-7 membered ring structure with the sulfur atom which said A couple | bonded, The said ring may have a substituent.

In A, it is preferable that the said ring is a 5-7 membered ring structure, and it is more preferable that it is a 5 or 6 membered ring structure.

As a substituent which the said ring may have, the thing similar to what was illustrated as a substituent which the aryl group of said R <^1> may have is mentioned.

Especially as a cation part of a compound (B1), the cation part represented by the following general formula (b1'-1) or (b1'-2) is preferable.

[Formula 7]

In formula, R <^8> and R <^9> is a phenyl group, a naphthyl group, or a C1-C5 alkyl group which may respectively independently have a substituent. As this alkyl group, a methyl group is especially preferable.

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

In formula (b1-1), the aromatic group of R <^2> may be a hydrocarbon group comprised only of a carbon atom and a hydrogen atom, and may be a hetero atom containing group containing a carbon atom, a hydrogen atom, and hetero atoms other than those. Specifically, the aryl group which removed one hydrogen atom from the ring of aromatic hydrocarbons, such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, a phenanthryl group, etc. ; Heteroaryl group by which some carbon atoms which comprise the ring of these aryl groups were substituted by hetero atoms, such as an oxygen atom, a sulfur atom, and a nitrogen atom; Aryl alkyl groups, such as a benzyl group, a phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group, etc. are mentioned.

It is preferable that it is 1-4, as for carbon number of the alkyl chain in the said arylalkyl group, it is more preferable that it is 1-2, and it is especially preferable that it is one.

The aromatic group of R ² may have a substituent. As this substituent, the thing similar to what was illustrated as a substituent which the aryl group of said R <^1> may have is mentioned.

In R <^2> , as a C1-C10 linear alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, etc. are mentioned, for example. Can be. Among these, a methyl group is preferable.

Examples of the branched alkyl group having 1 to 10 carbon atoms include 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 alkyl group of R ² may have a substituent. As this substituent, the thing similar to what was illustrated as a substituent which the alkyl group of said R <^1> may have is mentioned.

Carbon atoms, a linear or branched alkenyl group of 2 to 10 the R ² is a carbon number of 2-5 is preferable, and 2 to 4 is preferable, and 3 is particularly preferable. Specifically, a vinyl group, a propenyl group (allyl group), butynyl group, 1-methylpropenyl group, 2-methylpropenyl group, etc. are mentioned, for example, A propenyl group is especially preferable.

The alkenyl group of R ² may have a substituent. As this substituent, the thing similar to what was illustrated as a substituent which the alkyl group of said R <^1> may have is mentioned.

Here, in R <^2> , "you may have a substituent" means that part or all of the hydrogen atoms in the aromatic hydrocarbon group, the linear or branched alkyl group, or the linear or branched alkenyl group It means that may be substituted by a substituent (an atom or group other than a hydrogen atom).

The number of substituents in R ² may be one or two or more.

n may be 0 or 1 may be sufficient as it.

Y ¹ is a C1-C4 alkylene group which may be fluorine-substituted.

Y, an alkylene group having from 1 to 4 carbon atoms which may be substituted with fluorine of ^1,

Etc. can be mentioned.

As Y <^1> , a C1-C4 alkylene group (alkyl fluoride group) substituted by fluorine is preferable, and the fluorinated alkylene group in which the carbon atom couple | bonded with the adjacent sulfur atom is especially fluorinated is preferable. As such a fluorinated alkylene group,

Etc. can be mentioned.

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

In this invention, as an anion part of a compound (B1), the anion part represented by the following general formula (b1 "-1) is preferable.

[Formula 8]

[In formula, Y <^1> is the same as the above, R <^53> is a C2-C10 alkenyl group or an aryl group, R <^54> is a C1-C5 linear or branched alkylene group.]

As R ⁵³ , a vinyl group, a phenyl group or a naphthyl group is preferable, and a vinyl group or a naphthyl group is more preferable.

As R ⁵⁴ , a linear alkylene group having 1 to 5 carbon atoms is preferable, and a methylene group is most preferable.

As a compound (B1) of this invention, the compound which consists of the cation part represented by the said General formula (b1'-1) or (b1'-2), and the anion part represented by the said General formula (b1 "-1) is preferable. Do.

<Method for Producing Compound (B1)>

It does not specifically limit as a manufacturing method of the compound (B1) of this invention, A well-known manufacturing method of a sulfonium salt can be used.

For example, compound (B1) can be obtained by making compound (b0-1) represented by the following general formula (b0-1) react with compound (b0-2) represented by the following general formula (b0-2).

[Formula 9]

^{[Wherein, R 2, n, Y 1} , A, R 3, n1, R 1 is ^{R 2, n, Y 1,} A, R 3, n1, R 1 in each formula (b1-1) Is the same as M ⁺ is an alkali metal ion and Xh ⁻ is a halogen ion]

Examples of the alkali metal ions of M ⁺ include sodium ions, lithium ions and potassium ions, and sodium ions or lithium ions are preferable.

Examples of the halogen ion of Xh ⁻ include chlorine ion, bromine ion, iodine ion, and the like, and chlorine ion or bromine ion is preferable.

The compound (b0-1) and the compound (b0-2) can be reacted by, for example, bringing these compounds into contact with a solvent such as water or dichloromethane.

Although the manufacturing method of a compound (b0-1) is not specifically limited, For example, in a solvent, such as tetrahydrofuran and water, the compound represented by the following general formula (b0-1-11) is sodium hydroxide, lithium hydroxide, etc. After reacting in an aqueous solution of an alkali metal hydroxide to obtain a compound represented by the following general formula (b0-1-12), the compound is represented by the following general formula (b0) in the presence of an acidic catalyst in an organic solvent such as benzene and dichloroethane. By dehydrating condensation with the alcohol represented by -1-13), the compound (compound represented by the following general formula (b0-1-01)) in which n in General Formula (b0-1) is 1 is obtained.

[Formula 10]

[Wherein, R ²¹ is an alkyl group having a carbon number of ^{1 ~ 5, Y 1, M} +, R 2 is Y ^1, M ^+, the same as R ^2, and each of Xh formula (b0-1) ^- Equation (b0 Is the same as Xh ^- in -2)]

For example, fluorine silver, the compound represented by the following general formula (b0-1-01), and the compound represented by the following general formula (b0-1-02) are made to react in organic solvents, such as anhydrous diglyme, The compound represented by the following general formula (b0-1-03) is obtained, and the compound is reacted with an alkali metal hydroxide such as sodium hydroxide and lithium hydroxide in an organic solvent such as tetrahydrofuran, acetone or methyl ethyl ketone. The compound (compound represented by the following general formula (b0-1-0)) whose n in general formula (b0-1) is 0 is obtained.

[Formula 11]

[Wherein, Y ^1, M ^+, R ² are each formula (b0-1) of the Y ^1, M ^+, the same, and Xh and R ^{2 -} are the same as ^- Xh of the formula (b0-2)]

Production method of compound (b0-2) it is not particularly limited, for example, to a compound represented by the sulfur atom represented by the general formula (b0-2-1), by known ^{methods, - [CH (R 3)} - It can obtain by introducing the group represented by CO] _n1- R <^1> .

As a specific example, for example, when n1 is 0, the compound represented by the following general formula (b0-2-1) is oxidized, and the -S- moiety in the compound is -S (= O)-. And an alkane such as methane or an aromatic hydrocarbon such as benzene in the presence of a catalyst such as aluminum chloride, to give a compound whose n1 in General Formula (b0-2) is 0. When n1 is 1, you may obtain and use a commercially available bromide body etc., for example.

[Formula 12]

[Wherein A is the same as above]

When n1 is 0, ie, when compound (B1) is a compound represented by the said general formula (b-1-1) (henceforth a compound (B1-1)), the compound (B1-1 As a manufacturing method of), the manufacturing method of the compound (B1-1) of this invention mentioned later is preferable.

<< Production Method of Compound (B1-1) >>

The manufacturing method (henceforth a manufacturing method (1)) of the compound (B1-1) of 2nd aspect of this invention is a compound (henceforth a compound (I)) represented by the following general formula (I), The process of making compound (B1-1) represented by following General formula (b1-1-1) react with the compound represented by the following general formula (II) (henceforth a compound (II)), and a copper catalyst. do.

By carrying out these steps, R ¹ in compound (I) is introduced into a sulfur atom of compound (II) to form a sulfonium ion, and the sulfonium ion and an anion portion of compound (I) form a compound. (B1-1) is obtained.

[Formula 13]

[In formula, A is a divalent group which forms the ring of a 3-7 membered ring structure with the sulfur atom which said A couple | bonded, The said ring may have a substituent and R <^2> may have a substituent. Is a C1-C10 linear or branched alkyl group which may have a hydrocarbon group, a substituent, or a C2-C10 linear or branched alkenyl group which may have a substituent, n is 0 or 1, Y is ¹ is a C1-C4 alkylene group which may be fluorine-substituted, and R <^1> is the aryl group or alkyl group which may respectively independently have a substituent.]

Wherein, A, R ^2, n, Y ^1, R ¹ is, each independently the same as A, R ^2, n, Y ^1, R ¹ in the formula (b-1).

Compound (I) used here is a novel compound. This compound (I) can be manufactured by the manufacturing method of compound (I) mentioned later, for example.

As compound (II), a commercially available thing may be used and you may synthesize | combine.

It is preferable that it is a bivalent copper catalyst as a copper catalyst, Specifically, the compound (henceforth a compound (III)) represented by the following general formula (III) is mentioned.

[Formula 14]

(R ⁶ COO) ₂ Cu... (Ⅲ)

[Wherein, R ⁶ is an aryl group which may have a substituent]

Wherein the aryl group which may have a substituent R ^6, may include the same as those exemplified as an aryl group which may have a substituent in the R ^1.

Specific examples of the compound (III) include copper benzoate (II) and the like.

As compound (III), a commercially available thing can be used.

Although it does not specifically limit as a method of making compound (I), a compound (II), and a copper catalyst react, For example, making compound (I), a compound (II), and a copper catalyst react in a reaction solvent. A method is mentioned.

As a reaction solvent, what is necessary is just what can melt | dissolve a raw material, Specifically, chlorobenzene, toluene, etc. are mentioned.

50-150 degreeC is preferable and 90-120 degreeC of reaction temperature is more preferable.

Although reaction time changes also with reactivity, reaction temperature, etc. of a compound (I) and a compound (II), 10 to 180 minutes are preferable normally, and 30 to 90 minutes are more preferable.

As for the usage-amount of compound (II), about 0.5-3 molar equivalent is preferable with respect to the usage-amount of compound (I), and 0.9-1.5 molar equivalent is more preferable.

As for the usage-amount of a copper catalyst, about 0.01-0.5 molar equivalent is preferable with respect to compound (I), and 0.02-0.1 molar equivalent is more preferable.

The structure of the compound (B1-1) obtained at the said process is ¹ H-nuclear magnetic resonance (NMR) spectroscopy, ¹³ C-NMR spectrum, ¹⁹ F-NMR spectrum, infrared absorption (IR) spectrum, mass spectrometry It can be confirmed by general organic analysis methods, such as (MS) method, elemental analysis method, and X-ray crystal diffraction method.

<Compound (Ⅰ) >>

The compound (I) of the third aspect of the present invention is represented by the general formula (I).

Equation (Ⅰ) of, ^{R 2, n, Y 1,} R 1 is, each is the same as ^{R 2, n, Y 1,} R 1 in the formula (b1-1).

Compound (I) is useful as a precursor of the said compound (B1-1), and is used preferably for the manufacturing method (1) of the said compound (B1-1).

In addition, compound (I) is itself usable as an acid generator, and can be mix | blended with a resist composition as an acid generator.

<< Production method of compound (I) >>

The manufacturing method of compound (I) of the 4th aspect of this invention is a compound represented by the following general formula (I-1) (henceforth a compound (I-1)), and the following general formula (I-2). It includes the step of reacting the compound (hereinafter referred to as compound (I-2)) to obtain compound (I).

[Formula 15]

[In formula, R <^2> may be an aromatic hydrocarbon group which may have a substituent, a C1-C10 linear or branched alkyl group which may have a substituent, or a C2-C10 linear or branched thing which may have a substituent. It is a type alkenyl group, n is 0 or 1, Y <^1> is a C1-C4 alkylene group which may be fluorine-substituted, M <^+> is an alkali metal ion, R <^1> may respectively independently have a substituent. Group or an alkyl group, R ⁷ is an alkyl group or a fluorinated alkyl group]

Wherein, ^{R 2, n, Y 1,} R 1 is, each is the same as ^{R 2, n, Y 1,} R 1 in the formula (b1-1).

Examples of alkali metal ions of M ⁺ include sodium ions, lithium ions and potassium ions.

The alkyl group or fluorinated alkyl group of R ⁷ may be linear, branched, or cyclic.

As said linear or branched alkyl group, it is preferable that it is C1-C10, It is more preferable that it is C1-C8, It is further more preferable that it is C1-C4.

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.

As said fluorinated alkyl group, the group by which one part or all part of the hydrogen atom of the said alkyl group was substituted by the fluorine atom is mentioned.

As R <^7> , an alkyl group is preferable, a linear alkyl group is preferable, and a methyl group is the most preferable.

Compound (I-1) can be synthesize | combined by the method similar to the manufacturing method of compound (b0-1) mentioned above, for example.

A commercially available thing can be used for compound (I-2).

Compound (I-1) and compound (I-2) can be made to react, for example by making these compounds contact in solvents, such as water and dichloromethane.

The structure of the compound obtained in the above process is ¹ H-nuclear magnetic resonance (NMR) spectroscopy, ¹³ C-NMR spectroscopy, ¹⁹ F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), Elemental analysis, X-ray crystal diffraction, etc. can be confirmed by the usual organic analysis methods.

<< acid generator >>

The acid generator of the fifth aspect of the present invention is composed of the compound (B1) of the first aspect.

The acid generator is useful as an acid generator for a chemically amplified resist composition, for example, as an acid generator component (B) of the resist composition of the sixth aspect of the present invention described later.

<< resist composition >>

The resist composition of the sixth aspect of the present invention is a base component (A) (hereinafter referred to as component (A)) whose solubility in an alkaline developer is changed by the action of an acid, and an acid generation which generates an acid by exposure. 1st component (B) (henceforth a component (B)) is contained, and the said (B) component contains the acid generator (B1) which consists of a compound represented by the said general formula (b1-1).

When a resist film formed using such a resist composition is subjected to selective exposure during the formation of a resist pattern, an acid is generated from the component (B), and the acid changes the solubility of the component (A) in the alkaline developer. As a result, the solubility in the alkali developer of the exposed portion of the resist film is changed, while the solubility in the alkali developer is not changed. Is dissolved and removed to form a resist pattern.

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

<(A) component>

As (A) component, the organic compound currently used as a base component for chemically amplified resists can be used individually by 1 type or in mixture of 2 or more types.

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

The said organic compound whose molecular weight is 500 or more is largely divided into the low molecular weight organic compound (henceforth a low molecular compound) whose molecular weight is 500 or more and 2000, and the high molecular weight resin (high molecular material) whose molecular weight is 2000 or more. As said low molecular weight compound, a nonpolymer is used normally. In the case of resin (polymer, copolymer), the mass average molecular weight of polystyrene conversion by GPC (gel permeation chromatography) shall be used as "molecular weight." Hereinafter, when only "resin" is called, it shall show resin whose molecular weight is 2000 or more.

As the component (A), a resin in which alkali solubility is changed by the action of an acid can be used, and a low molecular material in which alkali solubility is changed by the action of an acid can be used.

When the resist composition of the present invention is a negative resist composition, as the component (A), a soluble base component is used in an alkaline developer, and a crosslinking agent is blended in the negative resist composition.

When an acid is generated from (B) component by exposure, such a negative type resist composition will generate | occur | produce bridge | crosslinking between a base material component and a crosslinking agent, and will change to poor solubility with respect to alkaline developing solution. Therefore, in forming a resist pattern, if the resist film obtained by apply | coating the said negative resist composition on a board | substrate is selectively exposed, an exposure part will change to poor solubility with respect to an alkaline developing solution, while an unexposed part will remain soluble with respect to an alkaline developing solution. Since it does not change, the resist pattern can be formed by alkali development.

As (A) component of a negative resist composition, soluble resin (henceforth alkali-soluble resin) is used with respect to alkali developing solution.

As the alkali-soluble resin, a resin having a unit derived from at least one selected from α- (hydroxyalkyl) acrylic acid or lower alkyl ester of α- (hydroxyalkyl) acrylic acid forms a good resist pattern with little swelling. It is preferable because it can be done. Moreover, (alpha)-(hydroxyalkyl) acrylic acid is acrylic acid which the hydrogen atom couple | bonds with the carbon atom of the (alpha) position which a carboxy group couple | bonds, and a hydroxyalkyl group (preferably C1-C5 hydroxide) to this carbon atom of the (alpha) position. One or both of the (alpha)-hydroxyalkyl acrylic acid to which the hydroxyalkyl group) is couple | bonded is shown.

As a crosslinking agent, when using amino crosslinking agents, such as glycoluril which has a methylol group or the alkoxy methyl group, for example, normally, since the favorable resist pattern with little swelling can be formed, it is preferable. It is preferable that the compounding quantity of a crosslinking agent is 1-50 mass parts with respect to 100 mass parts of alkali-soluble resin.

In the case where the resist composition of the present invention is a positive resist composition, as the component (A), a base component having increased solubility in an alkaline developer due to the action of an acid is used. The component (A) is poorly soluble to the alkaline developer before exposure, and when acid is generated from the component (B) by exposure, the solubility in the alkaline developer is increased by the action of the acid. Therefore, in the formation of the resist pattern, when the positive resist composition is selectively exposed to the resist film obtained by coating the substrate, the exposed portion is changed from poorly soluble to soluble to an alkaline developer, while the unexposed portion is Since the alkali poor solubility is not changed as it is, the resist pattern can be formed by alkali development.

In the resist composition of the present invention, the component (A) is preferably a base component having increased solubility in an alkaline developer due to the action of an acid. That is, it is preferable that the resist composition of this invention is a positive resist composition.

The component (A) may be a resin component (A1) (hereinafter may be referred to as component (A1)) in which the solubility in an alkaline developer is increased by the action of an acid. The low molecular weight compound (A2) (henceforth a component (A2) component) by which solubility is increased may be sufficient, and a mixture thereof may be sufficient.

[(A1) component]

As (A1) component, the resin component (base resin) currently used as a base component for chemically amplified resist can be used individually by 1 type, or in mixture of 2 or more types.

In the present invention, the component (A1) preferably contains a structural unit derived from an acrylate ester.

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

"Acrylic acid ester" is taken as the concept including what the substituent (atoms other than a hydrogen atom or group) couple | bonded with the carbon atom of the (alpha) position other than the acrylate ester which the hydrogen atom couple | bonded with the carbon atom of the (alpha) position. As a substituent, a lower alkyl group, a halogenated lower alkyl group, etc. are mentioned.

In addition, the alpha position (carbon atom of an alpha position) of the structural unit derived from an acrylate ester means the carbon atom to which the carbonyl group couple | bonded unless there is particular notice.

In the acrylate ester, specifically, as a lower alkyl group as a substituent of the (alpha) position, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, tert- butyl group, a pentyl group, isopentyl group, Lower linear or branched alkyl groups, such as neopentyl group, are mentioned.

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

In this invention, what is couple | bonded with the (alpha) position of an acrylate ester is preferably a hydrogen atom, a lower alkyl group, or a halogenated lower alkyl group, It is more preferable that it is a hydrogen atom, a lower alkyl group, or a fluorinated lower alkyl group, It is easy to obtain industrially In one point, it is most preferable that they are a hydrogen atom or a methyl group.

It is preferable that (A1) component especially has a structural unit (a1) derived from the acrylate ester containing an acid dissociable, dissolution inhibiting group.

In addition, the component (A1) preferably has a structural unit (a2) derived from an acrylate ester containing a lactone-containing cyclic group in addition to the structural unit (a1).

The component (A1) preferably has a structural unit (a3) derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group in addition to the structural unit (a1) or in addition to the structural units (a1) and (a2). Do.

Construction unit (a1)

Before dissociation, the acid dissociable, dissolution inhibiting group in the structural unit (a1) has an alkali dissolution inhibiting property in which the entire component (A1) is poorly dissolved with respect to the alkali developer, and is dissociated with an acid to remove all of the component (A1). What is proposed as an acid dissociable, dissolution inhibiting group of the base resin for chemically amplified resists can be used so far as it improves the solubility to alkaline developing solution. Generally, the group which forms a cyclic or chain | strand-type tertiary alkyl ester with the carboxyl group in (meth) acrylic acid etc .; Acetal acid dissociable, dissolution inhibiting groups, such as an alkoxyalkyl group, are widely known.

Here, the "tertiary alkyl ester" means ester by being substituted with a chain or cyclic alkyl group by the hydrogen atom of a carboxyl group, and of the terminal of the carbonyloxy group (-C (O) -O-) The structure which the tertiary carbon atom of the said chain | strand or cyclic alkyl group couple | bonded with the oxygen atom is shown. In this tertiary alkyl ester, when an acid acts, the bond is cleaved between the oxygen atom and the tertiary carbon atom.

In addition, the chain or cyclic alkyl group may have a substituent.

Hereinafter, group which becomes acid dissociation by making a carboxy group and tertiary alkyl ester are called "tertiary alkyl ester type acid dissociable, dissolution inhibiting group" for convenience.

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

The "aliphatic branched chain" means having a branched chain structure having no aromaticity. Although the structure of an "aliphatic branched-type acid dissociable, dissolution inhibiting group" is not limited to the group (hydrocarbon group) which consists of a carbon atom and a hydrogen atom, 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, dissolution inhibiting group, a C4-C8 tertiary alkyl group is preferable, and a tert- butyl group, tert-pentyl group, tert-heptyl group, etc. are mentioned specifically ,.

An "aliphatic cyclic group" represents a monocyclic group or a polycyclic group having no aromaticity.

The "aliphatic cyclic group" in the structural unit (a1) may or may not have a substituent. As a substituent, a C1-C5 lower alkyl group, a fluorine atom, a C1-C5 fluorinated lower alkyl group substituted by the fluorine atom, an oxygen atom (= O), etc. are mentioned.

Although the structure of the basic ring except the substituent of an "aliphatic cyclic 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. It is preferable that "aliphatic cyclic group" is a polycyclic group.

As the aliphatic cyclic group, for example, polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane, tetracycloalkane, which may or may not be substituted with a lower alkyl group, a fluorine atom or a fluorinated alkyl group, may be used. The group etc. which removed more than one hydrogen atom are mentioned. More specifically, one or more hydrogen atoms are removed from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane. And the like can be mentioned.

Examples of the acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group include groups having a tertiary carbon atom on the ring skeleton of the cyclic alkyl group, and specifically 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group etc. are mentioned. Or in the structural unit represented by the following general formula (a1 "-1)-(a1" -6), like the group couple | bonded with the oxygen atom of the carbonyloxy group (-C (O) -O-), Aliphatic cyclic groups, such as a danyl group, a cyclohexyl group, a cyclopentyl group, a norbornyl group, a tricyclo decanyl group, a tetracyclo dodecanyl group, and a branched chain alkylene group which has a tertiary carbon atom couple | bonded with this The group can be mentioned.

[Formula 16]

[Wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; R ¹⁵ , R ¹⁶ Represents an alkyl group (which may be either a linear or branched chain, preferably having 1 to 5 carbon atoms)]

In General Formulas (a1 ''-1) to (a1 ''-6), the lower alkyl group or halogenated lower alkyl group of R is the same as the lower alkyl group or halogenated lower alkyl group which may be bonded to the α position of the acrylate ester. .

The "acetal acid dissociable, dissolution inhibiting group" is generally substituted with a hydrogen atom at the terminal of an alkali-soluble group such as a carboxyl group or a hydroxyl group and bonded to an oxygen atom. When an acid is generated by exposure, the acid acts to break the bond between the acetal-type acid dissociable, dissolution inhibiting group and the oxygen atom bonded to the acetal-type acid dissociable, dissolution inhibiting group.

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

[Formula 17]

[Wherein, R ^{1 ′} and R ^{2 ′} each independently represent a hydrogen atom or a lower alkyl group, n represents an integer of 0 to 3, and Y represents a lower alkyl group or an aliphatic cyclic group]

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

Examples of the lower alkyl group of R ^{1 '} and R ^{2' include} the same as those of the lower alkyl group of R, a methyl group or an ethyl group is preferred, and a methyl group is most preferred.

In the present invention, at least one of R ^{1 ′} and R ^{2 ′} is preferably a hydrogen atom. That is, it is preferable that acid dissociable, dissolution inhibiting group (p1) is group represented by the following general formula (p1-1).

[Formula 18]

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

As a lower alkyl group of Y, the same thing as the lower alkyl group of said R is mentioned.

As the aliphatic cyclic group of Y, any of monocyclic or polycyclic aliphatic cyclic groups that have been proposed in the conventional ArF resist or the like can be appropriately selected and used, and examples thereof can be the same as those described above for the "aliphatic cyclic group".

Moreover, as an acetal type acid dissociable, dissolution inhibiting group, the air represented by following General formula (p2) is mentioned.

[Formula 19]

[In formula, R <^17> , R <^18> is respectively independently a linear or branched alkyl group or a hydrogen atom, 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 the terminal of R ^{17 and} the terminal of 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 a linear or branched chain, it is preferably 1 to 5 carbon atoms, more preferably an ethyl group and a methyl group, most preferably an ethyl group.

When R <^19> is cyclic, it is preferable that it is C4-C15, It is more preferable that it is C4-C12, and C5-C10 is the most preferable. Specifically, the group 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. Specifically, a group in which one or more hydrogen atoms are removed from a monocycloalkane such as cyclopentane and cyclohexane, and a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane Etc. can be mentioned. Especially, the group remove | excluding one or more hydrogen atoms from amandan is preferable.

In the above formula, R ¹⁷ and R ¹⁹ are each independently a linear or branched alkylene group (preferably a C 1-5 alkylene group), and the terminal of R ^{19 and} the terminal of R ¹⁷ are bonded to each other. You may be.

In this case, a cyclic group is formed by R ¹⁷ and R ^19, and an oxygen atom and the oxygen atom and the carbon atom 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 tetrahydropyranyl group, tetrahydrofuranyl group and the like.

As structural unit (a1), it is preferable to use 1 or more types chosen from the group which consists of a structural unit represented by the following general formula (a1-0-1), and the structural unit represented by the following general formula (a1-0-2). Do.

[Formula 20]

[Wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; X ¹ represents an acid dissociable, dissolution inhibiting group]

[Formula 21]

[Wherein, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; X ² represents an acid dissociable, dissolution inhibiting group; Y ² represents an alkylene group or an aliphatic cyclic group]

In general formula (a1-0-1), the lower alkyl group or halogenated lower alkyl group of R is the same as the lower alkyl group or halogenated lower alkyl group which may be bonded to the α position of the acrylate ester.

If X ¹ is an acid dissociable, dissolution inhibiting group, it will not be specifically limited, For example, the above-mentioned tertiary alkyl ester type acid dissociable, dissolution inhibiting group, acetal type acid dissociable, dissolution inhibiting group, etc. are mentioned, Alkyl ester type acid dissociable, dissolution inhibiting groups are preferred.

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).

Y ² is preferably an alkylene group having 1 to 10 carbon atoms or a divalent aliphatic cyclic group, and as the aliphatic cyclic group, the description of the "aliphatic cyclic group" is used except that a group in which two or more hydrogen atoms are removed is used. The same can be used.

When Y <^2> is a C1-C10 alkylene group, it is more preferable that it is C1-C6, It is especially preferable that it is C1-C4, It is most preferable that it is C1-C3.

When Y <^2> is a divalent aliphatic cyclic group, it is especially preferable that 2 or more hydrogen atoms were removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, and tetracyclododecane. .

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

[Formula 22]

[In the formula, X 'represents a tertiary alkyl ester type acid dissociable, dissolution inhibiting group, and Y represents a C1-5 lower alkyl group or an aliphatic cyclic group; n represents an integer of 0 to 3; Y ² Represents an alkylene group or an aliphatic cyclic group; R is the same as above, and R ^{1 '} and R ^2' each independently represent a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms.]

In formula, X 'is the same as the tertiary alkyl ester type acid dissociable, dissolution inhibiting group illustrated in said X <^1> .

R ^{1 ',} R ^2', roneun ^{n, Y, R 1 ',} R 2' in the general formula (p1) illustrated in each of the above-described "acetal-type acid dissociable, dissolution inhibiting group" described in, n, The same thing as Y is 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.

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

Among the above, the structural unit represented by general formula (a1-1) is preferable, and specifically, (a1-1-1)-(a1-1-6) and (a1-1-35)-(a1-1-) 41) It is more preferable to use at least 1 sort (s) chosen from the group of phosphorus.

In addition, as a structural unit (a1), especially represented by the following general formula (a1-1-01) which covers the structural unit of Formula (a1-1-1)-a formula (a1-1-4), and Formula (a1) The following general formula (a1-1-02) which covers the structural unit of -1-35)-(a1-1-41) is also preferable.

[Formula 34]

(Wherein R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R ¹¹ Represents a lower alkyl group)

[Formula 35]

(Wherein R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R ¹² Represents a lower alkyl group. h represents an integer of 1 to 3)

In general formula (a1-1-01), R is the same as above.

The lower alkyl group of R ¹¹ is the same as the lower alkyl group in R, and a methyl group or an ethyl group is preferable.

In general formula (a1-1-02), R is the same as above.

The lower alkyl group of R ¹² is the same as the lower alkyl group in R, preferably a methyl group or an ethyl group, and most preferably an ethyl group. h is preferably 1 or 2, most preferably 2;

As the structural unit (a1), one type may be used alone, or two or more types may be used in combination.

In the component (A1), the proportion of the structural unit (a1) is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and more preferably 25 to 50 with respect to all the structural units constituting the (A1) component. Mol% is more preferred. By setting it as the lower limit or more, a pattern can be easily obtained when it is set as a resist composition, and it can balance with the other structural unit by setting it as the upper limit or less.

Construction unit (a2)

In the present invention, the component (A1) preferably has a structural unit (a2) derived from an acrylate ester containing a lactone-containing cyclic group in addition to the structural unit (a1).

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 referred to as a polycyclic group, regardless of its structure, in the case of a monocyclic group.

When the (A1) component is used for formation of a resist film, the lactone cyclic group of a structural unit (a2) is effective in improving adhesiveness with respect to the board | substrate of a resist film, or improving affinity with the developing solution containing water.

As a structural unit (a2), it does not specifically limit but arbitrary things can be used.

Specifically, the lactone-containing monocyclic group includes a group in which one hydrogen atom is removed from γ-butyrolactone. 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.

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

[Formula 36]

[Wherein, R is a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group, R 'is a hydrogen atom, a lower alkyl group, or a C1-5 alkoxy group, m is an integer of 0 or 1, and A is a C1-C1 5 is an alkylene group or an oxygen atom]

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

The lower alkyl group of R 'is the same as the lower alkyl group of R in the structural unit (a1).

As a C1-C5 alkylene group of A, a methylene group, an ethylene group, n-propylene group, an isopropylene group, etc. are mentioned specifically ,.

In view of general formula (a2-1) (a2-5)-R 'is easy to obtain industrially, a hydrogen atom is preferable.

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

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

As the structural unit (a2), at least one member selected from the group consisting of structural units represented by the 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 chemical formulas (a2-1-1), (a2-1-2), (a2-2-1), (a2-2-2), (a2-3-1), (a2-3-2 ), at least one member selected from the group consisting of structural units represented by (a2-3-9) and (a2-3-10) is preferable.

As the structural unit (a2), one type may be used alone, or two or more types may be used in combination.

In the component (A1), the proportion of the structural unit (a2) is preferably from 5 to 60 mol%, more preferably from 10 to 50 mol%, based on the total of all the structural units constituting the (A1) component, 20 50 mol% is more preferable. By setting it as the lower limit or more, the effect by containing a structural unit (a2) is fully acquired, and setting it as the upper limit or less can balance the other structural unit.

Construction unit (a3)

In the present invention, the component (A1) is a structural unit derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group in addition to the structural unit (a1) or in addition to the structural units (a1) and (a2). It is preferable to have (a3).

When the component (A1) has a structural unit (a3), the hydrophilicity of the component (A1) is increased, the affinity with the developer is increased, solubility in the alkaline developer in the exposed portion is improved, and contributes to improvement in resolution. .

As a polar group, a hydroxyl group, a cyano group, a carboxy group, the hydroxyalkyl group in which one part of the hydrogen atoms of an 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 a polycyclic aliphatic hydrocarbon group (polycyclic group) are mentioned. As the polycyclic group, for example, a resin for a resist composition for an ArF excimer laser can be appropriately selected from among those proposed in a large number. It is preferable that carbon number of this polycyclic group is 7-30.

Among them, a structural unit derived from an acrylate ester containing an aliphatic polycyclic group containing a hydroxyalkyl group (alkyl fluorinated alkyl) in which a part of the hydrogen atoms of a hydroxyl group, cyano group, carboxyl group or alkyl group is substituted with a fluorine atom is more preferable. Do. 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 a structural unit (a3), when the hydrocarbon group in a polar group containing aliphatic hydrocarbon group is a C1-C10 linear or branched hydrocarbon group, the structural unit derived from the hydroxyethyl ester of acrylic acid is preferable, and this hydrocarbon When group is a polycyclic group, the structural unit represented by following formula (a3-1), the structural unit represented by (a3-2), and the structural unit represented by (a3-3) are mentioned as a preferable thing.

[Formula 42]

(In formula, R is the same as the above, j is an integer of 1-3, k is an integer of 1-3, t 'is an integer of 1-3, l is an integer of 1-5, s is Is an integer of 1 to 3)

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

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

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

As the structural unit (a3), one type may be used alone, or two or more types may be used in combination.

5-50 mol% is preferable with respect to all the structural units which comprise (A1) component, and, as for the ratio of a structural unit (a3), in component (A1), 5-40 mol% is more preferable, and it is 5-25 Mol% is more preferred. By setting it as the lower limit or more, the effect by containing a structural unit (a3) is fully acquired, and setting it as the upper limit or less can balance the other structural unit.

Construction unit (a4)

The component (A1) may contain other structural units (a4) other than the structural units (a1) to (a3) in a range that does not impair the effects of the present invention.

The structural unit (a4) is not particularly limited as long as it is another structural unit not classified into the above-mentioned structural units (a1) to (a3), but is not limited to ArF excimer laser and KrF excimer laser (preferably for ArF excimer laser). A large number of conventionally known ones can be used as used for resins for resists such as

As the structural unit (a4), for example, a structural unit derived from an acrylate ester containing an acid non-dissociable aliphatic polycyclic group is preferable. The polycyclic group can exemplify the same as those exemplified in the case of the structural unit (a1), for example, and a resist composition such as an ArF excimer laser or a KrF excimer laser (preferably an ArF excimer laser). As what is used for the resin component of the above, many conventionally known things can be used.

It is especially preferable at the point of at least 1 type chosen from tricyclo decanyl group, adamantyl group, tetracyclo dodecanyl group, isobornyl group, norbornyl group, and easy industrial acquisition. These polycyclic groups may have a C1-C5 linear or branched alkyl group as a substituent.

As a structural unit (a4), what is a structure of the following general formula (a4-1) (a4-5) can be illustrated specifically ,.

[Formula 43]

(Wherein R is the same as above)

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

In this invention, it is preferable that (A1) component contains the copolymer which has a structural unit (a1), (a2), and (a3). As this copolymer, the copolymer which consists of structural units (a1), (a2), and (a3), the copolymer which consists of structural units (a1), (a2), (a3), and (a4), etc. are mentioned.

As such a copolymer, it is preferable to contain three types of structural units represented, for example by following General formula (A1-11).

[Formula 44]

[Wherein Ra, Rb and Rc are each independently the same as R and R ¹¹ is a lower alkyl group]

R ¹¹ in the formula (A1-11) of a lower alkyl group, the general formula (a1-1-01) of R ¹¹ And methyl or ethyl groups are preferred.

(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.

Further, in the (A1) component, 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, so that -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).

Although the mass mean molecular weight (Mw) (polystyrene conversion basis by gel permeation chromatography) of (A1) component is not specifically limited, 2000-50000 are preferable, 3000-30000 are more preferable, 5000-20000 are the most desirable. If smaller than the upper limit of this range, there is solubility in a resist solvent sufficient for use as a resist, and if larger than the lower limit of this range, dry etching resistance and resist pattern cross-sectional shape are favorable.

Moreover, 1.0-5.0 are preferable, as for dispersion degree (Mw / Mn), 1.0-3.0 are more preferable, and 1.2-2.5 are the most preferable. In addition, Mn represents a number average molecular weight.

[(A2) component]

As the component (A2), the molecular weight is 500 or more and less than 2000, and the low molecular weight compound having the acid dissociable, dissolution inhibiting group and the hydrophilic group exemplified in the description of the component (A1) described above is preferable. Specifically, a part in which the hydrogen atom of the hydroxyl group of the compound which has a some phenol skeleton was substituted by the said acid dissociable, dissolution inhibiting group is mentioned.

In addition, in the (A2) component, a "low molecular weight compound" means the compound which is not a resin component.

The component (A2) is obtained by substituting a part of a hydrogen atom of a hydroxyl group of a low molecular weight phenolic compound known as a sensitizer in a non-chemically amplified g-ray or i-ray resist or a heat resistance improving agent with the acid dissociable, dissolution inhibiting group. It is preferable to use it, and it can use arbitrarily from such.

As such a low molecular weight phenolic compound, it is bis (4-hydroxyphenyl) methane, bis (2, 3, 4- trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (4, for example. '-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-hydroxyphenyl) Ethyl] benzene, phenol, m-cresol, p-cresol or Silane phenol-formaldehyde condensate of 2, 3, such as a play, and the like 4 nuclei. Of course, it is not limited to these.

The acid dissociable, dissolution inhibiting group is also not particularly limited, and examples mentioned above may be mentioned.

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

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 be formed.

<(B) component>

(B) component contains the acid generator (B1) (Hereinafter, it may be called (B1) component) which consists of a compound represented by the said general formula (b1-1). This (B1) component is the same as that of the said compound (B1) of this invention.

A component (B1) can be used 1 type or in mixture of 2 or more types.

In the resist composition of the present invention, the content of the component (B1) in the component (B) is preferably 40% by mass or more, more preferably 70% by mass or more, and may be 100% by mass. Most preferably 100% by mass. When the resist pattern is formed using the resist composition of this invention by being more than the lower limit of the range, lithographic characteristics, such as resolution and linewise roughness (LWR), improve.

In the component (B), an acid generator (B2) (hereinafter referred to as component (B2)) other than the component (B1) may be used in combination with the component (B1).

The component (B2) is not particularly limited as long as it is other than the component (B1), and any of those proposed as an acid generator for chemically amplified resists can be used.

As such acid generators, onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyl diazomethanes, and poly (bissulfonyl) dia Various types of diazomethane acid generators such as crude methane, nitrobenzylsulfonate acid generators, iminosulfonate acid generators, and disulfone acid generators are known.

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

[Formula 45]

[Wherein, R ^{1 ″} to R ^{3 ″} and R ^{5 ″} to R ^{6 ″} each independently represent an aryl group or an alkyl group; Any two of R <^1> -R < ³ >> in a formula (b-1) may combine with each other, and may form a ring with the sulfur atom in a formula; R ^{4 ''} represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group; At least one of R ^{1 ''} to R ^{3 ''} represents an aryl group, and at least one of R ^{5 ''} to R ^{6 ''} represents an aryl group]

In formula (b-1), R <^1> -R <^3>" respectively independently represents an aryl group or an alkyl group. Moreover, any two of R <^1> -R <^{3> in} Formula (b-1) may combine with each other, and may form a ring with the sulfur atom in a formula.

Moreover, at least 1 represents an aryl group in R <^1> -R <^3> . ^{R 1 '' ~ R 3 '} ' of the two or more are preferable, and an aryl group, ^{R 1 '' ~ R 3 '} ' is an aryl group all of it is most preferred.

There is no restriction | limiting in particular as an aryl group of R <^1> -R <^3>" , For example, as a C6-C20 aryl group, one or all of the hydrogen atoms of this aryl group are an alkyl group, an alkoxy group, and a halogen atom Or a hydroxyl group or the like, or may not be substituted. As an aryl group, a C6-C10 aryl group is preferable at the point which can be synthesize | combined at low cost. Specifically, a phenyl group and a naphthyl group are mentioned, for example.

As an alkyl group which the hydrogen atom of the said aryl group may be substituted, the 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 in which the hydrogen atom of the said aryl group may be substituted, a C1-C5 alkoxy group is preferable and a methoxy group and an ethoxy group are the most preferable.

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

There is no restriction | limiting in particular as an alkyl group of R <^1> -R <^3>" , 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. A methyl group is mentioned as a thing preferable in the point which can be mentioned, and is excellent in resolution, and can be synthesize | combined at low cost.

Among these, R ^{1 ''} to R ^{3 ''} are most preferably a phenyl group or a naphthyl group, respectively.

When any two of R ^{1 ''} to R ^{3 ''} in formula (b-1) combine with each other to form a ring together with a sulfur atom in the formula, a sulfur atom is included to form a 3 to 10 membered ring. It is preferable to do it, and it is especially preferable to form the 5-7 membered ring.

When any two of R <^1> -R <^{3> in} Formula (b-1) combine with each other and form a ring with the sulfur atom in a formula, it is preferable that the other one is an aryl group. Examples of the aryl group include the same aryl groups as R ^{1 ″} to R ^{3 ″} .

R ^{4 ''} represents a linear, branched or cyclic alkyl group or a linear, branched or cyclic fluorinated alkyl group.

As said linear or branched alkyl group, it is preferable that it is C1-C10, It is more preferable that it is C1-C8, It is most preferable that it is C1-C4.

As said cyclic alkyl group, it is preferable that it is C4-C15 as a cyclic group shown by said R < ¹ >>, It is more preferable that it is C4-C10, It is most preferable that it is C6-C10.

As said fluorinated alkyl group, it is preferable that it is C1-C10, It is more preferable that it is C1-C8, It is most preferable that it is C1-C4. In addition, the fluorination rate (ratio of fluorine atoms in the alkyl group) of the fluorinated alkyl group is preferably 10 to 100%, more preferably 50 to 100%, and in particular, a fluorinated alkyl group in which all of the hydrogen atoms are replaced with fluorine atoms (perfluoro A roalkyl group) is preferable because the strength of the acid becomes stronger.

As R <^4> , it is most preferable that it is a linear or cyclic alkyl group, or a linear or cyclic fluorinated alkyl group.

In formula (b-2), R <^5> -R <^6>" respectively independently represents an aryl group or an alkyl group. At least one of R ^{5 ''} to R ^{6 ''} represents an aryl group. It is preferable that all of R <^5> -R < ⁶ >> are aryl groups.

As an aryl group of R <^5> -R < ⁶ >>, the same thing as the aryl group of R <^1> -R < ³ >> is mentioned.

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

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

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 its nonafluorobutanesulfonate, trifluoromethanesulfonate of monophenyldimethylsulfonium, heptafluoropropanesulfonate or its nonafluoro Butane sulfonate; Trifluoromethanesulfonate of diphenylmonomethylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, trifluoromethanesulfonate of (4-methylphenyl) diphenylsulfonium, heptafluoro Ropropansulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of (4-methoxyphenyl) diphenylsulfonium, heptafluoropropanesulfonate or its nonafluorobutanesulfonate, tri ( Trifluoromethanesulfonate of 4-tert-butyl) phenylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, and diphenyl (1- (4-methoxy) naphthyl) sulfonium Trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, trifluoromethanesulfonate of di (1-naphthyl) phenylsulfonium, heptafluoro Butane sulfonate ropan sulfonate or nonafluoro; Trifluoromethanesulfonate of 1-phenyltetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-methylphenyl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1-phenyltetrahydrothiopyranium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-hydroxyphenyl) tetrahydrothiopyranium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiopyranium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-methylphenyl) tetrahydrothiopyranium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, and the like.

Moreover, the onium salt in which the anion part of these onium salt was substituted by methanesulfonate, n-propanesulfonate, n-butanesulfonate, and n-octanesulfonate can also be used.

In addition, in the said general formula (b-1) or (b-2), the onium salt type acid generator which substituted the anion part by the anion part represented by the following general formula (b-3) or (b-4) can also be used. (The cation part is the same as (b-1) or (b-2).).

[Formula 46]

[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]

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. to be.

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. Preferably it is C1-C3.

The smaller the number of carbon atoms of the alkylene group of X '' or the carbon number of the alkyl group of Y '', Z '' is, for the reason that the solubility in the resist solvent is also good within the range of the 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 strength of the acid, and the higher energy light or electron beam of 200 nm or less. It is preferable because the transparency to the resin is improved. 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, perfluoroalkyl in which all hydrogen atoms are substituted with fluorine atoms. Ethylene group or perfluoroalkyl group.

Moreover, the sulfonium salt which has the cation part represented by following General formula (b-5) or (b-6) can also be used as an onium salt type acid generator.

[Formula 47]

[Wherein, R ⁴¹ to R ⁴⁶ 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, n ₆ is an integer of 0 to 2]

In R ⁴¹ to R ⁴⁶ , the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, Or tert-butyl group.

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

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.

In the case where the symbols n ₁ to n ₆ given to R ⁴¹ to R ⁴⁶ are integers of 2 or more, a plurality of R ⁴¹ to R ⁴⁶ may be the same or different.

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

n ₆ becomes like this. Preferably it is 0 or 1, More preferably, it is 1.

The anion part of the sulfonium salt which has a cation part represented by Formula (b-5) or (b-6) is not specifically limited, It may be the same as the anion part of the onium salt type acid generator currently proposed. 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 anion part etc. which are represented by the said general formula (b-3) or (b-4) are mentioned. Among these, fluorinated alkyl sulfonate ions are preferable, fluorinated alkyl sulfonate ions having 1 to 4 carbon atoms are more preferable, and linear perfluoroalkyl sulfonate ions having 1 to 4 carbon atoms are particularly preferable. Specific examples thereof include trifluoromethyl sulfonic acid ion, heptafluoro-n-propylsulfonic acid ion, and nonafluoro-n-butylsulfonic acid ion.

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 of a radiation. Since these oxime sulfonate-type acid generators are used abundantly for chemical amplification resist compositions, they can be selected arbitrarily and used.

[Formula 48]

(In 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

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 further 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. Moreover, a partially halogenated alkyl group means the alkyl group in which a part of hydrogen atoms were substituted by the halogen atom, and a 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.

4-20 are preferable, as for an aryl group, C4-C10 is more preferable, and C6-C10 is the most preferable. As the aryl group, a partially or fully halogenated aryl group is particularly preferable. Moreover, the partially halogenated aryl group means the aryl group in which a part of hydrogen atoms were 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 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 an oxime sulfonate-type acid generator, the compound represented by the following general formula (B-2) or (B-3) more preferable is mentioned.

[Formula 49]

[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]

[Formula 50]

[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 or halogenated alkyl group having no substituent. p '' is 2 or 3]

In the general formula (B-2), the alkyl group or halogenated alkyl group having no substituent of R ³³ is preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms. Do.

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 fluorinated, 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 a C1-C10 alkyl group, a halogenated alkyl group, and an alkoxy group. It is preferable that carbon number is 1-8, and, as for the alkyl group or halogenated alkyl group in this substituent, C1-C4 is more preferable. Moreover, it is preferable that this halogenated alkyl group is a fluorinated alkyl group.

The alkyl group or halogenated alkyl group not having a 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 at least 50% fluorinated, more preferably at least 70% fluorinated, and more preferably at least 90% fluorinated, increasing the strength of the acid generated. Particularly preferred. 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 alkyl group or halogenated alkyl group which does not have a substituent of R <^36> is the same as the alkyl group or halogenated alkyl group which does not have a substituent of said R <^33> .

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- Sopropyl sulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohex Senylacetonitrile, α- (isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (methylsulfonyloxyi Mino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -phenylacetonitrile, α- (trifluoromethylsul Ponyloxyimino) -p-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -p-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -p-methylphenylacetonitrile, α- ( Methylsulfonyloxyimino) -p-bromophenyl acetonitrile etc. are mentioned.

Moreover, the oxime sulfonate-type acid generator disclosed by Unexamined-Japanese-Patent No. 9-208554 (Paragraph [18]-[Formula 19] of paragraph [0012]-[0014], WO2004 / 074242A2 (65- The oxime sulfonate acid generator disclosed in Examples 1 to 40) on page 85 can also be preferably used.

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

[Formula 51]

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, 1 which is 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 (cyclohexylsulfonyldiazomethylsul Phenyl) hexane, 1, 10-bis (cyclohexyl sulfonyl diazommethyl sulfonyl) decane, etc. are mentioned.

As the component (B2), the acid generator may be used alone, or may be used in combination of two or more thereof.

Content of (B) component in the resist composition of this invention is 0.5-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-20 mass parts. Pattern formation is fully performed by setting it as the said range. Moreover, since a uniform solution is obtained and storage stability becomes favorable, it is preferable.

<Optional ingredient>

In order to improve the resist pattern shape, post-exposure time stability, etc., the resist composition of the present invention may further contain a nitrogen-containing organic compound (D) (hereinafter referred to as component (D)) as an optional component. Can be.

Since many kinds of this (D) component have already been proposed, what is necessary is just to use arbitrarily from a well-known thing, and especially an aliphatic amine, especially a secondary aliphatic amine and tertiary aliphatic amine is preferable. The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms.

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

Specific examples of the alkylamine and the alkyl alcohol amine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine; Dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine and dicyclohexylamine; Trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri trialkylamines such as -n-nonylamine, tri-n-decanylamine and tri-n-dodecylamine; Alkyl alcohol amines, such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine, are mentioned. Among these, the trialkylamine which three C5-10 alkyl groups couple | bonded with the nitrogen atom is preferable, and tri-n-pentylamine is the most preferable.

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

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

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

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.

In the resist composition of the present invention, in the group consisting of an organic carboxylic acid, an oxo acid of phosphorus and a derivative thereof, as an optional component, for the purpose of preventing deterioration in sensitivity, improving the resist pattern shape, stability over time after exposure, and the like. At least 1 sort (s) of compound (E) (henceforth a component (E)) selected can be contained.

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

Phosphoric acid, phosphonic acid, phosphinic acid, etc. are mentioned as an oxo acid and its derivative (s) of phosphorus, Among these, phosphonic acid is especially preferable.

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

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

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.

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

As (E) component, organic carboxylic acid is preferable and salicylic acid is especially preferable.

(E) component is used in the ratio of 0.01-5.0 mass parts per 100 mass parts of (A) component.

The resist composition of the present invention may further contain miscible additives, for example, additional resins for improving the performance of the resist film, surfactants for improving applicability, dissolution inhibitors, plasticizers, stabilizers, and colorants, as desired. , An anti-halation agent, a dye and the like can be appropriately added.

<Organic Solvent (S)>

The resist composition of this invention can be manufactured by melt | dissolving a material in the organic solvent (S) (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 a solvent of 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; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; Monomethyl ether, monoethyl ether of a compound having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the polyhydric alcohol or the compound having the ester bond, Derivatives of polyhydric alcohols such as monoalkyl ethers such as monopropyl ether and monobutyl ether or compounds having ether bonds such as monophenyl ether [In these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferable]; Cyclic ethers such as dioxane, esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate; Anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phentol, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, isopropyl benzene, toluene, xylene, cymene, mesitylene Aromatic organic solvents, such as these, are mentioned.

These organic solvents may be used independently and may be used as 2 or more types of mixed solvents.

Especially, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 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 shall be in the range of 2: 8-8: 2. desirable.

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

Although the usage-amount of (S) component is not specifically limited, Although it sets suitably according to the coating film thickness in the density | concentration which can be apply | coated to a board | substrate etc., generally solid content concentration of a resist composition is 2-20 mass%, Preferably it is 5-15 mass. Used to be in the range of%.

<< resist pattern formation method >>

The resist pattern forming method of the present invention includes a step of forming a resist film on a 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 coated on a support with a spinner or the like, and the prebaking (post-applied bake (PAB)) is applied for 40 to 120 seconds under a temperature condition of 80 to 150 ° C, preferably 60 After performing for 90 seconds and selectively exposing ArF excimer laser beam through a desired mask pattern with an ArF exposure apparatus etc., for example, PEB (post-exposure heating) is made into 40 under the temperature conditions of 80-150 degreeC. It is carried out for -120 second, Preferably it is 60-90 second. This is then developed using an alkaline developer, for example, an aqueous 0.1-10% by mass tetramethylammonium hydroxide (TMAH) solution, preferably rinsed with pure water, and dried. In some cases, a bake treatment (post bake) may be performed after the developing treatment. In this way, a resist pattern faithful to the mask 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, metal substrates, 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 described above. An inorganic antireflection film (inorganic BARC) is mentioned as an inorganic film. As an organic type film | membrane, an organic antireflection film (organic BARC) is mentioned.

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, etc. It can be done using radiation. The resist composition is effective for KrF excimer lasers, ArF excimer lasers, EB or EUV, in particular ArF excimer lasers.

Exposure of a resist film may be normal exposure (dry exposure) performed in inert gas, such as air and nitrogen, or liquid immersion exposure may be sufficient as it.

In the liquid immersion exposure, as described above, at the time of exposure, the portion between the lens, which is conventionally filled with an inert gas such as air or nitrogen, and the resist film on the wafer, is a solvent (immersion medium) having a refractive index larger than that of air. Perform exposure in the filled state.

More specifically, the liquid immersion exposure fills between the resist film obtained as described above and the lens at the lowest position of the exposure apparatus with a solvent (immersion medium) having a refractive index larger than that of air, and in that state, the desired mask pattern is filled. It can carry out by exposing (immersion exposure) through interposition.

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 by the immersion exposure 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 a resist film, water, a fluorine-type inert liquid, a silicone solvent, a hydrocarbon 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 because the medium used for the liquid immersion can be removed after the exposure is completed by a simple method.

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

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

The resist composition of the said invention is a novel thing not known conventionally.

In addition, the resist composition of the present invention also has good lithography characteristics such as sensitivity and resolution, and can form, for example, a fine resist pattern having a line width of the line and space pattern of 120 nm or less. In addition, in the case where the resist pattern is formed using a conventional resist composition, there is a problem that the resist pattern shape tends to be defective, such as the sagging of the resist pattern occurs at the substrate interface and the rectangularity is deteriorated. According to the composition, a resist pattern with reduced sagging can be formed.

In addition, the component (B1) used in the resist composition of the present invention has a wavelength of 200 nm or less, especially around 193 nm, compared to an acid generator, for example, triphenylsulfonium salt, which is conventionally used in a chemically amplified resist composition. High transparency to light. Therefore, in the resist composition of this invention, it is possible to increase the compounding quantity of (B) component compared with the conventional resist composition.

Moreover, the component (B1) is excellent also in the generation | occurrence | production efficiency of the acid at the time of exposure, and the resist composition of this invention is also favorable by containing this (B1) component as (B) component.

These effects are considered to be mainly influenced by the structure of the cation part of (B1) component.

In addition, (B1) component is, Y ¹ -SO ₃ ^- is considered that influence it with anionic portion of the functional groups are introduced into the structure-skeleton "the R ¹ -O- [CO] _n" of. That is, in no moiety of the anionic portion of this structure, Y ¹ a, fluorine, and nonafluoro to generate a conventional acid such as butane sulfonate having the carbon number of the alkylene group that may be substituted in spite of relatively small as 1 to 4. The In comparison, excessive diffusion of acid after exposure is suppressed. Therefore, it is thought that the resist pattern with favorable lithography characteristic can be formed.

Moreover, (B1) component is an alkyl chain of a C1-C4 alkylene group which Y <^1> may be fluorine-substituted, and bioaccumulation property is compared with the C6-C10 perfluoroalkyl chain being hardly decomposable. Safer in terms of handling.

(Example)

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

Example 1

5 ml of tetrahydrofuran was added to 1.0 g of aryloxytetrafluoroethanesulfonyl fluorides, and the aqueous solution which melt | dissolved 0.20 g of lithium hydroxide in 2.8 ml of pure waters was dripped at the solution, and it stirred in the water bath. Absorption of ¹⁹ F-NMR at -217.8 ppm by -SO ₂ F confirmed that all sulfonyl fluoride groups were converted to lithium sulfonate. Thereafter, the reaction solution was concentrated and dried to obtain a white viscous solid. The obtained crude product was dissolved in 3.35 ml of acetone, filtered to remove LiF as a by-product, and the filtrate was concentrated to obtain 0.58 g of compound (1-1) represented by the following formula (1-1).

[Formula 52]

H ₂ C = CHCH ₂ OCF ₂ CF ₂ SO ₃ ^- Li ⁺ (1-1)

Next, 10.00 g of diphenyl iodonium methanesulfonate was dissolved in 50.00 g of water, 6.81 g of compound (1-1) was added thereto, and the mixture was stirred at room temperature for 1 hour.

After the completion of the reaction, 68.9 g of ethyl acetate was added to carry out an extraction operation, and the organic layer was washed 5 times with 34.5 g of pure water. After washing, the obtained organic layer was concentrated to obtain 6.70 g of the target compound.

The obtained compound (hereinafter referred to as compound (I-11)) was analyzed by ¹ H-NMR and ¹⁹ F-NMR. The results are shown below.

From the results above, it was confirmed that the compound (I-11) had a structure shown below.

[Formula 53]

3.93 g of compound (I-11), 0.7745 g of pentamethylene sulfide and 0.060 g of copper benzoate (II) were dissolved in 5.90 g of chlorobenzene and reacted at 100 ° C for 1 hour. After completion of the reaction, the reaction solution was concentrated to dryness, and this was dissolved in 26.2 g of dichloromethane.

After washing this dichloromethane solution with water, 0.84 g of target compounds were obtained by concentrating.

The obtained compound (hereinafter, referred to as compound (b1-11)) was analyzed by ¹ H-NMR and ¹⁹ F-NMR. The results are shown below.

From the results above, it was confirmed that the compound (b1-11) had a structure shown below.

[Formula 54]

Example 2

To 5.0 g of 2-naphthylmethyloxytetrafluoroethanesulfonylfluoride, 6.7 ml of 1 tetrahydrofuran was added, and an aqueous solution of 0.98 g of lithium hydroxide dissolved in 13.6 ml of pure water was added dropwise to the solution in an ice bath. Thereafter, the mixture was stirred in an ice bath. Absorption of ¹⁹ F-NMR at -217.6 ppm by -SO ₂ F confirmed that all sulfonyl fluoride groups were converted to lithium sulfonate. Thereafter, the reaction solution was concentrated and dried to obtain a white viscous solid. The obtained crude product was dissolved in 14.2 ml of acetone, filtered to remove LiF as a by-product, and the filtrate was concentrated to obtain 5.50 g of compound (1-2) represented by the following formula (1-2).

[Formula 55]

Next, 7.64 g of diphenyl iodonium methanesulfonate was dissolved in 38.02 g of water, and 7.30 g of compound (1-2) was added thereto and stirred at room temperature for 1 hour. After the completion of the reaction, 38.02 g of ethyl acetate was added to carry out an extraction operation, and after separating, the organic layer was washed 5 times with 38.02 g of pure water. After washing, the powder obtained by crystallizing the organic layer with hexane was dried under reduced pressure to obtain 10.87 g of the target compound.

The obtained compound (hereinafter referred to as compound (I-12)) was analyzed by ¹ H-NMR and ¹⁹ F-NMR. The results are shown below.

From the results above, it was confirmed that the compound (I-12) had a structure shown below.

[Formula 56]

8.00 g of compound (I-12), 1.32 g of pentamethylene sulfide, and 0.10 g of copper benzoate (II) were dissolved in 12.00 g of chlorobenzene and reacted at 100 ° C for 1 hour. After completion of the reaction, the reaction solution was concentrated to dryness, and this was dissolved in 33.40 g of dichloromethane. After washing this dichloromethane solution with water, 0.53 g of target compounds were obtained by concentrating.

The obtained compound (hereinafter, referred to as compound (b1-12)) was analyzed by ¹ H-NMR and ¹⁹ F-NMR. The results are shown below.

From the results above, it was confirmed that the compound (b1-12) had a structure shown below.

[Formula 57]

Comparative Example 1

0.28 g of triphenylsulfonium bromide was dissolved in 5.0 ml of pure water, and 0.17 g of Compound (1-1) obtained in the same manner as in Example 1 was added to the solution, followed by stirring at room temperature for 14 hours, followed by dichloromethane 10 Ml was added and stirred, and the organic phase was separated and extracted.

The organic phase was further washed with 5.0 ml of pure water, followed by separating an organic phase. The extracted organic phase was concentrated and then dried to obtain 0.16 g of the target compound.

The obtained compound (hereinafter, referred to as compound (b2-11)) was analyzed by ¹ H-NMR and ¹⁹ F-NMR. The results are shown below.

From the results above, it was confirmed that the compound had a structure shown below.

[Formula 58]

Comparative Example 2

6.99 g of triphenylsulfonium bromide was dissolved in 125 ml of pure water, and 5.50 g of Compound (1-2) obtained in the same manner as in Example 2 was added to the solution, followed by stirring at room temperature for 19 hours, followed by 125 g of dichloromethane. Was added and stirred, and the organic phase was separated and extracted.

The organic phase was further washed with pure water 40 ml, then separated and the organic phase was extracted. The extracted organic phase was concentrated and dried to obtain 7.09 g of the target compound (yield: 75.2%).

The obtained compound (hereinafter referred to as compound (b2-12)) was analyzed by ¹ H-NMR and ¹⁹ F-NMR. The results are shown below.

From the results above, it was confirmed that the compound (b2-12) had a structure shown below.

[Formula 59]

Example 3

5.00 g of 1- (2-oxo-2-phenylethyl) tetrahydrothiophenium bromide was dissolved in 25 g of pure water, and 6.6 g of Compound (1-2) obtained in the same manner as in Example 2 was added thereto, followed by room temperature. Stirred for 2 hours. Thereafter, 25.0 g of dichloromethane was added, the dichloromethane layer was separated, washed with dilute hydrochloric acid, washed with water, and 250.0 g of n-hexane was added to the dichloromethane layer to obtain 8.5 g of the target compound as a white solid.

[Formula 60]

The obtained compound (hereinafter, referred to as compound (b1-13)) was analyzed by ¹ H-NMR and ¹⁹ F-NMR. The results are shown below. From this result, it was confirmed that a compound (b1-13) has a structure shown in the said chemical formula.

Solvent Solubility Evaluation

Compounds (b1-11), (b1-12), (b1-13), (b2-11), and (b2-12) obtained in Examples 1 to 3 and Comparative Examples 1 and 2, respectively, and the following formulas ( About solvent (b2-13) represented by b2-13), solvent solubility was evaluated in the following procedure.

Each compound was added to the propylene glycol monomethyl ether acetate (PGMEA), the propylene glycol monomethyl ether (PGME), and the ethyl lactate (EL) which are common resist solvents, respectively, and was added, and it stirred at 25 degreeC for 30 minutes. After completion of stirring, the concentration (mass%) in which each compound was completely dissolved was measured. The results are shown in Table 1.

[Formula 61]

As shown in Table 1, all of the compounds (b1-11) and (b1-12) and the compound (b2-13) according to the present invention had very high solubility in PGMEA, PGME, and EL.

On the other hand, the compound (b2-11) had relatively good solubility in PGME and EL, but had poor solubility in PGMEA. In addition, the compound (b2-12) had bad solubility in any solvent. Moreover, the solubility with respect to PGMEA improved about the compound (b1-13) which changed only the cation part from the compound (b2-12).

[Examples 4 to 6 and Comparative Example 3]

Each component shown in Table 2 was mixed and dissolved, and the positive resist composition was prepared.

In Table 2, the numerical value in [] shows a compounding quantity (mass part). In addition, the symbol in Table 2 represents the following, respectively. In addition, the compounding quantity of (B) component is equimolar amount.

(A) -1: Copolymer of Mw = 7000 and Mw / Mn = 1.8 represented by following General formula (A) -1 (In formula, l / m / n = 45/35/20 (molar ratio).).

(B) -1: the compound (b1-11) obtained in Example 1.

(B) -2: the compound (b1-12) obtained in Example 2.

(B) -3: the compound (b1-13) obtained in Example 3.

(B) -4: the compound (b2-13) represented by said formula (b2-13).

(D) -1: tri-n-pentylamine.

(E) -1: salicylic acid.

(S) -1: γ-butyrolactone.

(S) -2: Mixed solvent of PGMEA / PGME = 6/4 (mass ratio).

[Formula 62]

Using the obtained resist composition, a resist pattern was formed in the following procedures and lithographic characteristics were evaluated.

[Resolution and sensitivity]

On an 8-inch silicon wafer, an organic antireflection film composition "ARC29A" (trade name, manufactured by Blower Science Co., Ltd.) was applied using a spinner, and baked at 205 ° C for 60 seconds on a hot plate, followed by drying, thereby drying. An organic antireflection film was formed. On the anti-reflection film, the resist composition obtained above was applied using a spinner, respectively, and prebaking (PAB) treatment was performed on a hot plate at 110 ° C. for 60 seconds, followed by drying to form a resist film having a thickness of 150 nm. Formed.

Subsequently, an ArF exposure apparatus NSR-S302 (manufactured by Nikon Corporation; NA (number of apertures) = 0.60 and 2/3 annular illumination) was used to pass an ArF excimer laser (193 nm) through a mask pattern (6% halftone). It was investigated selectively. Then, a post-exposure heating (PEB) treatment was performed at 110 ° C for 60 seconds, and further developed at 23 ° C with a 2.38% by mass aqueous tetramethylammonium hydroxide (TMAH) solution under conditions of 30 seconds, and thereafter. Rinse with water using pure water for 30 seconds, dry while whisk.

As a result, also in any example, the resist pattern (L / S pattern) of the line-and-space (1: 1) of line width 120nm and pitch 240nm was formed.

At this time, the optimum exposure dose Eop (mJ / cm 2), that is, the sensitivity at which the L / S pattern having a line width of 120 nm and a pitch of 240 nm was formed was determined. The results are shown in Table 3.

[Line Wise Roughness (LWR)]

In each L / S pattern formed in the said Eop, the line width was measured 5 points in the longitudinal direction of a line by the measuring SEM (scanning electron microscope, brand name: S-9220, the Hitachi company make), and, as a result, The triple value (3s) of the standard deviation (s) was calculated as a measure of LWR. The results are shown in Table 3. The smaller the value of 3s, the smaller the roughness of the line width, which means that a more uniform width L / S pattern is obtained.

As shown in Table 3, LWR of the resist compositions of Examples 4-6 was favorable. On the other hand, LWR of the resist composition of Comparative Example 3 was bad.

Claims (13)

As a resist composition containing the base component (A) which changes the solubility to alkaline developing solution by the action of an acid, and the acid generator component (B) which generate | occur | produces an acid by exposure, The said acid generator component (B) contains the acid generator (B1) which consists of a compound represented with the following general formula (b1-1), The resist composition characterized by the above-mentioned. [Formula 5]

[Wherein, R ¹ is an aryl group or alkyl group which may have a substituent, R ³ is a hydrogen atom or an alkyl group, n1 is 0 or 1 and when n1 is 1, R ¹ And R ³ may be bonded to each other to form a ring having a 3 to 7 membered ring structure together with a carbon atom having R ¹ bonded thereto and a carbon atom having R ³ bonded thereto, and A is a sulfur atom having the A bonded thereto; It is a bivalent group which forms the ring of a 3-7 membered ring structure together, The said ring may have a substituent and R <^2> may be a C1-C10 linear group which may have an aromatic group and a substituent. Or a linear or branched alkenyl group having 2 to 10 carbon atoms which may have a branched alkyl group or a substituent, n is 0 or 1, and Y ¹ is an alkylene group having 1 to 4 carbon atoms which may be substituted with fluorine; The method of claim 1, The resist composition as described above wherein the base component (A) is a base component whose solubility in an alkaline developer is increased by the action of an acid. The method of claim 2, The said base component (A) contains the resin component (A1) by which the solubility to an alkaline developing solution increases by the action of an acid, and this resin component (A1) is derived from the acrylate ester containing an acid dissociable, dissolution inhibiting group. The resist composition which has a structural unit (a1). The method of claim 3, wherein The resist composition in which the said resin component (A1) has a structural unit (a2) further derived from the acrylate ester containing a lactone containing cyclic group. The method of claim 3, wherein The resist composition in which the said resin component (A1) further has a structural unit (a3) derived from the acrylate ester containing a polar group containing aliphatic hydrocarbon group. The method of claim 4, wherein The resist composition in which the said resin component (A1) further has a structural unit (a3) derived from the acrylate ester containing a polar group containing aliphatic hydrocarbon group. The method of claim 1, A resist composition containing a nitrogen containing organic compound (D). A step of forming a resist film on a support using the resist composition according to any one of claims 1 to 7, a step of exposing the resist film, and a step of alkali development of the resist film to form a resist pattern Resist Pattern Formation Method. The compound represented by the following general formula (b1-1). [Formula 1]

[Wherein, R ¹ is an aryl group or alkyl group which may have a substituent, R ³ is a hydrogen atom or an alkyl group, n1 is 0 or 1 and when n1 is 1, R ¹ And R ³ may be bonded to each other to form a ring having a 3 to 7 membered ring structure together with a carbon atom having R ¹ bonded thereto and a carbon atom having R ³ bonded thereto, and A is a sulfur atom having the A bonded thereto; It is a bivalent group which forms the ring of a 3-7 membered ring structure together, The said ring may have a substituent and R <^2> may be a C1-C10 linear group which may have an aromatic group and a substituent. Or a linear or branched alkenyl group having 2 to 10 carbon atoms which may have a branched alkyl group or a substituent, n is 0 or 1, and Y ¹ is an alkylene group having 1 to 4 carbon atoms which may be substituted with fluorine; General formula (including the process of reacting the compound represented by the following general formula (I), the compound represented by the following general formula (II), and a copper catalyst, and obtaining the compound represented by the following general formula (b1-1-1) ( The manufacturing method of a compound represented by b1-1-1). [Formula 2]

[In formula, A is a divalent group which forms the ring of a 3-7 membered ring structure with the sulfur atom which said A couple | bonded, The said ring may have a substituent and R <^2> may have a substituent. group, carbon atoms which may have a substituent of 1 to 10 for a linear or branched alkyl group, or a straight chain having 2 to 10 carbon atoms which may have a substituent-type or branched alkenyl group, n is 0 or 1, Y ¹ Is an alkylene group having 1 to 4 carbon atoms which may be fluorine-substituted, and R ¹ is each independently an aryl group or alkyl group which may have a substituent] The compound represented by the following general formula (I). [Formula 3]

[In formula, R <^2> is a C1-C10 linear or branched alkyl group which may have the aromatic group which may have a substituent, a C1-C10 linear or branched alkyl group which may have a substituent, or a substituent. Is an alkenyl group, n is 0 or 1, Y ¹ is an alkylene group having 1 to 4 carbon atoms which may be fluorine-substituted, and R ¹ is each independently an aryl group or alkyl group which may have a substituent] Represented by the general formula (I) including a step of reacting a compound represented by the following general formula (I-1) with a compound represented by the following general formula (I-2) to obtain a compound represented by the following general formula (I). Method of Preparation of the Compound. [Formula 4]

[In formula, R <^2> is a C1-C10 linear or branched alkyl group which may have the aromatic group which may have a substituent, a C1-C10 linear or branched alkyl group which may have a substituent, or a substituent. An alkenyl group, n is 0 or 1, Y ¹ is an alkylene group having 1 to 4 carbon atoms which may be fluorine-substituted, M ⁺ is an alkali metal ion, and R ¹ is an aryl group which may each independently have a substituent; Or an alkyl group, R ⁷ is an alkyl group or a fluorinated alkyl group] The acid generator which consists of a compound of Claim 9.