TW201731833A - Resist composition and resist pattern formation method, and compound and acid-producing agent providing the novel compound useful for the acid-producing agent used as the resist composition, the acid-producing agent, resist composition containing the acid-producing agent, and the resist patter formation method - Google Patents

Abstract

The topic of the present invention is to provide the novel compound useful for the acid-producing agent used as the resist composition, the acid-producing agent using same, resist composition containing the acid-producing agent, and the resist pattern formation method using the resist composition. The solution is to contain the resist composition containing the compound represented by the general formula (b1). In formula (b1), R<SP>b1</SP> is represented by the aromatic ring containing the electron attractive group formed by selecting from the group of fluorine atom, trifluoromethyl group, nitro group, cyano group, and –SO2R<SP>b10</SP> (but when the aforementioned aromatic ring is benzene ring, the aforementioned electron attractive group is bonded to the meta-position at one side of the benzene ring.) R<SP>b21</SP> and R<SP>b22</SP> represent the aromatic ring capable of containing the electron attractive group formed by selecting from the group of fluorine atom, trifluoromethyl group, nitro group, cyano group, and –SO2R<SP>b20</SP>. Z represents sulfur atom, oxygen atom, carbonyl group, or single bond. X<SP>-</SP> represents counter anion (but, except for BF4<SP>-</SP>).

Description

Resist composition and resist pattern formation method and compound and acid generator

The present invention relates to a resist composition and a resist pattern forming method, and a compound and an acid generator.

In the lithography technique, for example, a resist film formed of a resist material is formed on a substrate, the resist film is selectively exposed, and a development process is performed to form a specific shape on the resist film. The step of the resist pattern. The resist material in which the exposed portion of the resist film is changed to the characteristics of the developer is referred to as a positive type, and the resist portion in which the exposed portion of the resist film is changed to be insoluble in the developer is referred to as a negative type.

In recent years, in the manufacture of semiconductor elements or liquid crystal display elements, the miniaturization of patterns has progressed rapidly due to advances in lithography. As a method of miniaturization, generally, a short wavelength (high energy) of an exposure light source is performed. Specifically, conventionally, ultraviolet rays typified by g-line and i-line have been used, but mass production of semiconductor elements using KrF excimer lasers or ArF excimer lasers has been currently performed. Further, EUV (extreme ultraviolet ray), EB (electron beam), X-ray, etc., which are shorter wavelengths (high energy) than these excimer lasers, are also discussed.

For the resist material, the lithography characteristics such as the sensitivity of the exposure light source and the resolution of the pattern capable of reproducing the fine size are required.

As a resist material which satisfies such requirements, conventionally, a chemically amplified type containing a base material component which changes the solubility of a developer by an action of an acid and an acid generator component which generates an acid by exposure is used. Resist composition.

For example, when the developing solution is an alkali developing solution (alkali developing process), as a positive type chemically amplified resist composition, generally, the solubility in an alkali developing solution is increased by the action of an acid. The resin component (base resin) and the acid generator component. The resist film formed by using the resist composition is selectively exposed when the resist pattern is formed, and the acid is generated from the acid generator component in the exposed portion, and the base resin is caused by the action of the acid. The polarity is increased, and the exposed portion of the resist film becomes soluble for the alkali developer. Therefore, by performing alkali development, a positive pattern remaining as an unexposed portion of the resist film as a pattern is formed.

On the other hand, when such a chemically amplified resist composition is applied to a solvent developing process using a developing solution containing an organic solvent (organic developing solution), the polarity of the base resin is increased, and the organic developing is relatively Since the solubility of the liquid is lowered, the unexposed portion of the resist film is dissolved and removed by the organic developing solution, and the exposed portion of the resist film is formed as a negative resist pattern remaining as a pattern. Thus, a solvent developing process for forming a negative resist pattern is referred to as a negative developing process.

The base resin used in the chemically amplified resist composition generally has a plurality of constituents in order to improve lithography characteristics and the like. unit.

For example, in the case of a resin component which has an increased solubility in an alkali developer by the action of an acid, it is decomposed by an action of an acid generated by an acid generator or the like to increase the polarity of the acid. The constituent unit of the decomposable group is a constituent unit containing a cyclic group containing a lactone, a constituent unit containing a polar group such as a hydroxyl group, or the like.

Further, in the formation of the resist pattern, the behavior of the acid generated from the acid generator component by exposure is one of the factors that greatly affect the lithographic properties.

As the acid generator used in the chemical amplification resist composition, various proposals have been made so far. For example, an onium salt acid generator such as a phosphonium salt or a phosphonium salt, an oxime sulfonate acid generator, a diazomethane acid generator, a nitrobenzyl ester acid generator, or a sulfonate is known. An amine ester acid generator, a diterpene acid generator, and the like.

The sulfonium-based acid generator is mainly used for those having a ruthenium ion such as triphenylsulfonium in the cation portion. The anion portion of the sulfonium salt-based acid generator is generally a fluorinated alkylsulfonic acid ion in which a part or all of a hydrogen atom of an alkylsulfonic acid ion or an alkyl group thereof is substituted with a fluorine atom.

Further, in the formation of the resist pattern, in order to improve the lithographic properties, a sulfonium-based acid generator having a sulfonium ion having a dibenzothiophene structure has been proposed as a cation portion of the bismuth salt-based acid generator ( For example, refer to Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2008-273912

As the lithography technology progresses and the refinement of the resist pattern becomes more and more advanced, for example, lithography by electron beam or EUV is aimed at forming a fine pattern of several tens of nm. As such, the size of the resist pattern becomes smaller, and the resist composition is required to be highly sensitive to the exposure light source.

However, in the resist composition containing the conventional sulfonium-based acid generator as described above, when the exposure light source such as EUV is highly sensitive, it is difficult to obtain a desired shape of the resist pattern, and it is difficult to satisfy all of them. These characteristics.

The present invention has been made in view of the above circumstances, and a subject thereof is to provide a novel compound for use as an acid generator for a resist composition, an acid generator using the compound, a resist composition containing the acid generator, and A resist pattern formation method of the resist composition is used.

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

That is, the first aspect of the present invention is a resist composition which is a resist composition which generates an acid by exposure and which changes the solubility of the developer by the action of an acid, and is characterized in that Containing the action of acid, The substrate component (A) in which the solubility of the developer changes, and the compound (B1) represented by the following formula (b1).

^Wherein R ^b1 represents an aromatic ring having an electron attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b10 (except that the aforementioned aromatic ring is a benzene ring) In time, the electron-attracting group is bonded to at least one of the benzene rings. R ^b10 represents an alkyl group, a fluorinated alkyl group or an aryl group. R ^b21 and R ^b22 each independently represent an aromatic ring which may have an electron attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b20 . R ^b20 represents an alkyl group, a fluorinated alkyl group or an aryl group. Z represents a sulfur atom, an oxygen atom, a carbonyl group or a single bond. R ^b1 and R ^b21 may also be bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula. R ^b1 and R ^b22 may also be bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula. X ^- represents a relative anion (except BF ₄ ^- except).

According to a second aspect of the present invention, there is provided a method for forming a resist pattern, comprising: forming a resist film on a support using the resist composition of the first aspect; and exposing the resist film And the step of developing the resist film after the exposure to form a resist pattern.

A third aspect of the invention is a compound characterized by the following formula (b1).

^Wherein R ^b1 represents an aromatic ring having an electron attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b10 (except that the aforementioned aromatic ring is a benzene ring) In time, the electron-attracting group is bonded to at least one of the benzene rings. R ^b10 represents an alkyl group, a fluorinated alkyl group or an aryl group. R ^b21 and R ^b22 each independently represent an aromatic ring which may have an electron attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b20 . R ^b20 represents an alkyl group, a fluorinated alkyl group or an aryl group. Z represents a sulfur atom, an oxygen atom, a carbonyl group or a single bond. R ^b1 and R ^b21 may also be bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula. R ^b1 and R ^b22 may also be bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula. X ^- represents a relative anion (except BF ₄ ^- except).

A fourth aspect of the invention is an acid generator comprising the compound of the third aspect.

According to the present invention, there can be provided a novel compound for use as an acid generator for a resist composition, an acid generator using the same, a resist composition containing the same, and a resist using the resist composition. Pattern formation method.

According to the resist composition of the present invention, in the formation of the resist pattern, high sensitivity can be achieved, and a resist pattern of a good shape can be formed.

In the present specification and the scope of the present patent application, "aliphatic" means a concept of relativeness to aromatics, and is defined as a group or a compound which does not have aromaticity.

The "alkyl group" is a linear monovalent, branched chain or cyclic monovalent saturated hydrocarbon group unless otherwise specified. The alkyl group in the alkoxy group is also the same.

The "alkylene group" is a linear, branched, and cyclic divalent saturated hydrocarbon group unless otherwise specified.

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

The "fluorinated alkyl group" or "fluorinated alkyl group" means a group in which a part or all of a hydrogen atom of an alkyl group or an alkyl group is substituted with a fluorine atom.

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

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

"Exposure" is a concept that includes all of the radiation.

The "constituting unit derived from acrylate" means a constituent unit composed of cleavage of an ethylenic double bond of an acrylate.

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

In the acrylate, a hydrogen atom bonded to a carbon atom at the α-position may be substituted with a substituent. The substituent (R ^α0 ) substituted with a hydrogen atom bonded to a carbon atom at the α -position is an atom or a group other than a hydrogen atom, and examples thereof include an alkyl group having 1 to 5 carbon atoms and a halogenated alkane having 1 to 5 carbon atoms. Base. Further, the substituent ^(R α0) via an ester bond of substituents itaconic acid ester, or a substituent ^(R α0) hydroxyalkyl or modified by a hydroxyl group derived from the substituted α-hydroxy acrylate is also Included. Further, the carbon atom at the α position of the acrylate refers to a carbon atom to which a carbonyl group of acrylic acid is bonded, unless otherwise specified.

Hereinafter, an acrylate in which a hydrogen atom bonded to a carbon atom of the α -position is substituted with a substituent is referred to as an α- substituted acrylate. Further, the acrylate and the α- substituted acrylate are collectively referred to as "( α- substituted) acrylate".

"Constituent unit derived from acrylamide" means a constituent unit composed of ethylene double bond cracking of acrylamide.

In the acrylamide, the hydrogen atom bonded to the carbon atom at the α -position may be substituted with a substituent, and one or both of the hydrogen atoms of the amine group of the acrylamide may be substituted with a substituent. Further, the carbon atom at the α position of acrylamide refers to a carbon atom to which a carbonyl group of acrylamide is bonded unless otherwise specified.

The substituent substituted with a hydrogen atom bonded to the α -position carbon atom of acrylamide may be exemplified by the above-mentioned α- substituted acrylate, and the same as the substituent (the substituent (R ^α0 )) as the substituent at the α position. .

The "constituting unit derived from hydroxystyrene" means a constituent unit composed of ethyl double bond cracking of hydroxystyrene. The "constituting unit derived from a hydroxystyrene derivative" means a constituent unit composed of a vinyl double bond cracking of a hydroxystyrene derivative.

The "hydroxystyrene derivative" is a concept in which a hydrogen atom at the alpha position of the hydroxystyrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. The derivatives of these, include the α position may be substituted with a hydrogen atom substituted with a hydrogen atom of the hydroxyl group of hydroxystyrene are substituted by an organic group; the substituent other than a hydroxyl group bonded to a hydrogen atom of α position may be substituted The phenyl ring on which the hydroxystyrene is substituted, and the like. Further, the α position (the carbon atom of the α position) means a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The substituent of the hydrogen atom at the α -position of the substituted hydroxystyrene may be the same as those exemplified as the substituent at the α -position in the above-mentioned α- substituted acrylate.

The "constituting unit derived from a vinyl benzoic acid or a vinyl benzoic acid derivative" means a constituent unit composed of vinyl double bond cracking of a vinyl benzoic acid or a vinyl benzoic acid derivative.

The "vinyl benzoic acid derivative" is a concept in which a hydrogen atom at the alpha position of the vinyl benzoic acid is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. These derivatives include those in which the hydrogen atom of the carboxyl group of the vinyl benzoic acid which may be substituted by a substituent at the α -position is substituted with an organic group; the substituent other than the hydroxyl group and the carboxyl group may be bonded to the hydrogen atom at the α position. A benzoic acid of a vinyl benzoic acid substituted with a substituent, and the like. Further, the α position (the carbon atom of the α position) means a carbon atom to which a benzene ring is bonded, unless otherwise specified.

"Styrene" is a concept in which a hydrogen atom of the alpha position of styrene and styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group.

The "styrene derivative" is a concept in which a hydrogen atom containing an α -position of styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. Examples of such derivatives include those in which a substituent is bonded to a benzene ring of a hydroxystyrene in which a hydrogen atom at the α position is substituted with a substituent. Further, the α position (the carbon atom of the α position) means a carbon atom to which a benzene ring is bonded, unless otherwise specified.

The "constituting unit derived from styrene" and "the constituent unit derived from the styrene derivative" mean a constituent unit composed of ethylene double bond cracking of styrene or a styrene derivative.

The alkyl group which is a substituent of the above α position is preferably a linear or branched alkyl group, and specific examples thereof include an alkyl group having 1 to 5 carbon atoms (methyl group, ethyl group, propyl group, and iso group). Propyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl) and the like.

Moreover, as the position of the substituents α halogenated alkyl group, specific examples thereof include the above "as α position of a substituent alkyl" portion or the whole of hydrogen atoms, halogen atoms substituted group. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a fluorine atom.

In addition, the hydroxyalkyl group which is a substituent of the α -position is specifically a group in which one or all of the hydrogen atoms of the above-mentioned "alkyl group as a substituent at the α -position" is substituted with a hydroxyl group. The number of hydroxyl groups in the hydroxyalkyl group is preferably from 1 to 5, most preferably 1.

(resist composition)

The resist composition of the first aspect of the present invention is an acid which is generated by exposure and which has a change in solubility in a developing solution by the action of an acid.

In one embodiment of the composition of the resist, the substrate component (A) (hereinafter also referred to as "(A) component)) having a change in solubility in a developing solution by an action of an acid, and a general formula are included. (b1) A resist composition of the compound (B1) (hereinafter also referred to as "(B1) component").

When the resist film is formed by using the resist composition of the present embodiment, and the resist film is selectively exposed, an acid is generated from the (B1) component in the exposed portion of the resist film, by the action of the acid The solubility of the component (A) in the developer changes. On the other hand, in the unexposed portion of the resist film, the solubility of the component (A) does not change in the developer, and therefore the exposed portion and the unexposed portion are not changed. There is a difference in solubility between the developing solution. Therefore, when the resist film is developed, when the resist composition is positive, the exposed portion of the resist film is dissolved and removed to form a positive resist pattern, and the resist composition is negative. When the unexposed portion of the resist film is dissolved and removed, a negative resist pattern is formed.

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

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

Further, the resist composition of the present embodiment may be an alkali developing process using an alkali developing solution in the development process when the resist pattern is formed, or a developing solution containing an organic solvent may be used in the developing process (organic It is a solvent developing process for developing solution).

The resist composition of the present embodiment is an acid generating ability capable of generating an acid by exposure, and the component (A) may be produced by exposure to an acid other than the component (B1).

When the component (A) is produced by exposure, the component (A) is a "substrate component which generates an acid by exposure and which changes the solubility of the developer by the action of an acid". When the component (A) is a substrate component which generates an acid by exposure and the solubility of the developer changes by the action of an acid, it is preferred that the component (A1) described later is an acid generated by exposure. Further, the polymer compound which changes the solubility of the developer by the action of an acid. As such a polymer compound, a resin having a constituent unit which generates an acid by exposure can be used. A known unit of acid is generated by exposure, and a known person can be used.

<(A) component>

The component (A) is a substrate component which changes the solubility of the developer by the action of an acid.

In the present invention, "substrate component" means organic having film forming ability As the compound, an organic compound having a molecular weight of 500 or more is preferably used. When the molecular weight of the organic compound is 500 or more, the film forming ability is improved, and in addition, a nanometer-based resist pattern is easily formed.

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

As the non-polymer, those having a molecular weight of 500 or more and less than 4,000 are usually used. Hereinafter, the term "low molecular compound" means a non-polymer having a molecular weight of 500 or more and less than 4,000.

As the polymer, those having a molecular weight of 1,000 or more are usually used. Hereinafter, the term "resin", "polymer compound" or "polymer" means a polymer having a molecular weight of 1,000 or more.

The molecular weight of the polymer is a mass average molecular weight in terms of polystyrene obtained by GPC (gel permeation chromatography).

The resist composition of the present embodiment is a negative resistant composition for forming an alkali-developing process in a negative resist pattern, or a positive resist in a solvent developing process. In the case of the "former-type resist composition for a solvent-developing process", it is preferable to use a base component (A-2) which is soluble in an alkali developer as the component (A) (hereinafter referred to as "(A-2) ) component"), and further blending the crosslinking agent component. When the resist composition generates an acid from the (B1) component by exposure, for example, the acid acts to cause cross-linking between the component (A-2) and the crosslinking agent component, and as a result, alkali development The solubility of the liquid is reduced (the solubility in the organic developer is increased). Therefore, in the formation of the resist pattern, when the resist film is applied to the support and the resist film is selectively exposed, the resist film is exposed. The light portion is insoluble in the alkali developing solution (soluble in the organic developing solution), and the unexposed portion of the resist film remains soluble in the alkali developing solution (not soluble in the organic developing solution), and thus does not change. By developing with an alkali developer, a negative resist pattern is formed. Further, at this time, a positive resist pattern is formed by development with an organic developer.

As the component (A-2), a resin which is soluble in an alkali developer (hereinafter referred to as "alkali-soluble resin") can be used.

As the alkali-soluble resin, an alkyl ester having α- (hydroxyalkyl)acrylic acid or α- (hydroxyalkyl)acrylic acid (preferably having a carbon number of 1) as disclosed in JP-A-2000-206694 is disclosed. a resin of a constituent unit derived from at least one selected from the group consisting of alkyl esters of ~5; and a hydrogen atom bonded to a carbon atom having an α -position of a sulfonamide group disclosed in US Pat. No. 6,943,325 may be substituted with a substituent. the acrylic resin or a substituted polycycloolefin resin; U.S. Patent Publication No. 6,949,325, Japanese Laid-open Patent Publication No. 2005-336452, Japanese Patent Publication Laid-open No. 2006-317803 disclosed in α position carbon atoms of the fluorinated alcohol containing, and are bonded The acrylic resin having a hydrogen atom which may be substituted by a substituent; and a polycycloolefin resin having a fluorinated alcohol disclosed in JP-A-2006-259582, etc., preferably form a good resist pattern which is less swollen. .

Further, the above α- (hydroxyalkyl)acrylic acid is an acrylic acid in which a hydrogen atom to which a carbon atom bonded to the α -position is bonded may be substituted with a substituent, and a hydrogen atom bonded to the α -position of the carboxyl group is bonded to hydrogen. The acrylic acid of the atom and one or both of the α -hydroxyalkylacrylic acid having a hydroxyalkyl group (preferably a hydroxyalkyl group having 1 to 5 carbon atoms) bonded to the carbon atom at the α -position.

As a crosslinking agent component, for example, it is easy to form a good swelling. The resist pattern is preferably an amine-based crosslinking agent such as acetylene urea having a methylol group or an alkoxymethyl group, or a melamine-based crosslinking agent. The blending amount of the crosslinking agent component is preferably from 1 to 50 parts by mass based on 100 parts by mass of the alkali-soluble resin.

The resist composition of the present embodiment is a "positive resist composition for an alkali developing process" which forms a positive resist pattern in an alkali developing process, or a negative resist in a solvent developing process. In the case of the "a negative resist composition for a solvent developing process", as the component (A), it is preferred to use a substrate component (A-1) having an increased polarity by the action of an acid (hereinafter referred to as a component). "(A-1) ingredient"). By using the component (A-1), the polarity of the substrate component changes before and after the exposure, so that not only the alkali development process but also a good development contrast can be obtained in the solvent development process.

When the alkali developing process is applied, the component (A-1) is insoluble to the alkali developing solution before exposure, for example, when an acid is generated from the component (B1) by exposure, the polarity is increased by the action of the acid, and the alkali is increased. The solubility of the developer will increase. Therefore, in the formation of the resist pattern, when the resist film obtained by applying the resist composition onto the support is selectively exposed, the exposed portion of the resist film is poorly soluble to the alkali developer. The change is soluble, and on the other hand, the unexposed portion of the resist film maintains the alkali poorly soluble and does not change, so that a positive resist pattern is formed by alkali development.

On the other hand, when the solvent developing process is applied, the component (A-1) has high solubility in an organic developing solution before exposure, and when an acid is generated from the component (B1) by exposure, by the action of the acid, The polarity is increased, and the solubility to the organic developer is reduced. Therefore, in the formation of the resist pattern, the resistance is When the resist composition is applied to the support and the resist film is selectively exposed, the exposed portion of the resist film changes from soluble to poorly soluble, and on the other hand, the exposed portion of the resist film is maintained. Since it is soluble and does not change, by developing with an organic developing solution, it is possible to provide contrast between the exposed portion and the unexposed portion to form a negative resist pattern.

In the resist composition of the present embodiment, the component (A) is preferably the component (A-1). That is, the resist composition of the present embodiment is preferably a "positive resist composition for an alkali developing process" which forms a positive resist pattern in an alkali developing process, or a negative type in a solvent developing process. Resist pattern "Negative resist composition for solvent development process".

The component (A) is a polymer compound and/or a low molecular compound.

When the component (A) is the component (A-1), the component (A-1) preferably contains a polymer compound, and more preferably contains an acid-decomposable group having an increase in polarity by an action of an acid. The polymer compound (A1) (hereinafter also referred to as "(A1) component") of the constituent unit (a1).

. About (A1) ingredients

The component (A1) is a polymer compound having a constituent unit (a1).

As the component (A1), in addition to the constituent unit (a1), a constituent unit (a2) having a cyclic group containing a lactone, a ring group containing -SO ₂ - or a cyclic group containing a carbonate is preferably used. A polymer compound.

Further, as the component (A1), in addition to the constituent unit (a1), or in addition to the constituent unit (a1) and the constituent unit (a2), a constituent unit (a3) having an aliphatic hydrocarbon group containing a polar group is preferably used (a3) ( But equivalent to the constituent unit (a1) or a polymer compound other than the unit (a2).

In addition to the constituent units (a1) to (a3), the component (A1) may have a constituent unit (a4) containing an acid non-dissociable aliphatic cyclic group, and a formula (a9-1) described later. A constituent unit, a constituent unit derived from hydroxystyrene or styrene (st), a constituent unit which generates an acid by exposure, and the like.

≪ constituent unit (a1)≫

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

The "acid-decomposable group" is an acid-decomposable group having a bond capable of cracking at least a part of the structure of the acid-decomposable group by an action of an acid.

The acid-decomposable group which is increased in polarity by the action of an acid may, for example, be decomposed by the action of an acid to form a group of a polar group.

Examples of the polar group include a carboxyl group, a hydroxyl group, an amine group, a sulfo group (-SO ₃ H), and the like. Among these, a polar group containing -OH in the structure (hereinafter referred to as "polar group containing OH") is preferred, and a carboxyl group or a hydroxyl group is more preferred, and a carboxyl group is particularly preferred.

More specifically, examples of the acid-decomposable group include a group obtained by protecting the polar group with an acid dissociable group (for example, a hydrogen atom having a polar group containing OH, which is protected by an acid dissociable group).

The term "acid dissociable group" as used herein means (i) an acid dissociable group having a bond which is cleaved by a bond between an acid dissociable group and an atom adjacent to the acid dissociable group by an action of an acid, or , (ii) by the action of acid, part of the bond After the crack is formed, by further generating a decarboxylation reaction, both of the acid dissociable group and the bond between the atoms adjacent to the acid dissociable group can be cracked.

The acid dissociable group constituting the acid-decomposable group must be a group having a lower polarity than the polar group formed by dissociation of the acid-dissociable group, whereby the acid-dissociable group is caused by the action of an acid. Upon dissociation, a polar group having a higher polarity than the acid dissociable group is generated to increase the polarity. As a result, the polarity of the entire component (A1) increases. When the polarity is increased, the solubility in the developer is relatively changed. When the developer is an alkali developer, the solubility is increased. When the developer is an organic developer, the solubility is reduced.

Examples of the acid-dissociable group include those which have hitherto been used as the base dissociable group of the base resin for the chemically amplified resist composition.

Specific examples of the acid-dissociable group of the base resin for the chemically amplified resist composition include the "acetal type acid dissociable group" and the "third-stage alkyl ester type acid dissociation" described below. ", "3 alkoxycarbonyl acid dissociable group".

. Acetal acid dissociable group:

In the above-mentioned polar group, an acid dissociable group which protects a carboxyl group or a hydroxyl group, for example, an acid dissociable group represented by the following formula (a1-r-1) (hereinafter referred to as "acetal type acid dissociable group") .

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

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

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

In the formula (a1-r-1), the hydrocarbon group of Ra' ³ may, for example, be a linear or branched alkyl group or a cyclic hydrocarbon group.

The linear alkyl group preferably has a carbon number of 1 to 5, more preferably 1 to 4, still more preferably 1 or 2. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group or an n-butyl group is preferred; more preferably a methyl group or an ethyl group.

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

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

The aliphatic hydrocarbon group as a monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocycloalkane. The monocycloalkane is preferably a carbon number of 3 to 6, and specific examples thereof include cyclopentane and cyclohexane.

The polycyclic group-based aliphatic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a carbon number of 7 to 12, and specific examples thereof include adamantane and a descending Decane, isodecane, tricyclodecane, tetracyclododecane, and the like.

When the cyclic hydrocarbon group of Ra' ³ is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be a monocyclic ring or a polycyclic ring. The carbon number of the aromatic ring is preferably from 5 to 30, more preferably from 5 to 20, still more preferably from 6 to 15, and particularly preferably from 6 to 12.

Specific examples of the aromatic ring include an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene or phenanthrene; and an aromatic heterocyclic ring in which a part of the carbon atom of the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic hetero ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.

Specific examples of the aromatic hydrocarbon group in Ra' ³ include a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or the aromatic heterocyclic ring (aryl group or heteroaryl group); An aromatic ring (for example, biphenyl, anthracene, etc.) of an aromatic ring is obtained by removing one hydrogen atom; and a hydrogen atom of the aromatic hydrocarbon ring or the aromatic heterocyclic ring is substituted with an alkyl group (for example, A benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, an arylalkyl group such as a 2-naphthylethyl group, or the like). The carbon number of the alkyl group bonded to the aromatic hydrocarbon ring or the aromatic heterocyclic ring is preferably from 1 to 4, more preferably from 1 to 2, particularly preferably 1.

The cyclic hydrocarbon group in Ra' ³ may have a substituent. Examples of the substituent include -R ^P1 , -R ^P2 -OR ^P1 , -R ^P2 -CO-R ^P1 , -R ^P2 -CO-OR ^P1 , -R ^P2 -O-CO-R ^P1 , -R ^P2 - OH, -R ^P2 -CN or -R ^P2 -COOH (hereinafter, these substituents are also collectively referred to as "Ra ⁰⁵ ").

Here, R ^P1 is a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Further, R ^P2 is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms. However, part or all of one of the hydrogen atoms of the chain-like saturated hydrocarbon group, the aliphatic cyclic saturated hydrocarbon group and the aromatic hydrocarbon group of R ^P1 and R ^P2 may be substituted by a fluorine atom. The aliphatic cyclic hydrocarbon group may have one or more substituents of the above-mentioned one type, and may have one or more of a plurality of the above-mentioned substituents.

The monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group or a decyl group.

The monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group or a cyclododecyl group. Monocyclic aliphatic saturated hydrocarbon group; bicyclo [2.2.2] octyl, tricyclo [5.2.1.0 ^2,6 ] fluorenyl, tricyclo[3.3.1.1 ^3,7 ] fluorenyl, tetracyclic [6.2. 1.13, 6.0 ^2,7 ] A polycyclic aliphatic saturated hydrocarbon group such as dodecyl or adamantyl.

Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include a group obtained by removing one hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, anthracene, naphthalene, anthracene or phenanthrene.

When Ra' ³ is bonded to any of Ra' ¹ and Ra' ² to form a ring, the ring group is preferably a 4 to 7 member ring, more preferably a 4 to 6 member ring. Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.

. Grade 3 alkyl ester type acid dissociable group:

Among the above-mentioned polar groups, the acid-dissociable group which protects a carboxyl group is, for example, an acid dissociable group represented by the following formula (a1-r-2).

In addition, among the acid-dissociable groups represented by the following formula (a1-r-2), those which are composed of an alkyl group are referred to below as "a tertiary alkyl ester type acid dissociable group" for the sake of convenience.

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

Examples of the hydrocarbon group of Ra' ⁴ include a linear or branched alkyl group, a chain or cyclic alkenyl group, or a cyclic hydrocarbon group.

Ra 'group ⁴ of the linear or branched chain, the cyclic hydrocarbon group include the aforementioned Ra' are the ^{same. 3.}

The chain or cyclic alkenyl group in Ra' ⁴ is preferably an alkenyl group having 2 to 10 carbon atoms.

Examples of the hydrocarbon group of Ra' ⁵ and Ra' ^{6 are} the same as those of the above Ra' ³ .

When Ra' ⁵ and Ra' ^{6 are} bonded to each other to form a ring, the group represented by the following formula (a1 - r2-1), the group represented by the following formula (a1 - r2-2), and the following The formula (a1-r2-3) represents the base.

On the other hand, when Ra' ⁴ -Ra' ^{6 is} not bonded to each other, and is an independent hydrocarbon group, a group represented by the following formula (a1 - r2-4) can be mentioned.

[wherein, Ra' ¹⁰ represents an alkyl group having 1 to 10 carbon atoms, and Ra' ¹¹ represents a group which forms an aliphatic cyclic group together with a carbon atom to which Ra' ¹⁰ is bonded. Ya is a carbon atom, and Xa is a group which forms a divalent cyclic hydrocarbon group together with Ya. Part or all of one of the hydrogen atoms of the cyclic hydrocarbon group may also be substituted. Each of Ra ⁰¹ to Ra ⁰³ is independently a hydrogen atom, a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Part or all of one of the hydrogen atoms of the chain saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group may also be substituted. Two or more of Ra ⁰¹ to Ra ⁰³ may be bonded to each other to form a ring structure. Yaa is a carbon atom, and Xaa is a group which forms an aliphatic cyclic group together with Yaa. Ra ⁰⁴ is an aromatic hydrocarbon group which may have a substituent. The Ra' ¹² ~Ra' ¹⁴ series independently represent a hydrocarbon group. * indicates the bonding site (the same in the following description)].

In the formula (a1-r2-1), the alkyl group having 1 to 10 carbon atoms of Ra' ¹⁰ is preferably a linear or branched alkyl group as Ra' ^{3 in} the formula (a1-r-1). The basis of the enumeration. Ra' ^{10 is} preferably an alkyl group having 1 to 5 carbon atoms.

In the formula (a1-r2-1), the aliphatic cyclic group formed by Ra' ¹¹ and the carbon atom bonded to Ra' ¹⁰ is preferably a single of Ra' ^{3 in} the formula (a1-r-1). The group of the aliphatic or hydrocarbon group of the cyclo- or polycyclic group is exemplified.

In the formula (a1-r2-2), the divalent cyclic hydrocarbon group formed by Xa and Ya together may be a cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) in Ra' ³ in the above formula (a1-r-1). An aromatic hydrocarbon group) is obtained by further removing one or more hydrogen atoms.

The divalent cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. The substituent may be the same as the substituent which the cyclic hydrocarbon group in the above Ra' ³ may have.

In the formula (a1-r2-2), the monovalent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms in the range of Ra ⁰¹ to Ra ⁰³ may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. Heptyl, octyl, decyl and the like.

The monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in the Ra ⁰¹ to Ra ⁰³ may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a cyclic fluorene group. Monocyclic aliphatic saturated hydrocarbon group such as cyclyl or cyclododecyl; bicyclo[2.2.2]octyl, tricyclo[5.2.1.0 ^2,6 ]decyl, tricyclo[3.3.1.1 ^3,7 ]癸a polycyclic aliphatic saturated hydrocarbon group such as a tetracyclo[6.2.1.13, 6.0 ^2,7 ] dodecyl group or an adamantyl group.

Ra ⁰¹ ~ Ra ⁰³ is particularly preferably a hydrogen atom or a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms from the viewpoint of easiness of synthesis of a monomer compound derived from a structural unit (a1), more preferably A hydrogen atom, a methyl group or an ethyl group; particularly preferably a hydrogen atom.

The substituent of the chain-like saturated hydrocarbon group or the aliphatic cyclic saturated hydrocarbon group represented by the above-mentioned Ra ⁰¹ to Ra ⁰³ may, for example, be the same as the above-mentioned Ra ⁰⁵ .

Examples of the group containing a carbon-carbon double bond which is formed by a ring structure by two or more of Ra ⁰¹ to Ra ^{03 are} bonded to each other, and examples thereof include a cyclopentenyl group, a cyclohexenyl group, and a methylcyclopentenyl group. , methylcyclohexenyl, cyclopentylene vinyl, cyclohexylene vinyl, and the like. Among these, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylene group vinyl group are preferable from the viewpoint of easiness of synthesis of the monomer compound of the structural unit (a1).

In the formula (a1-r2-3), aliphatic cyclic group formed together Xaa and Yaa, preferably of formula (a1-r-1) as fat Ra ^'3 group of a monocyclic or polycyclic group, The group recited for the group of hydrocarbon groups.

In the formula (a1-r2-3), the aromatic hydrocarbon group in Ra ⁰⁴ may be one obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra ^{04 is} preferably obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms; more preferably, one or more hydrogen atoms are removed from benzene, naphthalene, anthracene or phenanthrene. More preferably, it is a base obtained by removing one or more hydrogen atoms from benzene, naphthalene or anthracene; particularly preferably a base obtained by removing one or more hydrogen atoms from benzene or naphthalene; A group obtained by removing one or more hydrogen atoms.

When Ra ⁰⁴ in the formula (a1-r2-3) is a naphthyl group, the bonding position of the Yaa bond in the above formula (a1-r2-3) may be any one or two of the naphthyl group. .

When Ra ⁰⁴ in the formula (a1-r2-3) is a fluorenyl group, the bonding position of the Yaa bond in the above formula (a1-r2-3) may be a 1-, 2- or 9-position of the fluorenyl group. Any of them.

The substituent which Ra ⁰⁴ in the formula (a1-r2-3) may have, for example, a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group A group (methoxy, ethoxy, propoxy, butoxy, etc.), an alkoxycarbonyl group or the like.

In the formula (a1-r2-4), Ra' ¹² and Ra' ¹⁴ are each independently an alkyl group having 1 to 10 carbon atoms, and the alkyl group is more preferably as Ra' in the formula (a1-r-1). ^a group of a linear or branched chain alkyl group of 3; more preferably a linear alkyl group having 1 to 5 carbon atoms; particularly preferably a methyl group or an ethyl group.

In the formula (a1-r2-4), Ra' ^{13 is} preferably a linear or branched alkyl group, a monocyclic group or a exemplified as the hydrocarbon group of Ra' ^{3 in} the formula (a1-r-1) or Polycyclic based aliphatic hydrocarbon groups. Among these, a group which is exemplified as the monocyclic or polycyclic aliphatic hydrocarbon group of Ra' ³ is more preferable.

Specific examples of the base represented by the above formula (a1-r2-1) are as follows.

Specific examples of the base represented by the above formula (a1 - r2-2) are listed below.

Specific examples of the base represented by the above formula (a1-r2-3) are as follows.

Specific examples of the base represented by the above formula (a1-r2-4) are as follows.

. Grade 3 alkoxycarbonyl acid dissociable group:

In the above-mentioned polar group, an acid dissociable group represented by the following formula (a1-r-3) is exemplified (hereinafter, for convenience, it is referred to as "3 alkoxycarbonyl acid dissociation". Base").

[wherein, Ra' ⁷ ~ Ra' ⁹ are each an alkyl group].

In the formula (a1-r-3), Ra' ⁷ to Ra' ^{9 are} preferably an alkyl group having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms.

Further, the total carbon number of each alkyl group is preferably from 3 to 7, more preferably from 3 to 5, most preferably from 3 to 4.

The constituent unit (a1) may, for example, be a constituent unit derived from an acrylate in which a hydrogen atom bonded to a carbon atom of the α -position may be substituted with a substituent, a constituent unit derived from acrylamide, or a hydroxystyrene or At least a part of a hydrogen atom in a hydroxyl group of a constituent unit derived from a hydroxystyrene derivative is derived from a constituent unit protected by a substituent of the acid-decomposable group, and is derived from a vinyl benzoic acid or a vinylbenzoic acid derivative. At least a part of the hydrogen atoms in the constituent unit -C(=O)-OH is constituted by a constituent unit which is protected by a substituent including the acid-decomposable group.

The constituent unit (a1) is preferably a constituent unit derived from an acrylate in which a hydrogen atom bonded to a carbon atom at the α -position can be substituted with a substituent.

Specific preferred examples of the constituent unit (a1) include constituent units represented by the following formula (a1-1) or (a1-2).

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms. Va ¹ is a divalent hydrocarbon group which may have an ether bond, n _a1 is 0 to 2, and Ra ¹ is an acid dissociable group represented by the above formula (a1-r-1) or (a1-r-2). ¹ is a WA n _a2 +1 monovalent hydrocarbon group, n _a2 is 1 to 3, the above-described acid of formula (a1-r-1) or (a1-r-3) represented by the dissociative group] Ra ² is.

In the above formula (a1-1), the alkyl group having 1 to 5 carbon atoms of R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include methyl group and ethyl group. Base, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and the like. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which one or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a fluorine atom.

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

In the above formula (a1-1), the divalent hydrocarbon group in Va ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group which is a divalent hydrocarbon group in Va ¹ may be saturated or unsaturated, and is usually preferably saturated.

More specifically, the aliphatic hydrocarbon group may, for example, be a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group having a ring in the structure.

The linear aliphatic hydrocarbon group preferably has a carbon number of 1 to 10, more preferably 1 to 6, more preferably 1 to 4, most preferably 1 to 3.

The linear aliphatic hydrocarbon group is preferably a linear alkyl group, and specific examples thereof include a methylene group [-CH ₂ -], an exoethyl group [-(CH ₂ ) ₂ -], and a Sanya. Methyl [-(CH ₂ ) ₃ -], tetramethylene [-(CH ₂ ) ₄ -], pentamethylene [-(CH ₂ ) ₅ -], and the like.

The branched chain aliphatic hydrocarbon group preferably has a carbon number of 2 to 10, more preferably 3 to 6, more preferably 3 or 4, most preferably 3.

The branched aliphatic hydrocarbon group is preferably a branched alkyl group, and specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - , etc. alkylmethylene ;-CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C( _{CH 2 CH 3) 2 -CH 2} - , etc. extending ethyl _{group; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - , etc. trimethylene group; -CH (CH ₃ ) an alkylalkylene group such as an alkyltetramethylene group such as CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - or the like. The alkyl group in the alkylalkyl group is preferably a linear alkyl group having 1 to 5 carbon atoms.

The aliphatic hydrocarbon group containing a ring in the above structure may, for example, be an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), or an alicyclic hydrocarbon group bonded to a linear or branched aliphatic group. The end of the hydrocarbon group The group or the alicyclic hydrocarbon group is present in the middle of a linear or branched aliphatic hydrocarbon group. The linear or branched aliphatic hydrocarbon group may be the same as the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group.

The alicyclic hydrocarbon group preferably has a carbon number of 3 to 20, more preferably 3 to 12.

The alicyclic hydrocarbon group may be a polycyclic ring or a monocyclic ring. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably a carbon number of 3 to 6, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from the polycycloalkane. The polycycloalkane is preferably a carbon number of 7 to 12, and specifically, adamantane , norbornane, isodecane, tricyclodecane, tetracyclododecane, and the like.

The aromatic hydrocarbon group which is a divalent hydrocarbon group in Va ¹ is a hydrocarbon group having an aromatic ring.

The aromatic hydrocarbon group preferably has a carbon number of 3 to 30, more preferably 5 to 30, still more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, the carbon number does not include the carbon number in the substituent.

Specific examples of the aromatic ring of the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, anthracene, naphthalene, anthracene, and phenanthrene; and a part of carbon atoms constituting the aromatic hydrocarbon ring are substituted by a hetero atom. An aromatic heterocyclic ring or the like. Examples of the hetero atom in the aromatic hetero ring include an oxygen atom, a sulfur atom, and a nitrogen atom.

Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring (arylene); A group in which one hydrogen atom of a group (aryl group) obtained by removing one hydrogen atom is substituted with an alkyl group (for example, from benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthyl group) The aryl group in the arylalkyl group such as a 1-naphthylethyl group or a 2-naphthylethyl group is further removed by one hydrogen atom). The carbon number of the alkylene group (alkyl chain in the arylalkyl group) is preferably from 1 to 4, more preferably from 1 to 2, particularly preferably 1.

In the above formula (a1-1), Ra ¹ is an acid dissociable group represented by the above formula (a1-r-1) or (a1-r-2). Among these, as Ra ¹ , it is easier to improve the characteristics (sensitivity, shape, and the like) of the lithography by electron beam or EUV, particularly the acid dissociation represented by the above formula (a1-r-2). The base is good.

Among the acid-dissociable groups represented by the above formula (a1-r-2), the group represented by the above formula (a1-r2-1), the group represented by the formula (a1-r2-2), and the formula (in particular) The group represented by a1-r2-3) and the group represented by the formula (a1-r2-4) are preferred, and among these, the group represented by the formula (a1-r2-2) and the formula (preferably) A1-r2-3) indicates the basis.

In the above formula (a1-2), the n _a2 +1 valent hydrocarbon group in Wa ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity, and may be saturated or unsaturated, and is usually preferably saturated. Examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, or an aliphatic hydrocarbon group in which a linear or branched chain is combined, and an aliphatic group containing a ring in the structure. The base of a hydrocarbon group.

The aforementioned n _a2 +1 valence is preferably 2 to 4 valence, more preferably 2 or 3 valence.

Hereinafter, a specific example of the constituent unit represented by the above formula (a1-1) will be described. In the following formulae, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

Hereinafter, a specific example of the constituent unit represented by the above formula (a1-2) is shown.

The constituent unit (a1) of the component (A1) may be one type or two or more types.

The constituent unit (a1) is more preferably a constituent unit represented by the above formula (a1-1), and more preferably a characteristic (sensitivity, shape, and the like) which can easily improve the lithography by electron beam or EUV. In the case where Ra ¹ is an acid dissociable group represented by the above formula (a1 - r-2), it is particularly preferable that Ra ¹ is a group represented by the above formula (a1 - r2-2), and a formula (a1) R2-3) indicates the base.

The ratio of the constituent unit (a1) in the component (A1) is preferably 5 to 60 mol%, more preferably 10 to 55 mol%, based on the total of all constituent units of the component (A1). More preferably, it is 20~50%.

By setting the ratio of the constituent unit (a1) to the lower limit or more, the resist pattern can be easily obtained, and the lithographic characteristics such as sensitivity, resolution, thickness improvement, and EL margin can be improved. Further, by being equal to or less than the upper limit value, the balance with other constituent units can be achieved.

≪ constituent unit (a2)≫

The constituent unit (a2) is a constituent unit containing a lactone-containing cyclic group, a -SO ₂ -containing cyclic group or a carbonate-containing cyclic group (except for the constituent unit (a1)).

The lactone-containing cyclic group of the constituent unit (a2), the -SO ₂ -containing cyclic group or the carbonate-containing cyclic group, is effective for improving the resist when the (A1) component is used to form the resist film. The adhesion of the film to the substrate. Further, by having the constituent unit (a2), the solubility of the resist film to the alkali developing solution is improved during development in the alkali developing process.

The "per lactone-containing cyclic group" means a cyclic group containing a ring (lactone) containing -O-C(=O)- in its ring skeleton. The lactone ring is counted as the first ring, and the lactone ring is called the monocyclic group. When it has other ring structures, it is called a polycyclic group. Ring containing lactone The formula may be a monocyclic group or a polycyclic group.

The cyclic group containing a lactone in the constituent unit (a2) is not particularly limited, and any of them may be used. Specifically, the groups represented by the following general formulae (a2-r-1) to (a2-r-7) are exemplified.

[wherein, Ra' ^{21 is} independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone-containing ring group, a carbonate-containing ring group, or a -SO ₂ -containing ring group; A" may contain an oxygen atom (-O-) or sulfur The atom (-S-) has a carbon number of 1 to 5, an alkyl group, an oxygen atom or a sulfur atom, n' is an integer of 0 to 2, and m' is 0 or 1].

In the above formula (a2-r-1) to (a2-r-7), the alkyl group in Ra' ²¹ is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group and the like. Among these, a methyl group or an ethyl group is preferred; a methyl group is particularly preferred.

The alkoxy group in Ra' ²¹ is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, the alkyl group exemplified as the alkyl group in the above Ra' ²¹ is bonded to an oxygen atom (-O-).

The halogen atom in Ra' ²¹ may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom.

As Ra ^'21 in the halogenated alkyl group include the Ra' part of hydrogen atoms in the alkyl group of ²¹ or all of the preceding groups substituted with a halogen atom. The halogenated alkyl group is preferably a fluorinated alkyl group, particularly preferably a perfluoroalkyl group.

In "COOR" and -OC(=O)R" in Ra' ²¹ , R" is a hydrogen atom, an alkyl group, a lactone-containing ring group, a carbonate-containing ring group, or a -SO ₂ group. - The ring base.

The alkyl group in R" may be any of a linear chain, a branched chain, and a cyclic group, and the carbon number is preferably from 1 to 15.

When R" is a linear or branched alkyl group, it preferably has a carbon number of 1 to 10, more preferably a carbon number of 1 to 5, particularly preferably a methyl group or an ethyl group.

When R" is a cyclic alkyl group, it is preferably a carbon number of 3 to 15, more preferably a carbon number of 4 to 12, most preferably a carbon number of 5 to 10. Specifically, it can be exemplified by a fluorine atom or fluorine. The alkyl group may be substituted with one or more hydrogen atoms in the unsubstituted monocycloalkane; and one or more hydrogen atoms may be removed from the polycycloalkane such as bicycloalkane, tricycloalkane or tetracycloalkane. More specifically, a group obtained by removing one or more hydrogen atoms from a monocycloalkane such as cyclopentane or cyclohexane; and adamantane, norbornane, isodecane, a base obtained by removing one or more hydrogen atoms from a polycycloalkane such as tricyclodecane or tetracyclododecane Wait.

The cyclic group containing a lactone in R" may be the same as the group represented by the above formula (a2-r-1) to (a2-r-7).

The carbonate-containing cyclic group in R" is the same as the carbonate-containing cyclic group described later, and specifically, the group represented by the formula (ax3-r-1) to (ax3-r-3) .

The cyclic group containing -SO ₂ - in R" is the same as the ring-form group containing -SO ₂ - described later, and specifically, the formula (a5-r-1) to (a5-r-4) Represented separately.

The hydroxyalkyl group in Ra' ²¹ is preferably a carbon number of 1 to 6, and specifically, a group in which at least one hydrogen atom of the alkyl group in the above Ra' ²¹ is substituted with a hydroxyl group.

In the above formula (a2-r-2), (a2-r-3), (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A" is preferably linear or The branched alkyl group may, for example, be a methylene group, an ethyl group, an n-propyl group or an extended isopropyl group. When the alkyl group contains an oxygen atom or a sulfur atom, specific examples thereof may be mentioned above. The terminal of the alkyl group or the carbon atom may have a group of -O- or -S-, and examples thereof include -O-CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ -, etc. As A", an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, is preferably a methylene group.

Specific examples of the groups represented by the general formulae (a2-r-1) to (a2-r-7) are as follows.

The "cyclic group containing -SO ₂ -" means a cyclic group containing a ring containing -SO ₂ - in its ring skeleton, specifically, a sulfur atom (S) in -SO ₂ - forms a ring A cyclic group of a portion of a ring skeleton of the formula. The ring containing -SO ₂ - in the ring skeleton is counted as the first ring, and the ring is only called the monocyclic group. When further having other ring structures, the structure is called a polycyclic group. . The cyclic group containing -SO ₂ - may be a monocyclic group or a polycyclic group.

Containing -SO ₂ - of the cyclic group, particularly preferably contained in the ring skeleton thereof -O-SO ₂ - group of cyclic, i.e. containing -O-SO ₂ - in the -OS- form part of the ring skeleton A cyclic group of a sultone ring.

More specifically, examples of the ring-form group containing -SO ₂ - include the groups represented by the following general formulae (a5-r-1) to (a5-r-4).

[wherein, Ra' ^{51 is} independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone-containing ring group, a carbonate-containing ring group, or a -SO ₂ -containing ring group; A" is a carbon number which may contain an oxygen atom or a sulfur atom ~5 alkyl, oxygen or sulfur atom, n' is an integer from 0 to 2].

In the above formula (a5-r-1) to (a5-r-2), A" is related to the above formula (a2-r-2), (a2-r-3), (a2-r-5) The middle A" is the same.

The alkyl group, the alkoxy group, the halogen atom, the halogenated alkyl group, the -COOR", the -OC(=O)R", and the hydroxyalkyl group in Ra' ⁵¹ can be exemplified by the above formula (a2-r-1). The ones listed in the description of Ra' ²¹ in ~(a2-r-7) are the same.

Specific examples of the groups represented by the general formulae (a5-r-1) to (a5-r-4) are as follows. The "Ac" in the formula represents an ethyl group.

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

The carbonate-containing cyclic group is not particularly limited, and any of them may be used. Specifically, the group represented by the following general formula (ax3-r-1) to (ax3-r-3) is exemplified.

^Wherein Ra' ^{x31 is} independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone-containing ring group, a carbonate-containing ring group, or a -SO ₂ -containing ring group; A" is a carbon number which may contain an oxygen atom or a sulfur atom ~5 alkyl, oxygen or sulfur atom, p' is an integer from 0 to 3, q' is 0 or 1].

In the above formula (ax3-r-2)~(ax3-r-3), A" is related to the above formula (a2-r-2), (a2-r-3), (a2-r-5) The middle A" is the same.

The alkyl group, the alkoxy group, the halogen atom, the halogenated alkyl group, the -COOR", the -OC(=O)R", and the hydroxyalkyl group in Ra' ³¹ can be respectively exemplified by the above formula (a2-r-1) The ones listed in the description of Ra' ²¹ in ~(a2-r-7) are the same.

Specific examples of the groups represented by the general formula (ax3-r-1) to (ax3-r-3) are as follows.

The constituent unit (a2) is particularly preferably a constituent unit derived from an acrylate in which a hydrogen atom bonded to a carbon atom at the α -position can be substituted with a substituent.

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

[In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms. Ya ²¹ is a single bond or a divalent linkage. La ²¹ is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO- or -CONHCS-, and R' represents a hydrogen atom or a methyl group. When La ²¹ is -O-, Ya ^{21 is} not -CO-. Ra ²¹ is a lactone-containing ring group, a carbonate-containing ring group, or a -SO ₂ -containing ring group.

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

The divalent linking group of Ya ²¹ is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.

. a divalent hydrocarbon group which may have a substituent:

When Ya ²¹ is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

. . Aliphatic hydrocarbon group in Ya ²¹

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

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

. . . Linear or branched aliphatic hydrocarbon group

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

The linear aliphatic hydrocarbon group is preferably a linear alkyl group, and specific examples thereof include a methylene group [-CH ₂ -], an exoethyl group [-(CH ₂ ) ₂ -], and a Sanya. Methyl [-(CH ₂ ) ₃ -], tetramethylene [-(CH ₂ ) ₄ -], pentamethylene [-(CH ₂ ) ₅ -], and the like.

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

The branched aliphatic hydrocarbon group is preferably a branched alkyl group, and specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - , etc. alkylmethylene ;-CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C( _{CH 2 CH 3) 2 -CH 2} - , etc. extending ethyl _{group; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - , etc. trimethylene group; -CH (CH ₃ ) an alkylalkylene group such as an alkyltetramethylene group such as CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - or the like. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

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

. . . An aliphatic hydrocarbon group containing a ring in the structure

Examples of the aliphatic hydrocarbon group containing a ring in the structure include a cyclic aliphatic hydrocarbon group which may include a substituent of a hetero atom in the ring structure (a group obtained by removing two hydrogen atoms from the aliphatic hydrocarbon ring), and the foregoing a group in which a cyclic aliphatic hydrocarbon group is bonded to a terminal of a linear or branched aliphatic hydrocarbon group, and the above-mentioned cyclic aliphatic hydrocarbon group is present in a base of a linear or branched aliphatic hydrocarbon group. . Examples of the linear or branched aliphatic hydrocarbon group include the same as described above.

The cyclic aliphatic hydrocarbon group preferably has a carbon number of 3 to 20, more preferably 3 to 12.

The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably a carbon number of 3 to 6, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a carbon number of 7 to 12, and specifically, adamantane or a descendant is mentioned. Decane, isodecane, tricyclodecane, tetracyclododecane, and the like.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group and the like.

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

The alkoxy group as the above substituent is preferably an alkoxy group having 1 to 5 carbon atoms; more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, or an n- group; Butoxy, tert-butoxy; most preferred is methoxy, ethoxy.

The halogen atom as the substituent may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom.

The halogenated alkyl group as the substituent may be a group in which one or all of the hydrogen atoms of the alkyl group are substituted by the halogen atom.

The cyclic aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom by a part of a carbon atom constituting the ring structure. The substituent containing a hetero atom is preferably -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O-.

. . Aromatic hydrocarbon group in Ya ²¹

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

The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be a single ring type or a polycyclic type. The carbon number of the aromatic ring is preferably from 5 to 30, more preferably from 5 to 20, still more preferably from 6 to 15, and particularly preferably from 6 to 12. However, the carbon number does not include the carbon number in the substituent. Specific examples of the aromatic ring include an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene or phenanthrene; and an aromatic heterocyclic ring in which a part of the carbon atom of the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic hetero ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.

Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or the aromatic heterocyclic ring (such as an aryl group or a heteroaryl group); and two or more aromatic rings are contained. An aromatic compound (such as biphenyl, anthracene, etc.) obtained by removing two hydrogen atoms; from the aforementioned aromatic hydrocarbon ring Or a radical in which one hydrogen atom of an aromatic heterocyclic ring (1 aryl group or heteroaryl group) is substituted with an alkyl group (for example, from a benzyl group, a phenethyl group, a 1-naphthyl group) The aryl group in the arylalkyl group such as a methyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group or a 2-naphthylethyl group is further removed by a hydrogen atom, and the like. The number of carbon atoms bonded to the alkyl group of the above aryl or heteroaryl group is preferably from 1 to 4, more preferably from 1 to 2, particularly preferably 1.

In the aromatic hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group and the like.

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

The alkoxy group, the halogen atom and the halogenated alkyl group as the substituent are exemplified as a substituent which substitutes a hydrogen atom which the cyclic aliphatic hydrocarbon group has.

. a divalent linking group containing a hetero atom:

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

When the aforementioned divalent linking group containing a hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)- And H may be substituted by a substituent such as an alkyl group or a thiol group. The substituent (alkyl group, thiol group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.

General formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(=O)-OY ²¹ -, -[Y ²¹ -C(=O ) -O] _m" -Y ²² -, -Y ²¹ -OC(=O)-Y ²² - or -Y ²¹ -S(=O) ₂ -OY ²² -, Y ²¹ and Y ²² are independently A divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group may be the same as those exemplified as the divalent linking group (a divalent hydrocarbon group which may have a substituent).

Y ^{21 is} preferably a linear aliphatic hydrocarbon group, more preferably a linear alkyl group, more preferably a linear alkyl group having a carbon number of 1 to 5, particularly preferably a methylene group. Or stretch ethyl.

Y ^{22 is} preferably a linear or branched aliphatic hydrocarbon group; more preferably a methylene group, an ethyl group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, most preferably a methyl group.

In the formula -[Y ²¹ -C(=O)-O] _m" -Y ²² - represents a group, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1. Very good for 1. In other words, as a group represented by the formula -[Y ²¹ -C(=O)-O] _m" -Y ²² -, it is particularly preferably a group represented by the formula -Y ²¹ -C(=O)-OY ²² -. Preferably, the group represented by the formula -(CH ₂ ) _a' -C(=O)-O-(CH ₂ ) _b' - is preferred. In the formula, a' is an integer from 1 to 10, preferably from 1 to 8. The integer, more preferably an integer from 1 to 5, more preferably 1 or 2, most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably from 1 to 5. An integer, more preferably 1 or 2, is preferably 1.

As Ya ²¹ , a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a linear or branched alkyl group, or a combination thereof is preferable.

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

The lactone-containing cyclic group, the -SO ₂ -containing cyclic group, and the carbonate-containing cyclic group in Ra ²¹ may be suitably exemplified by the above formula (a2-r-1) to (a2-r). -7) The base, the formula (a5-r-1)~(a5-r-4) respectively represent the base, and the formula (ax3-r-1)~(ax3-r-3) respectively base.

Especially preferred is a cyclic group containing a lactone or a cyclic group containing -SO ₂ -; more preferably the above formula (a2-r-1), (a2-r-2), (a2-r- 6) or (a5-r-1) respectively represent the basis. Specifically, it is more preferable to use the above chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-18), (r-lc-6-1), (r-sl-1-1), and (r-sl-1-18) each represent a base of any of them.

The constituent unit (a2) of the component (A1) may be one type or two or more types.

When the component (A1) has a constituent unit (a2), the ratio of the constituent unit (a2) is preferably from 1 to 80 mol%, more preferably from 1 to 80 mol%, based on the total of all constituent units constituting the component (A1). 10~70% by mole, more preferably 10~65% by mole, and particularly preferably 10~60% by mole.

By setting the ratio of the constituent unit (a2) to a lower limit or more, The effect of the constituent unit (a2) can be sufficiently obtained. On the other hand, by setting it to a lower limit or less, it is possible to achieve a balance with other constituent units, and various lithographic characteristics and pattern shapes are excellent.

≪ constituent unit (a3)≫

The constituent unit (a3) is a constituent unit containing an aliphatic hydrocarbon group containing a polar group (except for the constituent unit (a1) or the constituent unit (a2)).

The component (A1) has a structural unit (a3), and the hydrophilicity of the component (A) is improved, which contributes to an improvement in resolution.

The polar group may, for example, be a hydroxy group having a hydroxyl group, a cyano group, a carboxyl group or a hydrogen atom of an alkyl group substituted with a fluorine atom, and particularly preferably a hydroxyl group.

The aliphatic hydrocarbon group may, for example, be a linear or branched hydrocarbon group (preferably alkylene group) having 1 to 10 carbon atoms or a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be a monocyclic group or a polycyclic group, and may be used, for example, as appropriate among most of the proprietors of the resin for the ArF excimer laser resist composition. As the cyclic group, a polycyclic group is preferred, and the carbon number is more preferably from 7 to 30.

More preferably, it is a constituent unit derived from an aliphatic polycyclic group acrylate containing a hydroxyalkyl group in which one of a hydrogen atom having a hydroxyl group, a cyano group, a carboxyl group, or an alkyl group is partially substituted by a fluorine atom. The polycyclic group may be a group obtained by removing two or more hydrogen atoms from a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specifically, examples thereof include the removal of two or more hydrogenogens from a polycycloalkane such as adamantane, norbornane, isodecane, tricyclodecane or tetracyclododecane. The basis of the child and so on. Among these polycyclic groups, industrially, it is preferably a group obtained by removing two or more hydrogen atoms from adamantane, and a base obtained by removing two or more hydrogen atoms from norbornane, from tetracyclododecane. A base obtained by removing two or more hydrogen atoms.

The constituent unit (a3) is not particularly limited as long as it contains a polar group-containing aliphatic hydrocarbon group, and any of them can be used.

The constituent unit (a3) is preferably a constituent unit derived from an acrylate in which a hydrogen atom bonded to a carbon atom of the α -position can be substituted with a substituent, and which is a constituent unit of an aliphatic hydrocarbon group containing a polar group. .

When the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms as the constituent unit (a3), it is preferably a constituent unit derived from hydroxyethyl acrylate. When the hydrocarbon group is a polycyclic group, a constituent unit represented by the following formula (a3-1), a constituent unit represented by the formula (a3-2), and a constituent unit represented by the formula (a3-3) are preferable.

[In the formula, R is the same as the above, j is an integer from 1 to 3, k is an integer from 1 to 3, t' is an integer from 1 to 3, 1 is an integer from 1 to 5, and s is an integer from 1 to 3. ].

In the formula (a3-1), j is preferably 1 or 2, more preferably 1. When j is 2, it is preferred that the hydroxy group is bonded to the 3 and 5 positions of the adamantyl group. When j is 1, it is preferred that the hydroxy group is bonded to the adamantyl group.

j is preferably 1, particularly preferably a hydroxyl group bonded to the adamantyl group.

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

In the formula (a3-3), t' is preferably 1. 1 is preferably 1. s is preferably 1. These are preferably bonded to a 2-norbornyl group or a 3-norinyl group at the terminal of the carboxyl group of the acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5 or 6 position of the thiol group.

The constituent unit (a3) of the component (A1) may be one type or two or more types.

When the component (A3) has a constituent unit (a3), the ratio of the constituent unit (a3) is preferably 5 to 50 mol%, more preferably 5 to 50 mol%, based on the total of all constituent units constituting the component (A1). 5 to 40 mol%, and more preferably 5 to 35 mol%.

By setting the ratio of the constituent unit (a3) to a lower limit or more, the effect of containing the constituent unit (a3) can be sufficiently obtained, and on the other hand, it is easy to achieve the other than the upper limit. The balance of the constituent units.

≪ constituent unit (a4)≫

The constituent unit (a4) is an aliphatic cyclic group containing acid non-dissociable Constitute unit.

The (A1) component has a constituent unit (a4), which improves the dry etching resistance of the formed resist pattern. Moreover, the hydrophobicity of the component (A) is improved. The improvement of the hydrophobicity is considered to contribute to the improvement of the resolution, the shape of the resist pattern, and the like particularly in the case of the solvent developing process.

The "acid-non-dissociable cyclic group" in the constituent unit (a4) is when an acid is generated in the resist composition by exposure (for example, when an acid is generated from a component (B1) described later), even if the acid acts It does not dissociate and maintains the cyclic group remaining in the constituent unit.

The constituent unit (a4) is preferably, for example, a constituent unit derived from an acrylate containing an acid non-dissociable aliphatic cyclic group. The ring group can be used as a resin component of a resist composition such as ArF excimer laser or KrF excimer laser (preferably for ArF excimer laser), and is conventionally known. .

In particular, when it is at least one selected from the group consisting of a tricyclic fluorenyl group, an adamantyl group, a tetracyclododecyl group, an isodecyl group, and a fluorenyl group, it is preferably industrially easy to obtain. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specific examples of the constituent unit (a4) include constituent units represented by the following general formulae (a4-1) to (a4-7).

[wherein R ^α is the same as described above].

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

When the component (A1) has a constituent unit (a4), the ratio of the constituent unit (a4) is preferably 1 to 30 mol%, more preferably 1 to 30 mol%, based on the total of all constituent units constituting the component (A1). 3~20 mol%.

By setting the ratio of the constituent unit (a4) to a lower limit or more, the effect of containing the constituent unit (a4) can be sufficiently obtained, and on the other hand, it is easy to reach the other than the upper limit. The balance of the constituent units.

≪ constituent unit (a9)≫

The constituent unit (a9) is a constituent unit represented by the following general formula (a9-1).

[In the formula, R is the same as described above, and Ya ⁹¹ is a single bond or a divalent linking group, R ⁹¹ is a hydrocarbon group which may have a substituent, and Ya ⁹² is a divalent linking group].

In the above formula (a9-1), R is the same as described above.

R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or a methyl group in terms of industrial availability.

In the above formula (a9-1), the divalent linking group in Ya ⁹¹ is the same as the divalent linking group of Ya ²¹ in the above formula (a2-1). Ya ^{91 is} preferably a single button.

In the above formula (a9-1), the divalent linking group in Ya ⁹² may be the same as the divalent linking group of Ya ²¹ in the above formula (a2-1).

In the divalent linking group of Ya ⁹² , a divalent hydrocarbon group which may have a substituent is preferably a linear or branched aliphatic hydrocarbon group.

The linear aliphatic hydrocarbon group preferably has a carbon number of 1 to 10, more preferably 1 to 6, more preferably 1 to 4, most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkyl group, and specific examples thereof include a methylene group [-CH ₂ -], an exoethyl group [-(CH ₂ ) ₂ -], and a Sanya. Methyl [-(CH ₂ ) ₃ -], tetramethylene [-(CH ₂ ) ₄ -], pentamethylene [-(CH ₂ ) ₅ -], and the like.

The branched aliphatic hydrocarbon group preferably has a carbon number of 2 to 10, more preferably 3 to 6, more preferably 3 or 4, most preferably 3. The branched aliphatic hydrocarbon group is preferably a branched alkyl group, and specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - , etc. alkylmethylene ;-CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C( _{CH 2 CH 3) 2 -CH 2} - , etc. extending ethyl _{group; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - , etc. trimethylene group; -CH (CH ₃ ) an alkylalkylene group such as an alkyltetramethylene group such as CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - or the like. The alkyl group in the alkylalkyl group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Further, among the divalent linking groups in Ya ⁹² , examples of the divalent linking group which may have a hetero atom include -O-, -C(=O)-O-, -C(=O)-, and -OC ( =O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H may also be substituted by a substituent such as an alkyl group, a thiol group, etc.), -S- , -S(=O) ₂ -, -S(=O) ₂ -O-, -C(=S)-, general formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ - C(=O)-O-, -C(=O)-O--Y ²¹ , [Y ²¹ -C(=O)-O] _m' -Y ²² - or -Y ²¹ -OC(=O) -Y ²² - represents a group [wherein, Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m' is an integer of 0 to 3]. Among them, -C(=O)-, -C(=S)- is particularly preferred.

In the above formula (a9-1), the hydrocarbon group in R ⁹¹ may, for example, be an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group or an aralkyl group.

The alkyl group in R ⁹¹ preferably has a carbon number of 1 to 8, more preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and may be linear or branched. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group.

The monovalent alicyclic hydrocarbon group in R ⁹¹ preferably has a carbon number of 3 to 20, more preferably 3 to 12 carbon atoms, and may be a polycyclic ring or a monocyclic ring. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably a carbon number of 3 to 6, and specific examples thereof include cyclobutane, cyclopentane, and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from the polycycloalkane, and the polycycloalkane is preferably a carbon number of 7 to 12, specifically Adamantane, norbornane, isodecane, tricyclodecane, tetracyclododecane and the like are listed.

The aryl group in R ⁹¹ is preferably a carbon number of 6 to 18, more preferably a carbon number of 6 to 10, and particularly preferably a phenyl group.

The aralkyl group in R ⁹¹ is preferably an aralkyl group obtained by bonding an alkylene group having 1 to 8 carbon atoms to the above-mentioned "aryl group in R ⁹¹ ", more preferably a carbon number of 1 to 6 An aralkyl group obtained by bonding an alkyl group to the above-mentioned "aryl group in R ⁹¹ ", particularly preferably an alkylene group having 1 to 4 carbon atoms and the above-mentioned "aryl group in R ⁹¹ " base.

The hydrocarbon group in R ⁹¹ is preferably a part or all of a hydrogen atom of the hydrocarbon group substituted by a fluorine atom, more preferably 30 to 100% of a hydrogen atom of the hydrocarbon group is substituted by a fluorine atom. Among them, a perfluoroalkyl group in which all of the hydrogen atoms of the above alkyl group are substituted by a fluorine atom is particularly preferable.

The hydrocarbon group in R ⁹¹ may have a substituent. Examples of the substituent include a halogen atom, a pendant oxy group (=O), a hydroxyl group (-OH), an amine group (-NH ₂ ), and -SO ₂ -NH ₂ . Further, a part of the carbon atom constituting the hydrocarbon group may be substituted with a substituent containing a hetero atom. Examples of the hetero atom-containing substituent include -O-, -NH-, -N=, -C(=O)-O-, -S-, -S(=O) ₂ -, -S (= O) ₂ -O-.

In R ⁹¹ , examples of the hydrocarbon group having a substituent include a lactone-containing ring group represented by the above formula (a2-r-1) to (a2-r-7).

Further, in R ⁹¹ , examples of the hydrocarbon group having a substituent include a ring group containing -SO ₂ - represented by the above formula (a5-r-1) to (a5-r-4); A substituted aryl group, a monovalent heterocyclic group or the like.

Among the constituent units (a9), a constituent unit represented by the following general formula (a9-1-1) is preferable.

[In the formula, R is the same as defined above, and Ya ⁹¹ is a single bond or a divalent linking group, R ⁹¹ is a hydrocarbon group which may have a substituent, and R ⁹² is an oxygen atom or a sulfur atom].

In the general formula (a9-1-1), the descriptions of Ya ⁹¹ , R ⁹¹ and R are the same as described above. Further, R ⁹² is an oxygen atom or a sulfur atom.

Specific examples of the constituent units represented by the above formula (a9-1) or the formula (a9-1-1) are shown below. In the following formula, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The constituent unit (a9) contained in the component (A1) may be one type or two or more types.

When the component (A1) has a constituent unit (a9), the ratio of the constituent unit (a9) is preferably 1 to 40 mol%, more preferably 1 to 40 mol%, based on the total of all constituent units constituting the component (A1). 3~30% by mole, and especially good is 10~30% by mole.

When the ratio of the constituent unit (a9) is equal to or greater than the lower limit value, the lithographic characteristics such as the development characteristics and the EL margin are improved, and by setting it as the upper limit or less, it is easy to achieve a balance with other constituent units.

≪ constituent unit (st)≫

The constituent unit (st) is a constituent unit derived from hydroxystyrene or styrene.

The constituent unit (st) represented by the following general formula (I) and the constituent unit (st2) represented by the following general formula (II) are exemplified as the preferred constituent unit (st).

[wherein R ^st represents a hydrogen atom or a methyl group. m ₀₁ represents an integer from 1 to 3. R ⁰¹ represents an alkyl group having 1 to 5 carbon atoms. m ₀₂ represents 0 or an integer from 1 to 3].

In the above formula (I), R ^st is a hydrogen atom or a methyl group, preferably a hydrogen atom.

m ₀₁ is an integer of 1 to 3, preferably 1.

The bonding position of the hydroxyl group in the benzene ring may be any of the o-position, the m-position, and the p-position, but it is easily available and, at a low price, preferably m ₀₁ is 1, and The p-position has a hydroxyl group. When m ₀₁ is 2 or 3, any substitution position can be combined.

In the above formula (II), R ^st is a hydrogen atom or a methyl group, preferably a hydrogen atom.

R ^{01 is} preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. , pentyl, isopentyl, neopentyl and the like. Industrially preferred is methyl or ethyl.

m ₀₂ is an integer of 0 or 1 to 3. Among these, m _{02 is} preferably 0 or 1, and industrially more preferably 0. Further, when m ₀₂ is 1, the substitution position of R ⁰¹ in the benzene ring may be any of the o-position, the m-position, and the p-position, and when m ₀₂ is 2 or 3, any substitution may be combined. position.

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

When the component (A1) has a constituent unit (st), the ratio of the constituent unit (st) is preferably from 1 to 80 mol%, more preferably from 1 to 80 mol%, based on the total of all constituent units constituting the component (A1). 10 to 75 mol%, and more preferably 20 to 70 mol%.

When the ratio of the constituent unit (st) is equal to or higher than the lower limit value, the lithographic characteristics such as development characteristics and EL margin are improved, and the balance with other constituent units is easily achieved by setting it to the upper limit or lower.

In the resist composition of the present embodiment, the component (A) preferably contains the polymer compound (A1) having the constituent unit (a1).

The component (A1) contained in the resist composition may be used alone or in combination of two or more.

The polymer compound (hereinafter also referred to as "(A1-1) component)") having a repeating structure of a constituent unit (a1) and a constituent unit (a2), and a constituent unit (a1) are preferable as the component (A1). A polymer compound having a repeating structure of a constituent unit (st) (hereinafter also referred to as "(A1-2) component)".

Specific examples of the component (A1) include a polymer compound composed of a repeating structure of a constituent unit (a1) and a constituent unit (a2); a polymer compound composed of a repeating structure of a unit (a1), a constituent unit (a2), and a constituent unit (a9); a polymer compound composed of a repeating structure of a constituent unit (a1) and a constituent unit (st); a polymer compound composed of a repeating structure of a constituent unit (a1), a constituent unit (st), and a constituent unit (a9); a constituent unit (a1), a constituent unit (a2), a constituent unit (st), and a constituent unit (a9) a polymer compound or the like composed of a repeating structure.

Further, as the component (A), it is also preferred to use the component (A1-1) and the component (A1-2).

The ratio (mass ratio) of the component (A1-1) to the component (A1-2) is preferably (A1-1) component / (A1-2) component = 1/9 to 9/1, more preferably 3/. 7~7/3, and more preferably 5/5.

The mass average molecular weight (Mw) of the component (A1) (based on the polystyrene conversion standard of gel permeation chromatography (GPC)) is not particularly limited, but is preferably about 1,000 to 500,000, more preferably about 3,000 to 50,000.

When the Mw of the component (A1) is at most the above upper limit of the range, the solubility in the resist solvent is sufficient as a resist, and when it is more preferably the lower limit or more of the range, Good dry etch resistance or resist pattern cross-sectional shape.

The degree of dispersion (Mw/Mn) of the component (A1) is not particularly limited, but is preferably about 1.0 to 4.0, more preferably about 1.0 to 3.0, and particularly preferably about 1.5 to 2.5. Further, Mn represents a number average molecular weight.

The ratio of the component (A1) in the component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, and still more preferably 75% by mass or more, based on the total mass of the component (A). It can also be 100% by mass. The ratio In the case of 25% by mass or more, it is easy to form a resist pattern having excellent sensitivities such as high sensitivity or improvement in roughness. Such an effect is remarkable particularly in lithography performed by electron beam or EUV.

(A1) component manufacturing method:

The component (A1) can be added to a polymerization solvent by, for example, azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobisisobutyric acid, by dissolving a monomer derived from each constituent unit in a polymerization solvent. A radical polymerization initiator such as an ester (for example, V-601 or the like) is produced by polymerization. Further, in the polymerization, a chain transfer agent such as HS-CH ₂ -CH ₂ -CH ₂ -C(CF ₃ ) ₂ -OH may be used in combination, and -C(CF ₃ ) ₂ - may be introduced at the end. OH group. As described above, the copolymer of a hydroxyalkyl group in which a part of a hydrogen atom introduced into an alkyl group is substituted with a fluorine atom is effective in reducing the development defect or reducing the LER (line edge roughness: unevenness of the line side wall).

In the resist composition of the present embodiment, the component (A) may be used alone or in combination of two or more.

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

<(B1) component>

The resist composition of the present embodiment contains a compound represented by the following formula (b1) (component (B1)).

^Wherein R ^b1 represents an aromatic ring having an electron attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b10 (except that the aforementioned aromatic ring is a benzene ring) In time, the electron-attracting group is bonded to at least one of the benzene rings. R ^b10 represents an alkyl group, a fluorinated alkyl group or an aryl group. R ^b21 and R ^b22 each independently represent an aromatic ring which may have an electron attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b20 . R ^b20 represents an alkyl group, a fluorinated alkyl group or an aryl group. Z represents a sulfur atom, an oxygen atom, a carbonyl group or a single bond. R ^b1 and R ^b21 may also be bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula. R ^b1 and R ^b22 may also be bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula. X ^- represents a relative anion (except BF ₄ ^- except).

The cation part of the component (B1)

In the above formula (b1), R ^b1 represents an aromatic ring having an electron attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b10 (except for the aforementioned aromatic ring) In the case of a benzene ring, the electron-attracting group is bonded to at least one of the benzene rings.

The aromatic ring in R ^b1 is not particularly limited as long as it has a ring conjugated system of 4 n + 2 π electrons, and may be a monocyclic ring or a polycyclic ring. The carbon number of the aromatic ring is preferably from 5 to 30, more preferably from 5 to 20, still more preferably from 6 to 15, and particularly preferably from 6 to 12.

Examples of R ^b1 include a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, an anthracene ring or a phenanthrene ring; and preferably one or more are removed from the benzene ring or the naphthalene ring. A group derived from a hydrogen atom; more preferably a group obtained by removing one or more hydrogen atoms from the benzene ring.

In the R ^b1 -SO ₂ R ^b10 of R ^b10 represents an alkyl group, a fluorinated alkyl or aryl group.

The alkyl group in R ^b10 may, for example, be an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms.

As R ^b10 in the fluorinated alkyl group include a part of hydrogen atoms of the "alkyl group R ^b10 in the" all or the group substituted by fluorine atoms.

The aryl group in R ^b10 may be the same as R ^b1 .

The electron attracting group of the aromatic ring in R ^b1 is a group of fluorine atoms, trifluoromethyl groups, nitro groups, cyano groups and -SO ₂ R ^b10 , especially fluorine atoms and trifluoromethyl groups. The base is good.

The aromatic ring in R ^b1 has one or more kinds of electron attracting groups selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b10 , and the electron attracting group is aromatic The bonding position of the ring is not limited except for the case where the aromatic ring in R ^b1 is a benzene ring.

The number of the electron attracting groups which are bonded to the aromatic ring in R ^b1 may be one or two or more. When a plurality of the above electron attracting groups are bonded to the aromatic ring, the plurality of the electron attracting groups may be the same or different.

However, when the aromatic ring in R ^b1 is a benzene ring, the electron-attracting group is bonded to at least one of the benzene rings. The electron attracting group may be bonded to the meta position of both of the benzene rings. Further, in addition to the position between the benzene rings, the electron attracting group may be bonded to one or both of the ortho and para positions of the benzene ring.

The aromatic ring in R ^b1 is such that when the electron attracting group is bonded to the meta term benzene ring, the (B1) component is not easily hindered compared to the benzene ring in which the electron attracting group is not bonded to the meta position. Decomposition occurs in the composition of the agent, and the stability is excellent over time.

When R ^b1 is an aromatic ring other than a benzene ring, the bonding position of the electron attracting group to the aromatic ring is preferably not bonded by the sulfur atom (S) in the formula (b1) from the viewpoint of lithographic characteristics. Adjacent carbon atoms (position 2) of a carbon atom (defined as 1 position).

The aromatic ring in R ^b1 may have a substituent other than the above electron attracting group. Examples of the substituent other than the electron-attracting group include an alkyl group having 1 to 5 carbon atoms.

In the above formula (b1), R ^b21 and R ^b22 each independently represent an electron attracting group which may be selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b20 . Aromatic ring.

Examples of the aromatic ring in R ^b21 and R ^b22 include a heterocyclic ring structure which can be formed by R ^b21 and R ^b22 and a sulfur atom (S) in the formula (b1).

R ^b21 and R ^b22 in the -SO ₂ R ^b20 of R ^b20, represent an alkyl, aryl or fluorinated alkyl group include the same as those of the aforementioned R ^b10.

In the above formula (b1), Z represents a sulfur atom, an oxygen atom, a carbonyl group or a single bond. Among these, as Z, a single bond is preferred.

In the above formula (b1), R ^b1 and R ^b21 may be bonded via a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula.

Further, R ^b1 and R ^b22 may be bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula.

The preferred cationic portion of the component (B1) includes a cation represented by the following chemical formula (b1-c).

[wherein, Z represents a sulfur atom, an oxygen atom, a carbonyl group or a single bond. R ^b01 represents an electron attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b10 . When a plurality of R ^b01 are present in the formula (b1-c), the ones may be the same or different from each other. R ^b02 is an alkyl group having 1 to 5 carbon atoms. When a plurality of R ^b02 are present in the formula (b1-c), the ones may be the same or different from each other. n _b1 is an integer of 0 or 1 to 4. n _b3 and n _b5 are each independently 0 or an integer of 1 to 5. n _b2 is an integer of 0 or 1 to 4. n _b4 and n _b6 are each independently 0 or an integer of 1 to 5. However, 0≦n _b1 +n _b2 ≦4, 0≦n _b3 +n _b4 ≦5,0 ≦n _b5 +n _b6 ≦5].

In the above formula (b1-c), among the sulfur atom, the oxygen atom, the carbonyl group or the single bond, Z is preferably a single bond.

The electron attracting group in R ^b01 is preferably a fluorine atom or a trifluoromethyl group among a group of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group and -SO ₂ R ^b10 .

R ^{b02 is} preferably a methyl group or an ethyl group among the alkyl groups having 1 to 5 carbon atoms.

n _b1 , preferably 0 or 1.

n _b3 and n _b5 are preferably 0, 1, or 2, respectively; more preferably 0.

n _{b2 is} preferably 0 or 1, more preferably 0.

n _b4 and n _b6 are preferably 0, 1, or 2, respectively; more preferably 0.

Specific examples of the cation portion represented by the formula (b1-c) are described below.

Anion part of ≪(B1) component≫

In the above formula (b1), X ^- represents a relative anion (except for BF ₄ ^- ).

As X ^-, is not particularly limited, and the anion portion may be suitably used as the acid-generating agent component with the resist composition of the known anion.

For example, examples of X ^- include an anion represented by the following formula (b1-a1), an anion represented by the formula (b1-a2), or an anion represented by the formula (b1-a3).

[In the formula, R ¹⁰¹ and R ¹⁰⁴ to R ¹⁰⁸ are each independently a ring-form group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. R ¹⁰⁴ and R ¹⁰⁵ may also be bonded to each other to form a ring. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. V ¹⁰¹ to V ¹⁰³ are each independently a single bond, an alkylene group or a fluorinated alkyl group. L ¹⁰¹ ~ L ¹⁰² are each independently a single bond or an oxygen atom. L ¹⁰³ ~ L ¹⁰⁵ are each independently a single bond, -CO- or -SO ₂ -].

. Anion represented by the formula (b1-a1)

In the formula (b1-a1), R ¹⁰¹ is a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent.

a cyclic group which may have a substituent:

The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group which does not have aromaticity. Further, the aliphatic hydrocarbon group may be saturated or not Saturated, usually preferably saturated.

The aromatic hydrocarbon group in R ¹⁰¹ is a hydrocarbon group having an aromatic ring. The carbon number of the aromatic hydrocarbon group is preferably from 3 to 30, more preferably from 5 to 30, still more preferably from 5 to 20, particularly preferably from 6 to 15, most preferably from 6 to 10. However, the carbon number does not include the carbon number in the substituent.

Specific examples of the aromatic ring of the aromatic hydrocarbon group in R ¹⁰¹ include benzene, anthracene, naphthalene, anthracene, phenanthrene, biphenyl, or an aromatic group in which one of the carbon atoms constituting the aromatic ring is substituted with a hetero atom. Heterocyclic and the like. Examples of the hetero atom in the aromatic hetero ring include an oxygen atom, a sulfur atom, and a nitrogen atom.

Specific examples of the aromatic hydrocarbon group in R ¹⁰¹ include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, a phenyl group or a naphthyl group); and one hydrogen atom of the above aromatic ring An alkyl group substituted with an alkyl group (for example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) Base, etc.). The carbon number of the alkylene group (alkyl chain in the arylalkyl group) is preferably from 1 to 4, more preferably from 1 to 2, particularly preferably 1.

The cyclic aliphatic hydrocarbon group in R ¹⁰¹ may, for example, be an aliphatic hydrocarbon group containing a ring in the structure.

The aliphatic hydrocarbon group containing a ring in the structure includes an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group bonded to a linear or branched aliphatic group. The group derived from the terminal of the hydrocarbon group or the alicyclic hydrocarbon group is present in the group in the middle of the linear or branched aliphatic hydrocarbon group.

The alicyclic hydrocarbon group preferably has a carbon number of from 3 to 20, more preferably from 3 to 12.

The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably a carbon number of 3 to 6, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably one obtained by removing one or more hydrogen atoms from the polycycloalkane, and the polycycloalkane is preferably a carbon number of 7 to 30. In particular, the polycycloalkane is more preferably a polycyclic alkane having a polycyclic skeleton of a crosslinked ring system such as adamantane, norbornane, isodecane, tricyclodecane or tetracyclododecane; A polycyclic alkane having a polycyclic skeleton having a condensed ring system such as a cyclic group of a steroid skeleton.

In particular, the cyclic aliphatic hydrocarbon group in R ¹⁰¹ is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or a polycycloalkane; more preferably, one hydrogen atom is removed from the polycycloalkane. And the base; especially good is adamantyl, thiol group; the best is adamantyl.

The linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group has a carbon number of preferably 1 to 10, more preferably 1 to 6, more preferably 1 to 4, most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkyl group, and specific examples thereof include a methylene group [-CH ₂ -], an exoethyl group [-(CH ₂ ) ₂ -], and a Sanya. Methyl [-(CH ₂ ) ₃ -], tetramethylene [-(CH ₂ ) ₄ -], pentamethylene [-(CH ₂ ) ₅ -], and the like.

The branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group has a carbon number of preferably 2 to 10, more preferably 3 to 6, more preferably 3 or 4, most preferably 3. The branched aliphatic hydrocarbon group is preferably a branched alkyl group, and specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) Alkyl methylene groups of ₂ - , -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -, etc. ;-CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C( _{CH 2 CH 3) 2 -CH 2} - , etc. extending ethyl _{group; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - , etc. trimethylene group; -CH (CH ₃ ) an alkylalkylene group such as an alkyltetramethylene group such as CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - or the like. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Further, the cyclic hydrocarbon group in R ¹⁰¹ may contain a hetero atom as in the case of a hetero ring or the like. Specific examples thereof include a lactone-containing cyclic group represented by the above formula (a2-r-1) to (a2-r-7), and the above formula (a5-r-1) to (a5-r). -4) a ring-form group containing -SO ₂ - and a heterocyclic group represented by the other chemical formulas (r-hr-1) to (r-hr-16), respectively.

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

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

The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms; more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group or an n-butoxy group. Tert-butoxy; most preferred is methoxy, ethoxy.

The halogen atom as a substituent may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom.

Examples of the halogenated alkyl group as a substituent include an alkyl group having 1 to 5 carbon atoms. A group obtained by partially or completely replacing one of hydrogen atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group with the above halogen atom.

The carbonyl group as a substituent is a group substituted with a methylene group (-CH ₂ -) constituting a cyclic hydrocarbon group.

a chain-like alkyl group which may have a substituent:

The chain alkyl group of R ¹⁰¹ may be any of a linear chain or a branched chain.

The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, most preferably 1 to 10 carbon atoms. Specific examples thereof include 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 decyl group, a decyl group, an undecyl group, a dodecyl group, and a tridecyl group. , isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, twentieth Monoalkyl, behenyl or the like.

The alkyl group having a branched chain shape preferably has a carbon number of 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Specifically, for example, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and the like.

A chain-like alkenyl group which may have a substituent:

The chain-like alkenyl group of R ¹⁰¹ may be any of a linear chain or a branched chain, and the carbon number is preferably 2 to 10, more preferably 2 to 5, still more preferably 2 to 4, and particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butenyl group. Examples of the branched alkenyl group include 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, and 2-methylpropenyl group.

The chain-like alkenyl group is preferably a linear alkenyl group among the above; more preferably a vinyl group or a propylene group; and particularly preferably a vinyl group.

Examples of the substituent in the chain alkyl group or alkenyl group of R ¹⁰¹ include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amine group, and a ring group in the above R ¹⁰¹ . .

Among the above, R ^{101 is} particularly preferably a cyclic group which may have a substituent; more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, it is preferably a group obtained by removing one or more hydrogen atoms from a phenyl group, a naphthyl group or a polycycloalkane; and the above formula (a2-r-1) to (a2-r-7) The cyclic group containing a lactone, and the ring group containing -SO ₂ - represented by the above formula (a5-r-1) to (a5-r-4), respectively.

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

When ^Y101 is a divalent linking group containing an oxygen atom, the ^Y101 may further contain an atom other than an oxygen atom. Examples of the atom other than the oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, and a nitrogen atom.

Examples of the divalent linking group containing an oxygen atom include an oxygen atom (ether bond: -O-), an ester bond (-C(=O)-O-), and an oxycarbonyl group (-OC(=O)-). a non-hydrocarbon-containing oxygen atom such as a guanamine bond (-C(=O)-NH-), a carbonyl group (-C(=O)-), or a carbonate bond (-OC(=O)-O-) a linking group; a combination of a non-hydrocarbon-based linking group containing an oxygen atom and an alkylene group. Further, a sulfonyl group (-SO ₂ -) may be further bonded to the combination. The divalent linking group containing an oxygen atom may, for example, be a linking group represented by the following general formula (y-al-1) to (y-al-7).

[In the formula, V' ¹⁰¹ is a single bond or an alkylene group having 1 to 5 carbon atoms, and V' ¹⁰² is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms].

The divalent saturated hydrocarbon group in V' ¹⁰² is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms.

As V ^'101 and V' ¹⁰² in the alkylene may be straight-chain alkylene group may also be the extension of the branched chain alkyl group, preferably straight chain alkylene of.

Examples of the alkylene group in V' ¹⁰¹ and V' ¹⁰² include a methylene group [-CH ₂ -]; -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C. (CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - or the like Methyl group; exoethyl [-CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ - , -CH(CH ₂ CH ₃ )CH ₂ - or the like alkyl group ethyl; trimethylene (n-propyl) [-CH ₂ CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ - or the like alkyl trimethylene; tetramethylene [-CH ₂ CH ₂ CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - or the like alkyltetramethylene; pentamethylene [-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -].

Further, a methylene group of a part of the alkylene group in V' ¹⁰¹ or V' ¹⁰² may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The aliphatic cyclic group is preferably a cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group or polycyclic aliphatic hydrocarbon group) of Ra' ^{3 in} the above formula (a1-r-1). A divalent group obtained by removing one hydrogen atom; more preferably a cyclohexyl group, a 1,5-adamantyl group or a 2,6-adamantyl group.

Y ^{101 is} preferably a divalent linking group containing an ester bond or a divalent linking group containing an ether bond; more preferably, the above formula (y-al-1) to (y-al-5) are respectively linked. base.

In the formula (b1-a1), V ¹⁰¹ is a single bond, an alkylene group or a fluorinated alkyl group. The alkylene group or the fluorinated alkyl group in V ¹⁰¹ is preferably a carbon number of 1 to 4. ¹⁰¹ V as in the fluorinated alkylene, V may include a portion of hydrogen atoms in the alkylene group of ¹⁰¹ or all substituted by fluorine atoms of the group. Among them, V ^{101 is} preferably a single bond or a fluorinated alkyl group having 1 to 4 carbon atoms.

In the formula (b1-a1), R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R ^{102 is} preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom.

Specific examples of the anion moiety represented by the above formula (b1-a1) include, for example, a single bond of Y ¹⁰¹ , and a fluorinated alkylsulfonic acid such as a trifluoromethanesulfonate anion or a perfluorobutanesulfonate anion. When the ester ¹⁰¹ is a divalent linking group containing an oxygen atom, an anion represented by any one of the following formulas (an-1) to (an-3) may be mentioned.

[wherein R" ¹⁰¹ is an aliphatic cyclic group which may have a substituent, a group represented by the above formula (r-hr-1) to (r-hr-6), or a chain which may have a substituent An alkyl group; R" ¹⁰² is an aliphatic cyclic group which may have a substituent, a cyclic group containing a lactone represented by the above formula (a2-r-1) to (a2-r-7), or the aforementioned The formula (a5-r-1) to (a5-r-4) respectively represent a ring-form group containing -SO ₂ -; R" ¹⁰³ is an aromatic ring group which may have a substituent, and a fat which may have a substituent a cyclic group-based group or a chain-like alkenyl group which may have a substituent; the v" system is independently an integer of 0 to 3, and the q" system is independently an integer of 1 to 20, and t" is 1 to 3 Integer, n" is 0 or 1].

An aliphatic cyclic group which may have a substituent of R" ¹⁰¹ , R" ¹⁰² and R" ¹⁰³ , and is preferably exemplified as the cyclic aliphatic hydrocarbon group in the above ^R101 . The substituent is the same as the substituent of the cyclic aliphatic hydrocarbon group which may be substituted for R ¹⁰¹ .

The aromatic cyclic group which may have a substituent in R" ¹⁰³ , preferably exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in the above R ^101. As the above substituent, a substitutable R ¹⁰¹ may be mentioned. The substituent of the aromatic hydrocarbon group in the same is the same.

A chain-like alkyl group which may have a substituent in R" ¹⁰¹ , preferably a group exemplified as the chain-like alkyl group in the above R ^101. A chain-like alkenyl group which may have a substituent in R" ¹⁰³ It is preferably exemplified as the chain-like alkenyl group in the above R ¹⁰¹ .

. Anion represented by the formula (b1-a2)

In the formula (b1-a2), R ¹⁰⁴ and R ¹⁰⁵ are each independently a ring group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. The same as R ¹⁰¹ in the formula (b1-a1) can be listed separately. However, R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring.

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

The number of carbon atoms of the chain alkyl group is preferably from 1 to 10, more preferably from 1 to 7, and more preferably from 1 to 3. The carbon number of the chain-like alkyl group of R ¹⁰⁴ and R ¹⁰⁵ is preferably in the range of the above carbon number because the solubility in the solvent for the resist is also good. Further, among the chain-like alkyl groups of R ¹⁰⁴ and R ¹⁰⁵ , the more the number of hydrogen atoms substituted by fluorine atoms, the stronger the strength of the acid, and the transparency to high-energy light or electron beams of 200 nm or less It is better to improve. The proportion of the fluorine atom in the chain-like alkyl group, that is, the fluorination ratio, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms. .

In the formula (b1-a2), V ¹⁰² and V ¹⁰³ are each independently a single bond, an alkylene group or a fluorinated alkyl group, and each of them is the same as V ¹⁰¹ in the formula (b1-a1).

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

. Anion represented by the formula (b1-a3)

In the formula (b1-a3), R ¹⁰⁶ to R ¹⁰⁸ are each independently a ring group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. The same as R ¹⁰¹ in the formula (b1-a1) can be ^cited .

In the formula (b1-a3), L ¹⁰³ to L ¹⁰⁵ are each independently a single bond, -CO- or -SO ₂ -.

In the above formula (b1), X ^- may also be a halogen anion. Here, examples of the halogen anion include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion.

Among the above, the anion portion of the component (B1) is preferably an anion represented by the formula (b1-a1). In particular, the anion represented by any one of the above formulas (an-1) to (an-3) is more preferably, and more preferably expressed by any of the formula (an-1) or (an-2). Anion.

Specific examples of the suitable (B1) components are listed below.

In the resist composition of the present embodiment, the component (B1) may be used alone or in combination of two or more.

In the resist composition of the present embodiment, the content of the component (B1) is preferably from 1 to 80 parts by mass, more preferably from 1 to 50 parts by mass, even more preferably 100 parts by mass of the component (A). It is 1 to 30 parts by mass.

When the content of the component (B1) is at least the above-mentioned lower limit, the lithography characteristics of sensitivity, CDU, pattern collapse, resolution, LWR (line width), shape, etc., when the resist pattern is formed Will be more improved. On the other hand, when it is a preferable upper limit or less, when the components of the resist composition are dissolved in an organic solvent, a uniform solution is easily obtained, and the storage stability as a resist composition is further improved.

<arbitrary component>

The resist composition of the present embodiment may further contain components (optional components) other than the components (A) and (B1).

Examples of the optional component include (B2) component, (D) component, (E) component, (F) component, and (S) component shown below.

≪(B2) component: acid generator component ≫

The resist composition of the present embodiment may contain an acid generator component other than the component (B1) (hereinafter referred to as "(B2) component") within a range that does not impair the effects of the present invention.

The component (B2) is not particularly limited, and those which have hitherto been used as an acid generator for a chemically amplified resist composition can be used.

Examples of such an acid generator include a phosphonium salt generator such as a phosphonium salt or a phosphonium salt; an oxime sulfonate acid generator; a dialkyl or bisarylsulfonyldiazomethane, poly (double) A diazomethane acid generator such as a sulfonyl group, a diazomethane or the like; a nitrobenzyl sulfonate acid generator, a sulfonate ester acid generator, a diterpene acid generator, and the like.

The guanidine-based acid generator may, for example, be a compound represented by the following formula (b-1) (hereinafter also referred to as "(b-1) component") or a compound represented by the formula (b-2) (hereinafter Also known as "(b-2) component") or a compound represented by the general formula (b-3) (hereinafter also referred to as "(b-3) component").

[In the formula, R ¹⁰¹ and R ¹⁰⁴ to R ¹⁰⁸ are each independently a ring-form group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. R ¹⁰⁴ and R ¹⁰⁵ may also be bonded to each other to form a ring. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. V ¹⁰¹ to V ¹⁰³ are each independently a single bond, an alkylene group or a fluorinated alkyl group. L ¹⁰¹ ~ L ¹⁰² are each independently a single bond or an oxygen atom. L ¹⁰³ ~ L ¹⁰⁵ are each independently a single bond, -CO- or -SO ₂ -. m is an integer of 1 or more, and M' ^m+ is an m-valent ruthenium cation].

{anion}

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

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

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

{cation part}

In the above formula (b-1), formula (b-2), and formula (b-3), M' ^m+ represents a m-valent phosphonium cation, and is preferably a phosphonium cation or a phosphonium cation.

m is an integer of 1 or more.

The preferred cationic moiety ((M' ^m+ ) _1/m ) is an organic cation represented by the following general formulae (ca-1) to (ca-4).

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

Examples of the aryl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferred.

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

The number of carbon atoms in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² is preferably 2 to 10.

Examples of the substituent which R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amine group, an aryl group, and the following formula (ca- R-1)~(ca-r-7) respectively represent the basis.

[In the formula, R' ²⁰¹ is each independently a hydrogen atom, a ring group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent.

R ^'201 may be the group having a cyclic substituent, the alkyl group may have a substituent group of the chain, or a chain of the alkenyl substituent group, include R as in the above formula (b1-a1) ¹⁰¹ In addition, as the cyclic alkyl group which may have a substituent or the chain-type alkyl group which may have a substituent, the same is the same as the acid dissociable group represented by the above formula (a1-r-2).

When R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ , and R ²¹¹ to R ^{212 are} bonded to each other and form a ring together with a sulfur atom in the formula, a hetero atom such as a sulfur atom, an oxygen atom or a nitrogen atom may be interposed; or a functional group such as a carbonyl group, -SO-, -SO ₂ -, -SO ₃ -, -COO-, -CONH- or -N(R _N )- (the R _N is an alkyl group having 1 to 5 carbon atoms) Bonding. The ring formed includes one ring of a sulfur atom in the ring skeleton in the ring skeleton, and the sulfur atom preferably contains a ring of 3 to 10 members, particularly preferably a ring of 5 to 7 members. Specific examples of the ring formed include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, and a thiophene ring. Ring, morphine ring, tetrahydrothiophene ring, tetrahydrothiopyranium ring, and the like.

R ²⁰⁸ to R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. When it is an alkyl group, it may be bonded to each other to form a ring. .

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

The aryl group in R ²¹⁰ may, for example, be an unsubstituted aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group.

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

As the alkenyl group in R ²¹⁰ , the carbon number is preferably from 2 to 10.

The -SO ₂ -containing cyclic group which may have a substituent in R ²¹⁰ is preferably a "polycyclic group containing -SO ₂ -", more preferably represented by the above formula (a5-r-1) The basis.

Y ²⁰¹ independently represents an extended aryl group, an alkylene group or an extended alkenyl group.

The aryl group in Y ²⁰¹ may be a group obtained by removing one hydrogen atom from the aryl group exemplified as the aromatic hydrocarbon group in R ¹⁰¹ in the above formula (b1-a1).

The alkylene group and the alkenyl group in Y ²⁰¹ may be exemplified by the removal of one hydrogen atom from the group exemplified as the chain-like alkyl group or the chain-like alkenyl group in R ¹⁰¹ in the above formula (b1-a1). And the basis.

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

W ²⁰¹ is a (x+1) valence, that is, a divalent or trivalent linkage.

The divalent linking group in W ²⁰¹ is preferably a divalent hydrocarbon group which may have a substituent, and a divalent hydrocarbon group which may have a substituent similar to Ya ²¹ in the above formula (a2-1). The divalent linking group in W ²⁰¹ may be any of a linear chain, a branched chain, and a ring, and is preferably a ring. In particular, it is preferred to combine two carbonyl groups at both ends of the aryl group. Examples of the aryl group include a phenyl group and a naphthyl group, and particularly preferably a phenyl group.

3 as W ²⁰¹ of the divalent linking group include the self-W ²⁰¹ in the divalent linking group obtained by removing one hydrogen atom of the group, the divalent linking group to the further group is bonded, the divalent linking group of Wait. As the trivalent linking group in W ²⁰¹ , a group having two carbonyl groups bonded to an extended aryl group is preferred.

Specific examples of the cation represented by the above formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-71).

[wherein, g1, g2, and g3 represent the number of repetitions, g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 0 to 20].

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

Specific examples of the cation represented by the above formula (ca-2) include a diphenylphosphonium cation and a bis(4-tert-butylphenyl)phosphonium cation.

Specific examples of the cation represented by the above formula (ca-3) include cations represented by the following formulae (ca-3-1) to (ca-3-6).

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

Among the above, the cation moiety ((M' ^m+ ) _1/m ) is preferably a cation represented by the formula (ca-1), more preferably a formula (ca-1-1) to (ca-1-71). ) cations are indicated separately.

In the resist composition of the present embodiment, the component (B2) may be used alone or in combination of two or more.

When the resist composition contains the component (B2), the content of the component (B2) in the resist composition is preferably 80 parts by mass or less, more preferably 1 to 50, per 100 parts by mass of the component (A). The mass fraction is more preferably 1 to 30 parts by mass.

By setting the content of the component (B2) to the above range, the pattern formation system proceeds sufficiently. Further, when the respective components of the resist composition are dissolved in an organic solvent, a uniform solution is easily obtained, and the stability of the resist composition is good, which is preferable.

≪(D) component: acid diffusion control agent ≫

The resist composition of the present embodiment may further contain an acid diffusion controlling agent component (hereinafter referred to as "(D) component") in addition to the component (A) and the component (B1). The component (D) acts as a quencher (acid diffusion controlling agent) which traps an acid generated in the resist composition by exposure.

The component (D) is, for example, a photodisintegrable base (D1) (hereinafter referred to as "(D1) component)) which is decomposed by exposure, loses acid diffusion controllability, and does not correspond to the component (D1). The nitrogen-containing organic compound (D2) (hereinafter referred to as "(D2) component") or the like.

. About (D1) ingredients

By forming a resist composition containing the component (D1), when the resist pattern is formed, the contrast between the exposed portion and the unexposed portion of the resist film can be further improved.

The component (D1) is not particularly limited as long as it is decomposed by exposure and loses acid diffusion controllability, and is preferably selected from compounds represented by the following formula (d1-1) (hereinafter referred to as "(d1) -1) Component"), a compound represented by the following formula (d1-2) (hereinafter referred to as "(d1-2) component") and a compound represented by the following formula (d1-3) (hereinafter referred to as " (d1-3) Component ") One or more compounds of the group formed.

(d1-1)~(d1-3) component decomposes in the exposed portion of the resist film and loses acid diffusion controllability (alkaline), so it does not act as a quencher, and is not exposed to the resist film. It acts as a quencher.

[wherein, Rd ¹ to Rd ⁴ are a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent. However, a fluorine atom is not bonded to a carbon atom adjacent to the S atom in Rd ² in the formula (d1-2). Yd ¹ is a single bond or a divalent linking group. m is an integer of 1 or more, and M ^m+ is each independently an m-valent organic cation].

{(d1-1) component} . . Anion

Formula (D1-1) in, Rd ¹ is a cyclic group may have a substituent group, the alkyl group may have a substituent group of the chain, or a chain of the alkenyl substituent group, include those of the formula ( R ¹⁰¹ in b1-a1) is the same.

Among these, as the Rd ¹ , an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkyl group which may have a substituent is preferable. Examples of the substituent which these groups may have include a hydroxyl group, a pendant oxy group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, and the above formula (a2-r-1) to (a2-r-7). Represented by a lactone-containing ring group, an ether bond, an ester bond, or a combination thereof. When an ether bond or an ester bond is contained as a substituent, an alkyl group may be interposed, and the substituent at this time is preferably a linking group represented by the above formula (y-al-1) to (y-al-5). .

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

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

The chain-like alkyl group preferably has 1 to 10 carbon atoms, and specific examples thereof include 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 decyl group, and an anthracene group. a linear alkyl group such as a radical; 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 a branched alkyl group such as methylpentyl, 2-methylpentyl, 3-methylpentyl or 4-methylpentyl.

When the chain-like alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the carbon number of the fluorinated alkyl group is preferably from 1 to 11, more preferably from 1 to 8, more preferably It is 1~4. The fluorinated alkyl group may also contain atoms other than a fluorine atom. Examples of the atom other than the fluorine atom include an oxygen atom, a sulfur atom, and a nitrogen atom.

As all of the hydrogen atoms Rd ^1, it is preferably a part or all of the hydrogen atoms constituting the linear alkyl group substituted by a fluorine atom of the fluorinated alkyl group, particularly preferably a linear alkyl group composed of a fluorine atom is substituted by the A fluorinated alkyl group (linear perfluoroalkyl group).

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

. . Cationic part

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

The organic cation of M ^m+ is preferably the same as the cation represented by the above formula (ca-1) to (ca-4), more preferably the cation represented by the above formula (ca-1), and more preferably It is a cation represented by the above formula (ca-1-1) to (ca-1-71), respectively.

(d1-1) The components may be used alone or in combination of two or more. use.

{(d1-2) ingredient} . . Anion

In the formula (d1-2), R ² is a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and may be exemplified by the above formula (b1) R ^{101 in} -a1) is the same.

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

As Rd ² , a chain-like alkyl group which may have a substituent or an aliphatic ring group which may have a substituent is preferable. The chain alkyl group preferably has a carbon number of 1 to 10, more preferably 3 to 10. The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isodecane, tricyclodecane or tetracyclododecane (may have a substituent) ); a base obtained by removing one or more hydrogen atoms from camphor or the like.

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

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

. . Cationic part

In the formula (d1-2), M ^m+ is an m-valent organic cation which is the same as M ^m+ in the above formula (d1-1).

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

{(d1-3) ingredient} . . Anion

In the formula (d1-3), R ³ is a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and is exemplified by the above formula (b1) The same as R ^{101 in} -a1) is preferably a cyclic group containing a fluorine atom, a chain alkyl group, or a chain-like alkenyl group. Among them, a fluorinated alkyl group is preferred, and a fluorinated alkyl group of the above Rd ¹ is more preferred.

In the formula (d1-3), R ⁴ is a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and is exemplified by the above formula (b1) R ^{101 in} -a1) is the same.

Among them, an alkyl group, an alkoxy group, an alkenyl group or a cyclic group which may have a substituent is preferred.

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

The alkoxy group in Rd ⁴ is preferably an alkoxy group having 1 to 5 carbon atoms, and the alkoxy group having 1 to 5 carbon atoms, and specific examples thereof include a methoxy group, an ethoxy group, and an n-propoxy group. Base, iso-propoxy, n-butoxy, tert-butoxy. Among them, a methoxy group and an ethoxy group are preferred.

The alkenyl group in Rd ⁴ may be the same as R ¹⁰¹ in the above formula (b1-a1), and is preferably a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group or a 2-methylpropene group. base. These groups may further have a C 1 to 5 alkyl group or a C 1 to 5 halogenated alkyl group as a substituent.

The ring group in Rd ⁴ may be the same as R ¹⁰¹ in the above formula (b1-a1), preferably from cyclopentane, cyclohexane, adamantane, norbornane, isodecane, tricyclic ring. An alicyclic group obtained by removing one or more hydrogen atoms from a cycloalkane such as decane or tetracyclododecane; or an aromatic group such as a phenyl group or a naphthyl group. When Rd ⁴ is an alicyclic group, the lithographic properties are excellent by dissolving the resist composition in an organic solvent well. Further, when Rd ⁴ is an aromatic group, in the lithography using EUV or the like as an exposure light source, the resist composition has excellent light absorption efficiency, and the sensitivity or lithography characteristics are good.

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

The divalent linking group in Yd ¹ is not particularly limited, and examples thereof include a divalent hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group) which may have a substituent, and a divalent linking group containing a hetero atom. These may be the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom which are listed in the description of the divalent linking group in Ya ²¹ in the above formula (a2-1). .

As Yd ¹ , a carbonyl group, an ester bond, a guanamine bond, an alkylene group or a combination thereof is preferred. The alkylene group is more preferably a linear or branched alkyl group, more preferably a methylene group or an ethyl group.

Preferred specific examples of the anion portion of the component (d1-3) are shown below.

. . Cationic part

In the formula (d1-3), M ^m+ is an m-valent organic cation which is the same as M ^m+ in the above formula (d1-1).

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

The component (D1) may be used alone or in combination of two or more of the above components (d1-1) to (d1-3).

When the resist composition contains the component (D1), the content of the component (D1) in the resist composition is preferably 100 parts by mass based on the component (A). 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, still more preferably 1 to 8 parts by mass.

When the content of the component (D1) is preferably at least the lower limit, it is easy to obtain particularly excellent lithographic properties and a resist pattern shape. On the other hand, when it is less than the upper limit, the sensitivity can be favorably maintained, and the throughput is also excellent.

(D1) component manufacturing method:

The method for producing the component (d1-1) and the component (d1-2) is not particularly limited, and it can be produced by a known method.

Further, the method for producing the component (d1-3) is not particularly limited, and is produced, for example, in the same manner as the method described in US2012-0149916.

. About (D2) ingredients

The acid diffusion controlling agent component may contain a nitrogen-containing organic compound component (hereinafter referred to as "(D2) component") which does not correspond to the above (D1) component.

The component (D2) is not particularly limited as long as it functions as an acid diffusion controlling agent and does not correspond to the component (D1), and may be used arbitrarily by a person skilled in the art. Among them, an aliphatic amine is preferred, and particularly preferably a grade 2 aliphatic amine or a tertiary aliphatic amine.

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

The aliphatic amine may, for example, be an amine (alkylamine or alkylolamine) or a cyclic amine obtained by substituting at least one hydrogen atom of ammonia NH ₃ with an alkyl group having 12 or less carbon atoms or a hydroxyalkyl group.

Specific examples of the alkylamine and the alkylolamine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, and n-decylamine; diethylamine; a dialkylamine such as di-n-propylamine, di-n-heptylamine, di-n-octylamine or dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine , tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-decylamine, tri-n-dodecylamine Alkylamines such as trialkylamine; diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, and the like. Among these, a trialkylamine having 5 to 10 carbon atoms is more preferable, and particularly preferably tri-n-pentylamine or tri-n-octylamine.

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

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

The aliphatic polycyclic amine is preferably a carbon number of 6 to 10, and specific examples thereof include 1,5-diazabicyclo[4.3.0]-5-nonene and 1,8-diaza Bicyclo [5.4.0]-7-undecene, hexamethylenetetramine, 1,4-diazabicyclo[2.2.2]octane, and the like.

As other aliphatic amines, ginseng (2-methoxymethoxyethyl)amine, gin {2-(2-methoxyethoxy)ethyl}amine, and {2-(2- Methoxyethoxymethoxy)ethyl}amine, gin {2-(1-methoxyethoxy)ethyl}amine, gin {2-(1-ethoxyethoxy)ethyl }amine, ginseng {2-(1-ethoxypropoxy)ethyl}amine, ginseng [2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triethyl An acid ester or the like is preferably triethanolamine triacetate.

Further, as the component (D2), an aromatic amine can also be used.

Examples of the aromatic amine include 4-dimethylaminopyridine, pyrrole, hydrazine, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, and N-tert- Butoxycarbonylpyrrolidine and the like.

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

When the resist composition contains the component (D2), the component (D2) in the resist composition is usually used in an amount of 0.01 to 5 parts by mass based on 100 parts by mass of the component (A). When it is in the above range, the shape of the resist pattern, the stability over time after exposure, and the like are improved.

≪ (E) component: at least one compound selected from the group consisting of organic carboxylic acids and phosphorus oxyacids and derivatives thereof

The resist composition of the present embodiment may contain an oxyacid selected from an organic carboxylic acid and phosphorus and its derivative for the purpose of preventing deterioration of sensitivity, or improving shape of a resist pattern, stability over time after exposure, and the like. At least one compound (E) (hereinafter referred to as "(E) component") of the group formed by the substance is an optional component.

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

Examples of the oxo acid of phosphorus include phosphoric acid, phosphonic acid, and hypophosphorous acid. Among them, phosphite is preferred.

Examples of the oxo acid-containing derivative of phosphorus include an ester obtained by substituting a hydrogen atom of the above-mentioned oxo acid with a hydrocarbon group, and examples of the hydrocarbon group include carbon. An alkyl group having 1 to 5 carbon atoms and an aryl group having 6 to 15 carbon atoms.

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

Examples of the derivative of the phosphonic acid include phosphonates such as dimethyl phosphonate, di-n-butyl phosphonate, phenyl phosphonate, diphenyl phosphonate, and dibenzyl phosphonate.

Examples of the derivative of hypophosphorous acid include a hypophosphite or phenyl hypophosphite.

In the resist composition of the present embodiment, the component (E) may be used alone or in combination of two or more.

When the resist composition contains the component (E), the content of the component (E) is usually 0.01 to 5 parts by mass based on 100 parts by mass of the component (A).

≪(F) component: fluorine additive component ≫

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

For the component (F), for example, JP-A-2010-002870, JP-A-2010-032994, JP-A-2010-277043, JP-A-2011-13569, and JP-A-2011- The fluorine-containing polymer compound described in Japanese Patent Publication No. 128226.

More specifically, the component (F) is a polymer having a constituent unit (f1) represented by the following formula (f1-1). The polymer is preferably a polymer composed of a constituent unit (f1) represented by the following formula (f1-1). a copolymer of the constituent unit (f1) and the constituent unit (a1); a copolymer of the constituent unit derived from acrylic acid or methacrylic acid and the constituent unit (a1). Here, the constituent unit (a1) which is copolymerized with the constituent unit (f1) is preferably a constituent unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, and is (methyl). a constituent unit derived from 1-methyl-1-adamantyl acrylate.

[In the formula, R is the same as defined above, and Rf ¹⁰² and Rf ¹⁰³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Rf ¹⁰² and Rf ¹⁰³ Can be the same or different. Nf ¹ is an integer of 1 to 5, and Rf ¹⁰¹ is an organic group containing a fluorine atom].

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

In the formula (f1-1), examples of the halogen atom of Rf ¹⁰² and Rf ¹⁰³ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and particularly preferably a fluorine atom. Examples of the alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include the same as the alkyl group having 1 to 5 carbon atoms of R, and a methyl group or an ethyl group is preferred. Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms of Rf ¹⁰² and Rf ¹⁰³ include a group in which one or all of hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a fluorine atom. Among them, Rf ¹⁰² and Rf ^{103 are} preferably a hydrogen atom, a fluorine atom or an alkyl group having 1 to 5 carbon atoms; more preferably a hydrogen atom, a fluorine atom, a methyl group or an ethyl group.

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

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

The hydrocarbon group containing a fluorine atom may be any of a linear chain, a branched chain or a ring, and the carbon number is preferably from 1 to 20, more preferably from 1 to 15, and particularly preferably from 1 to 10.

Further, in the hydrocarbon group containing a fluorine atom, it is preferred that 25% or more of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably 50% or more, to improve the hydrophobicity of the resist film during immersion exposure. Particularly preferred is more than 60% fluorinated.

Wherein, as Rf ¹⁰¹ , a fluorinated hydrocarbon group having a carbon number of 1 to 5 is particularly preferable; particularly preferably a trifluoromethyl group, -CH ₂ -CF ₃ , -CH ₂ -CF ₂ -CF ₃ , -CH (CF _{3 ) 2} , -CH ₂ -CH ₂ -CF ₃ , -CH ₂ -CH ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₃ .

The mass average molecular weight (Mw) of the component (F) (based on polystyrene conversion by gel permeation chromatography) is preferably from 1,000 to 50,000, more preferably from 5,000 to 40,000, most preferably from 10,000 to 30,000. When it is less than or equal to the upper limit of the range, it is sufficient solubility of the solvent for the resist used as a resist, and when it is at least the lower limit of the range, dry etching resistance or resist diagram The shape of the cross section is good.

The degree of dispersion (Mw/Mn) of the component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, most preferably 1.2 to 2.5.

In the resist composition of the present embodiment, the component (F) may be used alone or in combination of two or more.

When the resist composition contains the component (F), the content of the component (F) is usually from 0.5 to 10 parts by mass based on 100 parts by mass of the component (A).

≪(S) component: organic solvent component ≫

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

As the component (S), any component to be used may be dissolved to obtain a homogeneous solution, and any one of those conventionally known as a solvent for a chemically amplified resist composition may be appropriately selected and used.

Examples of the (S) component include lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, and 2- a ketone such as heptanone; a polyhydric alcohol such as ethylene glycol, diethylene glycol, propylene glycol or dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or a compound having an ester bond such as dipropylene glycol monoacetate; a monoalkyl group such as a monomethyl ether, a monoethyl ether, a monopropyl ether or a monobutyl ether of the above polyol or a compound having an ester bond; a derivative of a polyhydric alcohol such as an ether bond-containing compound such as an ether or a monophenyl ether; among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol are preferred. Monomethyl ether (PGME)]; a cyclic ether such as dioxane; or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, acetone An ester of ethyl acetate, methyl methoxypropionate or ethyl ethoxypropionate; anisole, ethylbenzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether An aromatic organic solvent such as phenethyl ether, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, cumene, toluene, xylene, isopropyl toluene or mesitylene; Methyl sulfoxide (DMSO) and the like.

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

Among them, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferred.

Further, it is also preferred to mix a mixed solvent of PGMEA and a polar solvent. The blending ratio (mass ratio) may be appropriately determined in consideration of compatibility between PGMEA and a polar solvent, etc., but is preferably in the range of 1:9 to 9:1, more preferably 2:8 to 8:2. It is better.

More specifically, when blending EL or cyclohexanone as a polar solvent, the mass ratio of PGMEA:EL or cyclohexanone is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Further, when PGME is blended as a polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, still more preferably 3:7 to 7:3. . Further, a mixed solvent of PGMEA, PGME and cyclohexanone is also preferred.

Further, as the component (S), a mixed solvent of at least one selected from PGMEA and EL and γ-butyrolactone is also preferable. At this point, just mix In proportion, the quality of the former and the latter is preferably 70:30~95:5.

The amount of the component (S) to be used is not particularly limited, and is appropriately set depending on the coating film thickness at a concentration that can be applied to a substrate or the like. In general, the (S) component is used in such a manner that the solid content concentration of the resist composition is in the range of 1 to 20% by mass, preferably 2 to 15% by mass.

The resist composition of the present embodiment may further contain a filler additive as appropriate, such as an additive resin, a dissolution inhibitor, a plasticizer, a stabilizer, or a colorant for improving the properties of the resist film. , anti-fog, dyes, etc.

(Resist pattern formation method)

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

As an embodiment of the resist pattern forming method, for example, a resist pattern forming method as described below can be cited.

First, the resist composition of the above embodiment is applied to a support by a spinner or the like, and baked (applicable after baking (PAB)) for 40 to 120 seconds, for example, at a temperature of 80 to 150 ° C. It is preferably 60 to 90 seconds to form a resist film.

Next, the resist film is formed by using an exposure apparatus such as an ArF exposure apparatus, an electron beam drawing apparatus, or an EUV exposure apparatus. After selective exposure such as exposure of a mask of a specific pattern (mask pattern) or direct illumination of an electron beam that does not pass through a mask pattern, for example, baking is performed at a temperature of 80 to 150 ° C (exposure) Post-baking (PEB) treatment is 40 to 120 seconds, preferably 60 to 90 seconds.

Next, the aforementioned resist film is developed. In the case of the alkali development process, the development process is performed using an alkali developer; in the case of a solvent development process, the development process is performed using a developer (organic developer) containing an organic solvent.

After the development treatment, it is preferred to carry out a rinsing treatment. In the case of the alkali developing process, the rinsing treatment is preferably a water rinsing using pure water; in the case of a solvent developing process, the rinsing treatment is preferably a rinsing liquid containing an organic solvent.

In the case of the solvent developing process, the developing solution or the rinsing liquid adhering to the pattern may be removed by supercritical fluid after the development processing or the rinsing treatment.

After the development treatment or after the rinsing treatment, it is dried. Further, the baking treatment (post-baking) may be performed after the development processing as described above.

In this way, a resist pattern can be formed.

The support is not particularly limited, and a conventionally known one may be used, and examples thereof include a substrate for an electronic component or a specific wiring pattern formed thereon. More specifically, a substrate made of a metal such as a germanium wafer, copper, chromium, iron, or aluminum, or a glass substrate or the like can be given. As a material of the wiring pattern, for example, copper, aluminum, nickel, gold, or the like can be used.

Further, as the support, an inorganic or/or organic film may be provided on the substrate as described above. Inorganic antireflection film (Inorganic BARC). The organic film may be an organic film such as an organic antireflection film (organic BARC) or a lower organic film in a multilayer resist method.

Here, the multilayer resist method refers to a resistant pattern in which at least one organic film (lower organic film) and at least one resist film (upper resist film) are formed on a substrate to form an upper resist film. The type of mask is used to pattern the underlying organic film, and it is considered that a high aspect ratio pattern can be formed. That is, according to the multilayer resist method, the desired thickness can be ensured by the underlying organic film, so that the resist film can be thinned and a fine pattern of high aspect ratio can be formed.

In the multilayer resist method, it is basically divided into a method of forming a two-layer structure of an upper resist film and a lower organic film (two-layer resist method), and one or more layers between the upper resist film and the lower organic film. A method of three-layer or more multilayer structure of an intermediate layer (metal thin film or the like) (three-layer resist method).

The wavelength used for the exposure is not particularly limited, and an ArF excimer laser, a KrF excimer laser, an F ₂ excimer laser, an EUV (very ultraviolet ray), a VUV (vacuum ultraviolet ray), an EB (electron beam), an X-ray can be used. It is carried out by radiation such as soft X-rays. The above-mentioned resist composition is useful for KrF excimer laser, ArF excimer laser, EB or EUV, and is more useful as ArF excimer laser, EB or EUV, as EB or EUV. It has a very high usefulness.

The exposure method of the resist film may be a usual exposure (dry exposure) or a liquid immersion exposure (Liquid Immersion Lithography) performed in an inert gas such as air or nitrogen.

Liquid immersion exposure, in advance, the resist film and the lowest position of the exposure device An exposure method in which exposure (immersion exposure) is performed in a state where a solvent having a refractive index greater than the refractive index of air (liquid immersion medium) is filled between the lenses.

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

The solvent having a refractive index greater than the refractive index of air and smaller than the refractive index of the resist film may, for example, be water, a fluorine-based inactive liquid, an anthraquinone solvent, a hydrocarbon solvent or the like.

Specific examples of the fluorine-based inactive liquid include fluorine 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 . The liquid or the like is preferably a boiling point of 70 to 180 ° C, more preferably 80 to 160 ° C. When the fluorine-based inactive liquid has a boiling point in the above range, it is preferable to carry out the removal of the medium for liquid immersion by a simple method after the completion of the exposure.

As the fluorine-based inactive liquid, a perfluoroalkyl compound in which all hydrogen atoms of an alkyl group are substituted with a fluorine atom is particularly preferred. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.

More specifically, examples of the perfluoroalkyl ether compound include perfluoro(2-butyl-tetrahydrofuran) (boiling point: 102° C.), and examples of the perfluoroalkylamine compound include perfluorotributylamine (boiling point). 174 ° C).

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

The alkali developer used for the development treatment in the alkali development process may, for example, be an aqueous solution of 0.1 to 10% by mass of tetramethylammonium hydroxide (TMAH).

The organic solvent contained in the organic developing solution used for the development processing in the solvent development process may be any one of the known organic solvents as long as it can dissolve the component (A) (component (A) before exposure). Specific examples thereof include a ketone solvent, an ester solvent, an alcohol solvent, a nitrile solvent, a guanamine solvent, a polar solvent such as an ether solvent, and a hydrocarbon solvent.

The ketone solvent is an organic solvent containing C-C(=O)-C in the structure. The ester solvent is an organic solvent containing C-C(=O)-O-C in the structure. The alcohol solvent is an organic solvent containing an alcoholic hydroxyl group in the structure. The "alcoholic hydroxyl group" means a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. The nitrile solvent is an organic solvent containing a nitrile group in the structure. The amide-based solvent is an organic solvent containing a guanamine group in the structure. The ether solvent is an organic solvent containing C-O-C in the structure.

Among the organic solvents, there are also organic solvents having a plurality of functional groups which impart a characteristic to each of the above-mentioned respective solvents, and in this case, it is defined to correspond to any solvent type including a functional group of the organic solvent. For example, diethylene glycol monomethyl ether is equivalent to any of an alcohol solvent or an ether solvent in the above classification.

The hydrocarbon solvent is a hydrocarbon solvent which is formed of a halogenated hydrocarbon and which does not have a substituent other than a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom.

The organic solvent contained in the organic developing solution is preferably a polar solvent, and more preferably a ketone solvent, an ester solvent or a nitrile solvent.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, and 2-hexanone. Diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl ketone, acetone acetone, ionone, diacetone alcohol, Ethyl mercaptoate, acetophenone, methylnaphthyl ketone, isophorone, propyl carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone) and the like. Among these, as the ketone solvent, methyl amyl ketone (2-heptanone) is preferred.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, and propylene glycol. Methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate , diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, two Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acid, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, formic acid Ester, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, pyruvic acid Propyl ester, butyl pyruvate, methyl acetate methyl acetate, B Ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methyl propionate Oxy ester, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, and the like. Among these, the ester solvent is preferably butyl acetate.

Examples of the nitrile-based solvent include acetonitrile, propionitrile, valeronitrile, and butyronitrile.

In the organic developer, a known additive may be blended as needed. As such an additive, a surfactant is mentioned, for example. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used. As the surfactant, a nonionic surfactant is preferred; a nonionic fluorine-based surfactant or a nonionic lanthanide surfactant is more preferred.

When the surfactant is blended, the blending amount thereof is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass based on the total amount of the organic developing solution.

The development treatment can be carried out by a known development method, and for example, a method of immersing the support in a developer for a certain period of time (dipping method), and a method of swelling the developer on the surface of the support by a surface tension for a certain period of time (for a certain period of time) Paddle method), a method of spraying a developer on a surface of a support (spray method), and a method of continuously applying a developer while spraying a developer at a constant speed on a support rotating at a constant speed (dynamic dispensing) (dynamic dispense) method).

The organic solvent contained in the rinsing liquid used for the rinsing treatment after the development treatment in the solvent developing process can be, for example, the organic system Among the organic solvents exemplified as the organic solvent used for the liquid solution, those who do not easily dissolve the resist pattern are appropriately used. Usually, at least one solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent is used. Among these, at least one selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent is preferred; more preferably, it is selected from an alcohol solvent and an ester solvent. At least one of them; particularly preferred is an alcohol solvent.

The alcohol solvent used in the rinse liquid is preferably a hydrocarbon having 6 to 8 carbon atoms, and the monohydric alcohol may be any of a linear chain, a branched chain or a cyclic chain. Specific examples thereof include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, and 3-octanol. , 4-octanol, benzyl alcohol, and the like. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferable; more preferably 1-hexanol or 2-hexanol.

These organic solvents may be used alone or in combination of two or more. Further, it may be used by mixing with an organic solvent other than the above or water. However, in consideration of the development property, the blending amount of water in the rinse liquid is preferably 30% by mass or less, more preferably 10% by mass or less, and still more preferably 5% based on the total amount of the rinse liquid. The mass% or less is particularly preferably 3% by mass or less.

In the rinse solution, a known additive may be blended as needed. As such an additive, a surfactant is mentioned, for example. The surfactant is preferably the same as the above, and is preferably a nonionic surfactant; more preferably a nonionic fluorine-based surfactant or a nonionic lanthanide surfactant.

When the surfactant is blended, the blending amount is relative to the entire lotion The amount is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass.

The rinsing treatment (washing treatment) using the rinsing liquid can be carried out by a known rinsing method. As a method of the rinsing treatment, for example, a method of continuously applying a rinsing liquid to a support rotating at a constant speed (spin coating method), and a method of immersing the support in the rinsing liquid for a certain period of time (dipping method) ), a method of spraying a lotion on the surface of the support (spray method), and the like.

The resist composition of the present embodiment described above contains the compound (B1) represented by the formula (b1) as an acid generator component. Therefore, in the resist pattern forming method of the above embodiment, high sensitivity can be achieved while maintaining the lithographic properties such as resolution, thickness improvement, and shape.

The component (B1) has an aromatic ring (R ^b1 ) having a specific electron attracting group. Further, the component (B1) has, in addition to the aromatic ring (R ^b1 ), a thiophene ring composed of two aromatic rings (R ^b21 and R ^b22 ) and a bond between the two aromatic rings (R ^b1 ) and the respective aromatic rings. Multi-ring base. With the component (B1) having such a structure, the production efficiency of acid due to exposure is improved.

Further, the resist composition containing the component (B1) and the substrate component (A) can easily obtain high sensitivity to an exposure light source, and in particular, it is easy to obtain high sensitivity to an EB or EUV light source. Therefore, the resist composition of the present embodiment is particularly suitable as a photosensitive material for lithography for EB or EUV.

(compound)

The compound of the third aspect of the present invention is represented by the following formula (b1) By.

^Wherein R ^b1 represents an aromatic ring having an electron attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b10 (except that the aforementioned aromatic ring is a benzene ring) In time, the electron-attracting group is bonded to at least one of the benzene rings. R ^b10 represents an alkyl group, a fluorinated alkyl group or an aryl group. R ^b21 and R ^b22 each independently represent an aromatic ring which may have an electron attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b20 . R ^b20 represents an alkyl group, a fluorinated alkyl group or an aryl group. Z represents a sulfur atom, an oxygen atom, a carbonyl group or a single bond. R ^b1 and R ^b21 may also be bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula. R ^b1 and R ^b22 may also be bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula. X ^- represents a relative anion (except BF ₄ ^- except).

The compound of the third aspect is the same as the component (B1) in the description of the resist composition of the first aspect.

[Method for producing compound ((B1) component)]

The component (B1) can be produced by a known method.

The production method of the component (B1) includes, for example, a production method including the first to second steps shown below.

The compound used in each step can be used as a commercial one or a synthetic one.

The solvent used in the respective reactions in the first to second steps may be, for example, dichloromethane, dichloroethane, chloroform, tetrahydrofuran or N, as long as the compound used in each step is soluble and does not react with the compound. , N-dimethylformamide, dimethylacetamide, dimethyl hydrazine, acetonitrile, propionitrile, and the like.

. Step 1

In the first step, a reaction liquid containing the precursor compound (III) is obtained by reacting the compound (I) and the compound (II) with TMS-X in a solvent.

The mixing time at the time of the mixing is appropriately set depending on the reactivity of the compounds, the reaction temperature, and the like.

After the reaction liquid was obtained, water was added to the obtained reaction liquid, and the solvent was extracted from the aqueous phase and concentrated to dryness to give Compound (IV).

[wherein, R ^b1 , R ^b21 , R ^b22 and Z are the same as R ^b1 , R ^b21 , R ^b22 and Z in the formula (b1). X _h represents a halogen atom. TMS means trimethyldecylalkyl. X" represents a relative anion].

In the above formula, the halogen atom in X _h may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Examples of the relative anion in X" include Br ^- , Cl ^- , CF ₃ SO ₃ ^- and the like.

. Step 2

In the second step, the target compound (b1-1) (component (B1)) is obtained by mixing the compound (III) in a solvent and the compound (IV) for salt exchange (salt exchange reaction).

The temperature (reaction temperature) at the time of the mixing is preferably about 0 to 100 ° C, more preferably about 0 to 50 ° C.

The mixing time is appropriately set depending on the reactivity of the compounds, the reaction temperature, and the like, and is preferably, for example, 10 minutes or longer and 24 hours or shorter, more preferably 10 minutes or longer and 12 hours or shorter.

[wherein, R ^b1 , R ^b21 , R ^b22 , Z and X ^- are the same as R ^b1 , R ^b21 , R ^b22 , Z and X ^- in the formula (b1). X" represents a relative anion. M' ⁺ is an ammonium cation].

After completion of the salt exchange reaction, the compound in the reaction solution may be isolated and purified. The separation and purification can be carried out by a conventionally known method, and for example, concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, or the like can be appropriately used.

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

(acid generator)

The acid generator of the fourth aspect of the present invention is composed of the compound of the third aspect described above.

The acid generator has an acid generator component for use as a chemically amplified resist composition. By using the acid generator component in the chemically amplified resist composition, the lithographic characteristics of exposure margin, CDU, resolution, LWR, etc. are well maintained in the formation of the resist pattern, and high achievable Sensitive. Especially for EB or EUV light sources, high sensitivity is easily obtained.

[Examples]

The invention is illustrated in more detail below by way of examples, but the invention is not limited by the examples.

In the present embodiment, the compound represented by the chemical formula (1) is expressed as "compound (1)", and the compounds represented by other chemical formulas are also expressed in the same manner. Said.

<Production Example of Compound> (Example 1)

Magnesium metal (13.75 g) and tetrahydrofuran (THF) were added to a 1000 mL three-necked flask, and the mixture was stirred at 50 ° C to obtain a solution. A solution of 3,5-difluorobromobenzene (108.08 g) in tetrahydrofuran (236.16 g) was added dropwise to the solution, and the mixture was stirred with heating for 1 hour to prepare a 3,5-difluorophenyl magnesium bromide solution.

In a 2000 mL three-necked flask, trimethylsulfonyltrifluoromethanesulfonate (TMSTF) (248.93 g) was added to a solution of hydrazine A (37.38 g) in tetrahydrofuran (323.61 g), and stirred in an ice bath to obtain a reaction. Solution. The 3,5-difluorophenyl magnesium bromide solution was added to the reaction solution, and the mixture was aged for 1 hour.

Then, the reaction was traced by liquid chromatography (LC), and pure water was added to stop the reaction. The extract was extracted from the aqueous phase with dichloromethane, and concentrated to dryness to obtain 50 g of the target precursor (1).

The obtained precursor (1) was subjected to NMR measurement, and its structure was identified from the following measurement results.

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 8.51 (d, Ph, 2H), 8.41 (d, Ph, 2H), 7.98 (t, Ph, 2H), 7.76 (t, Ph, 2H ), 7.69 (tt, Ph, 1H), 7.49 (d, Ph, 2H)

To the dichloromethane solution of the precursor (1) (5.00 g), the compound (1) (4.34 g) for salt exchange was added, and the mixture was stirred at room temperature for 30 minutes to obtain a reaction mixture solution.

After stirring, pure water (78.9 g) was added to the reaction mixture solution to stop the reaction. The aqueous phase was removed, and the organic phase was washed 4 times with pure water.

After washing, the organic phase was concentrated to dryness to give 5.75 g of the title compound (B1-4).

Further, in the following reaction formula, " ^- OTf" means an trifluoromethanesulfonate anion.

(Example 2)

A salt exchange reaction or the like was carried out in the same manner as in Example 1 except that the compound for salt exchange was changed to obtain the target compound (B1-7).

In other words, the compound (2) (4.50 g) for salt exchange was added to a dichloromethane solution of the precursor (1) (5.00 g), and the mixture was stirred at room temperature for 30 minutes to obtain a reaction mixture solution.

After stirring, pure water (65.9 g) was added to the reaction mixture solution to stop the reaction. The aqueous phase was removed, and the organic phase was washed 4 times with pure water.

After washing, the organic phase was concentrated to dryness to give the title compound (B1-7).

(Examples 3 to 38)

A salt exchange reaction or the like was carried out in the same manner as in Example 2 except that the compound for salt exchange was changed, and the target compound (B1-1) to the compound (B1-3), the compound (B1-5), and the compound (B1-6) were obtained. ), compound (B1-8) to compound (B1-38).

(Example 39)

Magnesium metal (12.83 g) and tetrahydrofuran (THF) were added to a 1000 mL three-necked flask, and the mixture was stirred at 50 ° C to obtain a solution. A tetrahydrofuran solution (235.15 g) of 3-trifluoromethylbromobenzene (117.58 g) was added dropwise to the solution, and the mixture was stirred under heating for 1 hour to prepare a 3-trifluoromethylphenyl magnesium bromide solution.

Trimethyl decyl trifluoromethanesulfonate (TMSTF) (232.27 g) was added to a solution of yttrium A (34.88 g) in tetrahydrofuran (301.95 g) in a 2000 mL three-necked flask, and stirred in an ice bath to obtain a reaction solution. . In the opposite The 3-trifluoromethylphenyl magnesium bromide solution was added to the solution, and the mixture was aged for 1 hour.

Then, the reaction was traced by liquid chromatography (LC), and pure water was added to stop the reaction. The extract was extracted from the aqueous phase with dichloromethane, and concentrated to dryness to obtain 50 g of the target precursor (2).

The obtained precursor (2) was subjected to NMR measurement, and its structure was identified from the following measurement results.

¹ H-NMR (400MHz, DMSO-d6) δ (ppm) = 8.60 (s, Ph, 1H), 8.52 (d, Ph, 2H), 8.41 (d, Ph, 2H), 8.08 (d, Ph, 1H) ), 7.98 (t, Ph, 2H), 7.78 (t, Ph, 2H), 7.70 (t, Ph, 1H), 7.34 (d, Ph, 1H)

The compound (1) (5.33 g) for salt exchange was added to a dichloromethane solution of the precursor (2) (5.00 g), and the mixture was stirred at room temperature for 30 minutes to obtain a reaction mixture solution.

After stirring, pure water (92.7 g) was added to the reaction mixture solution to stop the reaction. The aqueous phase was removed, and the organic phase was washed 4 times with pure water.

After washing, the organic phase was concentrated to dryness to give the title compound (B1-42) 7.42 g.

Further, in the following reaction formula, " ^- OTf" means an trifluoromethanesulfonate anion.

(Embodiment 40)

A salt exchange reaction or the like was carried out in the same manner as in Example 39 except that the compound for salt exchange was changed to obtain the title compound (B1-45).

In other words, the compound (2) (4.20 g) for salt exchange was added to a dichloromethane solution of the precursor (2) (5.00 g), and the mixture was stirred at room temperature for 30 minutes to obtain a reaction mixture solution.

After stirring, pure water (66.5 g) was added to the reaction mixture solution to stop the reaction. The aqueous phase was removed, and the organic phase was washed 4 times with pure water.

After washing, the organic phase was concentrated to dryness to give the title compound (B1-45).

(Examples 41 to 76)

A salt exchange reaction or the like was carried out in the same manner as in Example 40 except that the compound for salt exchange was changed, and the target compound (B1-39) to the compound (B1-41), the compound (B1-43), and the compound (B1-44) were obtained. ), compound (B1-46) ~ compound (B1-76).

The structures of the cation portion and the anion portion of the obtained compound (B1-1) to the compound (B1-76) and the results of NMR measurement are as follows.

Cationic part of compound (B1-1)~ compound (B1-38)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 8.51 (d, Ph, 2H), 8.41 (d, Ph, 2H), 7.98 (t, Ph, 2H), 7.76 (t, Ph, 2H ), 7.69 (tt, Ph, 1H), 7.49 (d, Ph, 2H)

Cationic part of compound (B1-39)~compound (B1-76)

¹ H-NMR (400MHz, DMSO-d6) δ (ppm) = 8.60 (s, Ph, 1H), 8.52 (d, Ph, 2H), 8.41 (d, Ph, 2H), 8.08 (d, Ph, 1H) ), 7.98 (t, Ph, 2H), 7.78 (t, Ph, 2H), 7.70 (t, Ph, 1H), 7.34 (d, Ph, 1H)

Anion of compound (B1-1) and compound (B1-39)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 4.40 (t, 2H, CH 2), 4.21 (t, 2H, CH 2), 1.61-1.98 (m, 15H, Adamantyl)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -106.6

Anion of compound (B1-2) and compound (B1-40)

¹ H-NMR (400 MHz, DMSO-d6) δ (ppm) = 4.40 - 4.50 (m, 4H, CH ₂ )

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -106.7, -154.0, -160.0, -16.

Anion of compound (B1-3) and compound (B1-41)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 4.41 (t, 2H, CH 2), 4.23 (t, 2H, CH 2), 0.79-2.89 (m, 21H, Undecanoyl)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -106.8

Anion of compound (B1-4) and compound (B1-42)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 4.78 (m, 1H, CH), 4.66 (t, 1H, CH), 3.88 (t, 1H, CH), 3.31-3.36 (m, 1H ,CH), 2.47-2.49 (m,1H,CH), 1.73-2.21 (m,4H,CH ₂ )

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -107.7

Anion of compound (B1-5) and compound (B1-43)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 8.74-8.82 (m, 2H, Py-H), 7.84 (dd, 2H, Py-H), 4.54-4.61 (m, 4H, CH 2 CH ₂ )

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -106.5

Anion of compound (B1-6) and compound (B1-44)

¹ H-NMR (400 MHz, DMSO-d6) δ (ppm) = 5.46 (t, 1H, oxo-norbornane), 4.97 (s, 1H, oxo-norbornane), 4.71 (d, 1H, oxo-norbornane), 4.57 (d, 1H, oxo-norbornane), 2.69-2.73 (m, 1H, oxo-norbornane), 2.06-2.16 (m, 2H, oxo-norbornane).

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -107.1

Anion of compound (B1-7) and compound (B1-45)

¹ H-NMR (400 MHz, DMSO-d6) δ (ppm) = 4.55 (t, 2H, CF ₂ CH ₂ ), 1.64-1.96 (m, 15H, Adamantyl)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -111.2

Anion of compound (B1-8) and compound (B1-46)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 4.40 (t, 2H, CH 2), 4.20 (t, 2H, CH 2), 2.05 (s, 2H, CH 2), 1.53-1.95 ( m, 15H, Adamantyl)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -111.2

Anion of compound (B1-9) and compound (B1-47)

¹ H-NMR (400 MHz, DMSO-d6) δ (ppm) = 4.19 (s, 2H, CH ₂ ), 1.55-1.87 (m, 15H, Adamantyl)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -77.7

Anion of compound (B1-10) and compound (B1-48)

¹ H-NMR (400 MHz, DMSO-d6) δ (ppm) = 2.77-2.81 (m, 1H, Cyclohexyl), 2.04-2.08 (m, 2H, Cyclohexyl), 1.73-1.75 (m, 2H, Cyclohexyl), 1.56 -1.59 (m, 1H, Cyclohexyl), 1.07-1.33 (m, 5H, Cyclohexyl)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -74.7

Anion of compound (B1-11) and compound (B1-49)

¹ H-NMR (400 MHz, DMSO-d6) δ (ppm) = 1.55-1.88 (m, 15H, Adamantyl)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -74.5

Anion of compound (B1-12) and compound (B1-50)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 2.13 (m, 3H, Adamantyl), 1.56-1.96 (m, 12H, Adamantyl)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -69.2, -76.0, -112.9

Anion of compound (B1-13) and compound (B1-51)

¹ H-NMR (400 MHz, DMSO-d6) δ (ppm) = 7.51 - 7.96 (m, 7H, Naph), 5.20 (s, 2H, CH ₂ )

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -80.5, -113.7

Anion of compound (B1-14) and compound (B1-52)

¹ H-NMR (400 MHz, DMSO-d6) δ (ppm) = 2.09 (s, 3H, Adamantyl), 1.56-1.96 (m, 12H, Adamantyl)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -70.1, -113.4

Anion of compound (B1-15) and compound (B1-53)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -73.7

Anion of compound (B1-16) and compound (B1-54)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -161.1, -149.7, -131.6, -76.2

Anion of compound (B1-17) and compound (B1-55)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 2.88 (d, 1H, CH), 2.66-2.74 (m, 1H, CH), 2.37 (d, 1H, CH), 2.17-2.24 (m , 1H, CH), 1.90 (t, 1H, CH), 1.74-1.89 (m, 2H, CH ₂ ), 1.22-1.29 (m, 2H, CH ₂ ), 1.03 (s, 3H, CH ₃ ), 0.71 (s, 3H, CH ₃ )

Anion of compound (B1-18) and compound (B1-56)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -77.3, -111.5, -118.1, -122.4

Anion of compound (B1-19) and compound (B1-57)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -75.0

Anion of compound (B1-20) and compound (B1-58)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -77.3, -112.5, -121.7

Anion of compound (B1-21) and compound (B1-59)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -116.9, -123.0

Anion of compound (B1-22) and compound (B1-60)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -75.9, -76.0, -114.7

Anion of compound (B1-23) and compound (B1-61)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 5.83-5.92 (m, 1H, anion CH), 5.41 (dd, 1H, anion CH), 5.21 (dd, 1H, anion CH), 4.45 ( s, 2H, anion CH ₂ )

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -80.0, -113.0

Anion of compound (B1-24) and compound (B1-62)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 4.49-4.51 (m, 2H, O-CH 2), 4.30-4.32 (m, 2H, O-CH 2), 2.31 (t, 2H, CO-CH ₂ ), 1.51-1.56 (m, 2H, CH ₂ ), 1.15-1.35 (m, 6H, CH ₂ ), 0.87 (t, 3H, CH ₃ )

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -106.7

Anion of compound (B1-25) and compound (B1-63)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 4.50-4.54 (m, 4H, OCH 2 CH 2 O), 3.57 (d, 1H, CH 2 SO 2), 3.36 (sd, 1H, CH ₂ SO ₂ ), 2.24 - 2.34 (m, 2H, camphor), 2.07 (t, 1H, camphor), 1.92-1.99 (m, 2H, camphor), 1.56-1.62 (m, 1H, camphor), 1.42-1.45 (m, 1H, camphor), 1.04 (s, 3H, CH ₃ ), 0.84 (s, 3H, CH ₃ ).

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -106.5

Anion of compound (B1-26) and compound (B1-64)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 4.22 (s, 2H, CH 2 O), 4.05 (t, 2H, CH 2 CF 2), 2.24 (br s, 2H, Adamantyl), 1.53 -1.99 (m, 15H, Adamantyl + CH ₃ )

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -111.0

Anion of compound (B1-27) and compound (B1-65)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 4.84 (ddd, 1H, CH 2 O), 4.68 (ddd, 1H, CH 2 O), 2.38-2.45 (m, 1H, camphanic), 1.93 -2.06 (m, 2H, camphanic), 1.55-1.61 (m, 1H, camphanic), 1.04 (s, 3H, CH ₃ ), 1.03 (s, 3H, CH ₃ ), 0.85 (s, 3H, CH ₃ ) .

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -111.0

Anion of compound (B1-28) and compound (B1-66)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 5.02 (s, 1H, CH), 4.21 (s, 1H, CH), 2.93 (s, 1H, CH), 1.41-2.29 (m, 10H , Hyper-lactone).

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -107.3

Anion of compound (B1-29) and compound (B1-67)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 4.39-4.60 (m, 4H, OCH 2 CH 2 O), 2.36-2.53 (m, 1H, Camphane), 1.88-2.03 (m, 2H, Camphane), 1.47-1.62 (m, 1H, Camphane), 0.81-1.11 (m, 9H, CH ₃ )

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -106.6

Anion of compound (B1-30) and compound (B1-68)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 6.01 (s, 1H, C = CH), 5.62 (s, 1H, C = CH), 3.95-4.00 (t, 2H, CH 2), 3.09-3.15(t,2H,CH ₂ ), 1.83(s,3H,CH ₃ )

^{19 F-NMR (376MHz, DMSO} -d6) δ (ppm) = - 76.0

Anion of compound (B1-31) and compound (B1-69)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 5.21 (m, 1H, CFH), 4.82 (m, 1H, OCH 2), 4.57 (m, 1H, OCH 2), 2.51 (m, 1H ,Camphane), 2.03 (m, 2H, Camphane), 1.59 (m, 1H, Camphane), 1.10 (s, 6H, CH ₃ ), 0.85 (s, 3H, CH ₃ )

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -108.6, -116.5, -204.2

Anion of compound (B1-32) and compound (B1-70)

¹ H-NMR (400 MHz, DMSO-d6) δ (ppm) = 6.22 (m, 1H, CH=CH), 6.07 (m, 1H, CH=CH), 4.76 (m, 1H, sultone), 4.65-4.34 (m, 3H, CF ₂ CH ₂ + sultone), 3.87 (m, 1H, sultone), 3.58-3.38 (m, 3H, CHC=O+sultone), 3.11 (m, 2H, Norbornene), 2.37 (m, 1H, sultone), 2.16 (m, 1H, sultone), 1.89-1.66 (m, 3H, sultone), 1.44-1.21 (m, 2H, Norbornene)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -118.5~-118.9

Anion of compound (B1-33) and compound (B1-71)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 3.82-3.89 (t, 2H, CH 2), 3.00-3.08 (t, 2H, CH 2), 1.58-1.93 (m, 15H, Adamantane)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -73.2

Anion of compound (B1-34) and compound (B1-72)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 4.61 (dt, 4H, CH 2 CF 2), 2.40-2.65 (m, 8H, CH 2 CH 2), 1.72 (s, 6H, CH 3 ), 1.66 (s, 6H, CH ₃ ).

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -111.4

Anion of compound (B1-35) and compound (B1-73)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 6.1 (s, 1H, CH 2 = C), 5.74 (s, 1H, CH 2 = C), 4.58-4.67 (t, 2H, CH 2 ), 1.89 (s, 3H, CH ₃ ).

^{19 F-NMR (376MHz, DMSO} -d6) δ (ppm) = - 111.3

Anion of compound (B1-36) and compound (B1-74)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 5.76 (d, 1H, CH), 4.87-5.05 (m, 3H, CH), 4.23 (m, 1H, CH), 2.28-2.40 (m , 2H, oxosultone)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -106.7

Anion of compound (B1-37) and compound (B1-75)

^{1 H-NMR (400MHz, DMSO} -d6) δ (ppm) = 9.36 (m, 2H, ArH), 8.74 (s, 1H, ArH), 4.92 (t, 4H, CH 2)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -110.9

Anion of compound (B1-38) and compound (B1-76)

¹⁹ F-NMR (376 MHz, DMSO-d6) δ (ppm) = -129.6, -158.7, -163.2

<Production Example of Substrate Component (Polymer)>

The polymers A-1 to A-18 used in the examples were obtained by radical polymerization of the following monomers which are used as constituent units of the respective polymers in a specific molar ratio.

For the polymers A-1 to A-18, the copolymerization composition ratio of the polymer obtained by ¹³ C-NMR is shown in Table 1 (the ratio of each constituent unit in the polymer (mol ratio) The mass average molecular weight (Mw) and the molecular weight dispersion (Mw/Mn) in terms of standard polystyrene determined by GPC measurement.

<Preparation of Repressant Composition> (Examples 77 to 110, Comparative Examples 1 to 15)

The components shown in Tables 2 to 5 were mixed and dissolved, and the resist compositions of the respective examples were prepared.

In Tables 2 to 5, each symbol has the following meaning. The value in [ ] is the blending amount (parts by mass).

(A)-1~(A)-18: The above polymers A-1 to A-18.

(B1)-1: an acid generator prepared from the above compound (B1-4).

(B1)-2: an acid generator formed from the above compound (B1-7).

(B1)-3: an acid generator prepared from the above compound (B1-42).

(B1)-4: an acid generator prepared from the above compound (B1-45).

(B2)-1~(B2)-5: an acid generator prepared from the compounds (B2-1) to (B2-5) represented by the following chemical formulas (B2-1) to (B2-5).

(D)-1~(D)-10: an acid diffusion controlling agent formed by the compounds (D-1) to (D-10) represented by the following chemical formulas (D-1) to (D-10).

(S)-1: a mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 20/80 (mass ratio).

<Formation of resist pattern>

8 吋矽 substrate treated with hexamethyldioxane (HMDS) The resist compositions of the respective examples were coated with a spinner, and subjected to prebaking (PAB) treatment at a temperature of 100 ° C for 60 seconds on a hot plate, followed by drying to form a resist film having a film thickness of 30 nm.

Next, using the electron beam drawing device JEOL-JBX-9300FS (manufactured by JEOL Ltd.) for the resist film, a line and space chart with a target size of 1:1 line width of 50 to 26 nm was performed at an acceleration voltage of 100 kV. Drawing (exposure) of the type (hereinafter "LS pattern").

Then, at 23 ° C, a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used, and alkali development was carried out for 60 seconds.

Thereafter, the mixture was rinsed with pure water for 60 seconds, and subjected to post-exposure heating (PEB) treatment at 110 ° C for 60 seconds.

As a result, a 1:1 LS pattern with a line width of 50 to 26 nm is formed.

[Evaluation of Optimum Exposure (Eop)]

The optimum exposure amount Eop (μC/cm ² ) of the LS pattern of the target size was determined by the formation method of the above resist pattern. This is shown in the table as "Eop (μC/cm ² )".

[Evaluation of resolution]

The extreme resolution in the above Eop was obtained by using a scanning electron microscope S-9380 (manufactured by Hitachi High Technologies Co., Ltd.). Specifically, the exposure amount was slightly increased each time from the optimum exposure amount Eop to form an LS pattern. The smallest size of the pattern that does not collapse. Put it The "resolution performance (nm)" is shown in the table.

[LWR (Linewidth Width) Evaluation]

For the LS pattern formed in the above <Formation of Resistivity Pattern>, 3σ indicating the scale of LWR was obtained. This is shown in the table as "LWR (nm)".

"3σ" indicates that 400 points of the line position are measured in the longitudinal direction of the line by a scanning electron microscope (acceleration voltage 800V, trade name: S-9380, manufactured by Hitachi High Technologies Co., Ltd.), and the measurement result is obtained. 3 times the standard deviation (σ) (3σ) (unit: nm).

The smaller the value of 3σ, the smaller the thickness of the side wall of the line, the more uniform width LS pattern can be obtained.

[Evaluation of LS Pattern Shape]

The shape of the LS pattern formed by the formation of the above-mentioned <resist pattern pattern> was observed by a length measuring SEM (scanning electron microscope, acceleration voltage 800 V, trade name: S-9220, manufactured by Hitachi, Ltd.). The results are shown in the table as "shapes".

From the results shown in Tables 6 to 9, it was confirmed that when the resist composition of the embodiment of the present invention is applied, high sensitivity can be achieved under the lithographic characteristics of good resolution, thickness improvement, shape, and the like. Chemical.

<The stability of the compound over time> (Example 111, Comparative Example 16)

Each component shown in Table 10 was mixed and dissolved, and a test liquid for evaluation (solid content concentration: 10% by mass) was prepared.

In Table 10, each symbol has the following meaning.

(B1)-5: Compound (B1-77) represented by the following chemical formula (B1-77) (precursor (1) above).

(B2)-6: Compound (B2-6) represented by the following chemical formula (B2-6).

(D)-1: Compound (D-1) represented by the following chemical formula (D-1).

(S)-2: Propylene glycol monomethyl ether acetate (PGMEA).

[Evaluation of stability over time]

The test solutions of the respective examples were allowed to stand at room temperature (23 ° C) for 30 days.

After the storage, the respective decomposition rates of the (B1) component and the (B2) component contained in the test liquid were measured, and the stability with time of the compound was evaluated. This result is shown in Table 10 together as "decomposition rate (%)".

The respective decomposition rates of the (B1) component and the (B2) component were measured as follows.

0.1 g of the test solution of each of the examples before and after the storage was used as a sample, and a diluted solution obtained by accurately diluting 1 g of acetonitrile was used as a sample, and subjected to reverse phase high-speed liquid chromatography (HPLC).

The ratio of the peak area of the component (B1) and the peak area of the component (B2) to the change before and after storage in the chromatogram obtained in the measurement was defined as the decomposition rate (%).

From the results shown in Table 10, it was confirmed that the compound (B1-77) having a fluorine atom bonded to the meta position was compared with the compound (B2-6) having a fluorine atom bonded at the para position, and the decomposition rate was obtained. It is particularly low and has excellent stability over time.

Also, since the compound (B1-77) is used in combination with the compound (D-1) It is also stable, so it has an acid generator for use as a resist composition.

Claims (7)

A resist composition which is an resist which generates an acid by exposure and which has a change in solubility in a developing solution by an action of an acid, and is characterized in that it dissolves in a developing solution by an action of an acid a substrate component (A) having a change in properties, and a compound (B1) represented by the following formula (b1); ^Wherein R ^b1 represents an aromatic ring having an electron attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b10 (except that the aforementioned aromatic ring is a benzene ring) When the electron-attracting group is bonded to at least one of the benzene rings, R ^b10 represents an alkyl group, a fluorinated alkyl group or an aryl group; and R ^b21 and R ^b22 each independently represent An aromatic ring of an electron-attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group and -SO ₂ R ^b20 ; R ^b20 represents an alkyl group, a fluorinated alkyl group or an aryl group; a sulfur atom, an oxygen atom, a carbonyl group or a single bond; R ^b1 and R ^b21 may also be bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula; R ^b1 and R ^b22 It may also be bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula; X ^- represents a relative anion (except for BF ₄ ^- ). The resist composition of claim 1, wherein the content of the compound (B1) is from 1 to 50 parts by mass based on 100 parts by mass of the base component (A). The resist composition of claim 1 or 2, wherein the substrate component (A) contains a polymer compound (A1), and the polymer compound (A1) has a polarity which increases by an action of an acid The constituent unit (a1) of the acid-decomposable group. A resist pattern forming method, comprising: a step of forming a resist film by using a resist composition according to any one of claims 1 to 3 on a support, a step of exposing the resist film, and The step of developing the resist film after the exposure to form a resist pattern. The method of forming a resist pattern according to claim 4, wherein in the step of exposing the resist film, EUV (extreme ultraviolet ray) or EB (electron beam) is exposed to the resist film. a compound represented by the following formula (b1); ^Wherein R ^b1 represents an aromatic ring having an electron attracting group selected from the group consisting of a fluorine atom, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b10 (except that the aforementioned aromatic ring is a benzene ring) When the electron-attracting group is bonded to at least one of the benzene rings; R ^b10 represents an alkyl group, a fluorinated alkyl group or an aryl group; and R ^b21 and R ^b22 each independently represent a group selected from the group consisting of fluorine An aromatic ring of an electron-attracting group of a group of atoms, a trifluoromethyl group, a nitro group, a cyano group, and -SO ₂ R ^b20 ; R ^b20 represents an alkyl group, a fluorinated alkyl group or an aryl group; and Z represents a sulfur atom, An oxygen atom, a carbonyl group or a single bond; R ^b1 and R ^b21 may also be bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and form a ring together with a sulfur atom in the formula; R ^b1 and R ^b22 may also It is bonded through a sulfur atom, an oxygen atom, a carbonyl group or a single bond, and forms a ring together with a sulfur atom in the formula; X ^- represents a relative anion (except for BF ₄ ^- ). An acid generator consisting of the compound of claim 6.