KR20200006919A - Resist composition and method of forming resist pattern - Google Patents

Abstract

Provided are a resist composition, which can form a thick film resist film having a film thickness of 5 μm or more, and can form a pattern of a good shape while maintaining high sensitivity, and to a method for forming a resist pattern using the same. The resist composition which generates acid by exposure and changes solubility for a developing solution by an action of acid, comprises: (A) a base component having changeable solubility for a developing solution by an action of acid; and a tertiary monoamine compound (D0) represented by general formula (d0). The concentration of the base component (A) is 20 mass% or more, and content of the compound (Do) is 0.01 to 0.05 parts by weight with respect to 100 parts by weight of the base component (A). In the general formula (d0), Rx^1 to Rx^3 each independently represent a hydrocarbon group which may have a substituent, and two or more of Rx^1 to Rx^3 may bind to each other to form a ring structure.

Description

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

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

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

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

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

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

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

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

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

For example, in the case of the resin component which the solubility with respect to alkaline developing solution increases by the action of an acid, the structural unit containing the acid-decomposable group which decomposes by the action of the acid generated from an acid generator etc. and increases polarity is used, In addition, the structural unit containing a lactone containing cyclic group, the structural unit containing polar groups, such as a hydroxyl group, etc. are used together.

Moreover, in formation of a resist pattern, the behavior of the acid which generate | occur | produces from an acid generator component by exposure becomes an element which has a big influence on a lithographic characteristic.

On the other hand, the chemically amplified resist composition which has an acid-diffusion control agent which controls the diffusion | diffusion of the acid which generate | occur | produces from the acid generator component by exposure with an acid generator component is proposed.

For example, Patent Literature 1 discloses a chemically amplified resist material containing a specific solvent, a base polymer containing a fluorine atom, a crosslinking agent, an acid generator, and a basic compound as an acid diffusion control agent. For example, Patent Literature 2 discloses a chemically amplified positive resist composition containing an alkali-soluble resin, a specific crosslinking agent, an acid generator, and an amine compound having a specific structure as an acid diffusion control agent.

By the way, with the high integration of LSI and the high speed of communication, the increase of memory capacity is calculated | required and further refinement | miniaturization of a pattern is progressing rapidly. However, in lithography by electron beam or EUV, although the aim is to form fine patterns of several tens of nm, there are still many problems such as low productivity.

On the other hand, in addition to miniaturization, the development of the three-dimensional structure device which aims at the large capacity of a memory by the lamination which accumulates a cell is advanced.

Japanese Laid-Open Patent Publication 2001-174997 Japanese Unexamined Patent Publication No. 2004-347852

In the production of the three-dimensional structural device, a thick film resist film having a higher film thickness, for example, a film thickness of 5 μm or more is formed on the surface of the workpiece, and a resist pattern is formed to perform etching or the like. Have In the case where the chemically amplified resist composition is used here, the thicker the film thickness of the resist film becomes, the more difficult it is to maintain the sensitivity during exposure. Moreover, in a thick film resist film, the resolution with respect to image development falls and a desired resist pattern shape is hard to be obtained.

This invention is made in view of the said situation, The resist composition which can form the thick film resist film of 5 micrometers or more in film thickness, and can form a pattern of favorable shape, maintaining high sensitivity, and the resist composition It is a subject to provide the used resist pattern formation method.

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

That is, the 1st aspect of this invention is a resist composition which generate | occur | produces an acid by exposure and changes solubility with respect to a developing solution by the action of an acid, and is a base component whose solubility with respect to a developing solution changes with the action of an acid. (A) and the tertiary monoamine compound (D0) represented by the following general formula (d0), The density | concentration of the said base component (A) is 20 mass% or more, and content of the said compound (D0) is It is 0.01-0.05 mass parts with respect to 100 mass parts of said base material components (A), It is a resist composition characterized by the above-mentioned.

[Formula 1]

[Wherein, Rx ¹ to Rx ³ each independently represent a hydrocarbon group which may have a substituent. Two or more of Rx ¹ to Rx ³ may be bonded to each other to form a ring structure.]

According to a second aspect of the present invention, a step (i) of forming a resist film using the resist composition, a step (ii) of exposing the resist film, and a resist film after the exposure are developed to form a resist pattern. It is a resist pattern formation method which has a process (iii).

According to the present invention, there is provided a resist composition capable of forming a thick film resist film having a film thickness of 5 µm or more and forming a pattern having a good shape while maintaining high sensitivity, and a resist pattern forming method using the resist composition. can do.

In this specification and this patent application, an "aliphatic" is defined as a relative concept with respect to an aromatic and means a group, a compound, etc. which do not have aromaticity.

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

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

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

The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which part or all of hydrogen atoms of an alkyl group or an alkylene group are substituted with a fluorine atom.

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

When describing "you may have a substituent" or "you may have a substituent", when replacing a hydrogen atom (-H) with a monovalent group, and when replacing a methylene group (-CH _2- ) with a divalent group It includes both.

"Exposure" assumes the concept including the whole irradiation of radiation.

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

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

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

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

The "structural unit derived from acrylamide" means a structural unit which is formed by cleaving the ethylenic double bond of acrylamide.

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

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

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

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

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

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

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

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

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

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

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

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

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

(Resist composition)

The resist composition which concerns on the 1st aspect of this invention generate | occur | produces an acid by exposure, and the solubility to a developing solution changes by the action of an acid, and the base component which changes the solubility to a developing solution by the action of an acid. (A) (hereinafter also referred to as "(A) component") and tertiary monoamine compound (D0) (hereinafter also referred to as "(D0) component") represented by general formula (d0). Content of the said base material component (A) is 20 mass% or more, and content of the said compound (D0) is 0.01-0.05 mass parts with respect to 100 mass parts of said base material components (A).

When a resist film is formed using such a resist composition, a resist film having a film thickness of 5 m or more is formed.

When a resist film is formed using such a resist composition, and selective exposure is performed to the resist film, an acid is generated in the exposed portion of the resist film, and the solubility of the component (A) in the developer is changed by the action of the acid. On the other hand, in the unexposed part of the resist film, since the solubility of the (A) component in the developing solution does not change, a difference in solubility in the developing solution occurs between the exposed part and the unexposed part. Therefore, when the resist film is developed, the resist film exposed portion is dissolved and removed when the resist composition is positive, and the resist film unexposed portion is dissolved and removed when the resist composition is negative. A resist pattern of the type is formed.

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

The resist composition of this aspect may be a positive resist composition or a negative resist composition.

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

The resist composition of this aspect has an acid generating ability which generates an acid by exposure, (A) component may generate an acid by exposure, and the additive component mix | blended separately with (A) component is exposed by exposure. You may generate an acid.

The resist composition of this aspect may specifically contain the acid generator component (B) (henceforth "a component (B)") which generate | occur | produces an acid by exposure (1), (2) ( The component A) may be a component which generates an acid by exposure, (3) The component (A) may be a component which generates an acid by exposure, and may further contain the component (B).

That is, in the case of said (2) and (3), (A) component becomes "the base component which produces | generates an acid by exposure and changes solubility to a developing solution by the action of an acid." When the component (A) is a base component that generates an acid upon exposure and changes in solubility in a developer due to the action of an acid, the component (A1) described later generates an acid upon exposure, and It is preferable that it is a high molecular compound in which the solubility to a developing solution changes by the action of an acid. As such a high molecular compound, resin which has a structural unit which generate | occur | produces an acid by exposure can be used. As a structural unit which generate | occur | produces an acid by exposure, a well-known thing can be used.

Especially as mentioned above, such a resist composition is the case of said (1), ie, embodiment containing (A) component and (D0) component, and also containing (B) component is especially preferable.

<(A) component>

In the resist composition of the present embodiment, the component (A) is a base component whose solubility in a developer is changed by the action of an acid.

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

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

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

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

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

When the resist composition of this embodiment is a "negative resist composition for alkali image development processes" which form a negative resist pattern in an alkali image development process, or "solvent image formation which forms a positive resist pattern in a solvent image development process. In the case of "positive resist composition for processes", the base component (A-2) (hereinafter referred to as "(A-2) component") soluble in an alkali developer is preferably used as the component (A). The crosslinking agent component is blended. For example, when an acid is generated from component (B) by exposure, such a resist composition causes crosslinking between the component (A-2) and the crosslinking agent component, and as a result, solubility in an alkaline developer Decrease (solubility in organic developer) increases. Therefore, in formation of a resist pattern, when the resist film obtained by apply | coating the resist composition on a support body is selectively exposed, a resist film exposure part will change to poor solubility (soluble to an organic developing solution) with respect to an alkaline developing solution, and will resist Since the film unexposed portion does not change while being soluble in the alkaline developer (hardly soluble in the organic developer), the negative resist pattern is formed by developing with the alkaline developer. At this time, a positive resist pattern is formed by developing with an organic developer.

As a preferable thing of (A-2) component, soluble resin (henceforth "alkali soluble resin") is used with respect to alkaline developing solution.

As alkali-soluble resin, the alkyl ester of (alpha)-(hydroxyalkyl) acrylic acid or (alpha)-(hydroxyalkyl) acrylic acid disclosed by Unexamined-Japanese-Patent No. 2000-206694 (preferably C1-C1) Resin having a structural unit derived from at least one selected from alkyl ester of 5); Acrylic resin or polycycloolefin resin which the hydrogen atom couple | bonded with the carbon atom of the (alpha) position which has a sulfonamide group may be substituted by the substituent disclosed by US Patent 6949325; Acrylic resin which contains the fluorinated alcohol and which the hydrogen atom couple | bonded with the carbon atom of (alpha) position may be substituted by the substituent disclosed by US Patent 6949325, Unexamined-Japanese-Patent No. 2005-336452, and 2006-317803. ; The polycycloolefin resin etc. which have a fluorinated alcohol etc. which are disclosed by Unexamined-Japanese-Patent No. 2006-259582 are preferable at the point which can form the favorable resist pattern with little swelling.

In addition, the said (alpha)-(hydroxyalkyl) acrylic acid is acrylic acid which the hydrogen atom couple | bonds with the carbon atom of the (alpha) position which a carboxy group couple | bonds among the acrylic acids which the hydrogen atom couple | bonded with the carbon atom of the (alpha) position may be substituted by the substituent, and The one or both of the (alpha)-hydroxyalkyl acrylic acid which the hydroxyalkyl group (preferably C1-C5 hydroxyalkyl group) couple | bonds with the carbon atom of the (alpha) position is shown.

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

When the resist composition of this embodiment is a "positive resist composition for alkali image development processes" which form a positive resist pattern in an alkali image development process, or "solvent image formation which forms a negative type resist pattern in a solvent image development process. In the case of "negative resist composition for processes", as the component (A), the base component (A-1), which preferably increases in polarity by the action of an acid (hereinafter referred to as "(A-1) component") This is used. By using the component (A-1), since the polarity of the base component changes before and after exposure, good development contrast can be obtained not only in the alkali developing process but also in the solvent developing process.

In the case of applying the alkali developing process, the component (A-1) is poorly soluble in the alkaline developing solution before exposure. For example, when an acid is generated from the component (B) by exposure, it is polarized by the action of the acid. This increase increases the solubility in the alkaline developer. Therefore, in the formation of the resist pattern, when the resist composition is selectively exposed to a resist film obtained by applying the resist composition on a support, the resist film exposure portion changes from poorly soluble to soluble to an alkaline developer, while resist film minnows. Since the mining portion does not change while being insoluble in alkali, a positive resist pattern is formed by alkali development.

On the other hand, in the case of applying the solvent developing process, the component (A-1) has high solubility in the organic developer before exposure, and when acid is generated from the component (B) by exposure, the polarity is increased by the action of the acid. The solubility in organic developer is reduced. Therefore, in the formation of the resist pattern, when the resist composition is selectively exposed to the resist film obtained by applying the resist composition on the support, the resist film exposure portion changes from soluble to poorly soluble to an organic developer, while resist film minnows. Since the light portion does not change while being soluble, by developing with an organic developer, contrast can be provided between the exposed portion and the unexposed portion, and a negative resist pattern is formed.

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

In the resist composition of the present embodiment, the component (A) is preferably the component (A-1). That is, the resist composition of this embodiment is "the positive resist composition for alkali image development processes" which forms a positive resist pattern in an alkali image development process, or the "solvent image formation which forms a negative resist pattern in a solvent image development process. Negative resist composition for process ". As (A) component, at least one of a high molecular compound and a low molecular compound can be used.

When (A) component is (A-1) component, it is preferable to contain resin component (A1) (henceforth "(A1) component") as (A-1) component.

About (A1) component

It is preferable that (A1) component is a resin component and it contains the high molecular compound which has a structural unit (a1) containing the acid-decomposable group which increases polarity by the effect | action of an acid.

As (A1) component, in addition to a structural unit (a1), it is preferable to have a structural unit (a10) containing a hydroxy styrene skeleton further.

Moreover, as (A1) component, it is also preferable to have a structural unit (st) derived from styrene or its derivatives in addition to a structural unit (a1).

Moreover, (A1) component may have structural units other than a structural unit (a1), a structural unit (a10), and a structural unit (st).

`` Structural unit (a1) ''

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

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

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

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

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

An "acid dissociable group" is group which has acid dissociation property which the bond between the said acid dissociable group and the atom adjacent to this acid dissociable group can cleave by the action of (i) acid, or (ii) acid After some bonds are cleaved by the action of and decarboxylation reaction occurs, both of the groups capable of cleaving the bond between the acid dissociable group and atoms adjacent to the acid dissociable group can be cleaved.

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

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

As an acid dissociable group of the base resin for chemically amplified resist compositions, specifically, the "acetal acid dissociable group", the "tertiary alkyl ester type acid dissociable group" demonstrated below, and "tertiary Alkyloxycarbonyl acid dissociable group ”.

Acetal acid dissociation group:

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

[Formula 2]

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

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

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

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

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

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

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

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

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

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

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

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

Ra 'as the aromatic hydrocarbon group in the ^third Specifically, the aromatic hydrocarbon ring or a group removed a hydrogen atom from an aromatic heterocyclic ring (aryl or heteroaryl group); A group in which one hydrogen atom is removed from an aromatic compound (eg, biphenyl, fluorene, etc.) containing two or more aromatic rings; Groups in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic hetero ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2 And arylalkyl groups such as naphthylethyl group). It is preferable that carbon number of the alkylene group couple | bonded with the said aromatic hydrocarbon ring or aromatic heterocyclic ring is 1-4, It is more preferable that it is C1-C2, It is especially preferable that it is C1-C.

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 collectively referred to as "Ra ⁰⁵ ").

Here, R <^P1> is a C1-C10 monovalent chain-type saturated hydrocarbon group, a C3-C20 monovalent aliphatic cyclic saturated hydrocarbon group, or a C6-C30 monovalent aromatic hydrocarbon group. Moreover, R <^P2> is a single bond, a C1-C10 divalent linear saturated hydrocarbon group, a C3-C20 divalent aliphatic cyclic saturated hydrocarbon group, or a C6-C30 divalent aromatic hydrocarbon group. However, one part or all part of the hydrogen atom which the chain saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group, and aromatic hydrocarbon group of R <^P1> and R <^P2> have may be substituted by the fluorine atom. The aliphatic cyclic hydrocarbon group may have one or more of the substituents alone, or may have one or more of each of the substituents.

As a C1-C10 monovalent chain-type saturated hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, etc. are mentioned, for example.

As a C3-C20 monovalent aliphatic cyclic saturated hydrocarbon group, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, cyclododecyl group Monocyclic aliphatic saturated hydrocarbon groups such as these; Bicyclo [2.2.2] octanyl group, tricyclo [5.2.1.02,6] decanyl group, tricyclo [3.3.1.13,7] decanyl group, tetracyclo [6.2.1.13,6.02,7] dodecanyl group, Polycyclic type aliphatic saturated hydrocarbon groups, such as a danyl group, are mentioned.

As a C6-C30 monovalent aromatic hydrocarbon group, the group remove | excluding one hydrogen atom from aromatic hydrocarbon rings, such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene, is mentioned, for example.

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

Tertiary alkyl ester type acid dissociable group:

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

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

[Formula 3]

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

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

Examples of the linear or branched alkyl group and cyclic hydrocarbon group for Ra ' ⁴ (an aliphatic hydrocarbon group as monocyclic group, aliphatic hydrocarbon group as polycyclic group and aromatic hydrocarbon group) include the same as those for Ra' ³ . Can be.

The linear or cyclic alkenyl group for Ra ′ ⁴ is preferably an alkenyl group having 2 to 10 carbon atoms.

Examples of the hydrocarbon group for Ra ′ ⁵ and Ra ′ ^{6 include} the same groups as those for Ra ′ ³ .

When Ra ' ⁵ and Ra' ⁶ are bonded to each other to form a ring, the group represented by the following general formula (a1-r2-1), the group represented by the following general formula (a1-r2-2), and the following general formula (a1) The group represented by -r2-3) is mentioned preferably.

On the other hand, when Ra ' ⁴ to Ra' ⁶ do not bond with each other and are independent hydrocarbon groups, groups represented by the following general formula (a1-r2-4) are preferably mentioned.

[Formula 4]

[Wherein, Ra ^'10 of (a1-r2-1) is, represents a group represented by the group, or the following formula (a1-r2-r1) of 1 to 10 carbon atoms. Ra represents a group to form an aliphatic cyclic group with ^'11 is Ra, the carbon atom ¹⁰ is bonded. In formula (a1-r2-2), Ya is a carbon atom. Xa is group which forms a cyclic hydrocarbon group with Ya. One part or all part of the hydrogen atom which this cyclic hydrocarbon group has may be substituted. Ra ⁰¹ to Ra ⁰³ each independently represent a hydrogen atom, a C1-C10 monovalent chain saturated hydrocarbon group, or a C3-C20 monovalent aliphatic cyclic saturated hydrocarbon group. One part or all part of the hydrogen atom which this chain saturated hydrocarbon group and aliphatic cyclic saturated hydrocarbon group have may be substituted. Two or more of Ra ⁰¹ to Ra ⁰³ may be bonded to each other to form a cyclic structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is group which forms an aliphatic cyclic group with Yaa. Ra ⁰⁴ is an aromatic hydrocarbon group which may have a substituent. In formula (a1-r2-4), Ra ^'12 and Ra' ¹³ are each independently a C1-C10 monovalent linear saturated hydrocarbon group or hydrogen atom. One part or all part of the hydrogen atom which this linear saturated hydrocarbon group has may be substituted. Ra ^'14 is a hydrocarbon group which may have a substituent. * Represents a bonding hand (hereafter, same).]

[Formula 5]

[In formula, Ya ⁰ is a quaternary carbon atom. Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ are each independently a hydrocarbon group which may have a substituent. Provided that at least one of Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ is a hydrocarbon group having at least one polar group.]

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

In Formula (a1-r2-r1), Ya ⁰ is a quaternary carbon atom. That is, Ya ⁰ 4 carbon atoms bonded to the neighboring dog (carbon atom).

In the formula (a1-r2-r1), Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ are each independently a hydrocarbon group which may have a substituent. ^Examples of the hydrocarbon groups for Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ include a linear or branched alkyl group, a chain or cyclic alkenyl group, or a cyclic hydrocarbon group.

In Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ , the linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. are mentioned. Among these, a methyl group, an ethyl group, or n-butyl group is preferable, and a methyl group or ethyl group is more preferable.

The branched alkyl group in Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group and the like. It is preferable.

The linear or cyclic alkenyl group in Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ is preferably a C 2-10 alkenyl group.

In Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ , the cyclic hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or may be a polycyclic group or a monocyclic group.

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

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

The aromatic hydrocarbon group in Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 pi electrons, and may be monocyclic or polycyclic. It is preferable that carbon number of an aromatic ring is 5-30, 5-20 are more preferable, 6-15 are more preferable, and 6-12 are especially preferable. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene and phenanthrene; And an aromatic hetero ring in which part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. As a hetero atom in an aromatic hetero ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Specific examples of the aromatic hetero ring include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group include a group in which one hydrogen atom is removed from the aromatic hydrocarbon ring or aromatic hetero ring (aryl group or heteroaryl group); A group in which one hydrogen atom is removed from an aromatic compound (eg, biphenyl, fluorene, etc.) containing two or more aromatic rings; Groups in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic hetero ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2 And arylalkyl groups such as naphthylethyl group). It is preferable that carbon number of the alkylene group couple | bonded with the said aromatic hydrocarbon ring or aromatic heterocyclic ring is 1-4, It is more preferable that it is 1-2, It is especially preferable that it is one.

When the hydrocarbon groups represented by Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ are substituted, examples of the substituent include a hydroxyl group, a carboxy group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group ( Methoxy group, ethoxy group, propoxy group, butoxy group, etc.), an alkyloxycarbonyl group, etc. are mentioned.

Among the above, the hydrocarbon group which may have a substituent in Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ is preferably a linear or branched alkyl group which may have a substituent, and more preferably a linear alkyl group. .

However, at least one of Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ is a hydrocarbon group having at least a polar group.

The "hydrocarbon group having a polar group" includes both the methylene group (-CH _2- ) constituting the hydrocarbon group and the one substituted with the polar group or at least one hydrogen atom constituting the hydrocarbon group.

As such a "hydrocarbon group which has a polar group", the functional group represented by the following general formula (a1-p1) is preferable.

[Formula 6]

[In formula, Ra ⁰⁷ represents a C2-C12 bivalent hydrocarbon group. Ra ⁰⁸ represents a divalent linking group containing a hetero atom. Ra ⁰⁶ represents a C1-C12 monovalent hydrocarbon group. n _p0 is an integer of 1-6.]

In the formula (a1-p1), Ra ⁰⁷ represents a divalent hydrocarbon group having 2 to 12 carbon atoms.

The carbon number of Ra ⁰⁷ is 2 to 12, preferably 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, and particularly preferably 2 carbon atoms.

The hydrocarbon group for Ra ⁰⁷ is preferably a chain or cyclic aliphatic hydrocarbon group, and more preferably a chain hydrocarbon group.

As Ra ⁰⁷ , for example, an ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane- 1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12 Linear alkanediyl groups such as -diyl group; Propane-1,2-diyl group, 1-methylbutane-1,3-diyl group, 2-methylpropane-1,3-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4 Branched chain alkanediyl groups such as -diyl group; Cycloalkanediyl groups such as cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group and cyclooctane-1,5-diyl group; Polyvalent type divalent groups such as norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,5-diyl group, adamantane-2,6-diyl group Alicyclic hydrocarbon group etc. are mentioned.

Among the above, an alkanediyl group is preferable and a linear alkanediyl group is more preferable.

Ra ⁰⁸ represents a divalent linking group containing a hetero atom in the formula (a1-p1).

As Ra ⁰⁸ , for example, -O-, -C (= 0) -O-, -C (= 0)-, -OC (= 0) -O-, -C (= 0) -NH-, -NH-, -NH-C (= NH)-(H may be substituted by substituents, such as an alkyl group and an acyl group.), -S-, -S (= O) _2- , -S (= O) ₂ -O- etc. are mentioned.

Among these, from the point of solubility in a developing solution, -O-, -C (= O) -O-, -C (= O)-, -OC (= O) -O- is preferable, and -O-, -C (= 0)-is particularly preferred.

Ra ⁰⁶ represents a C1-C12 monovalent hydrocarbon group in the formula (a1-p1).

The carbon number of Ra ⁰⁶ is 1-12, in terms of solubility in a developing solution, preferably 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms, and 1 or 2 carbon atoms. Particularly preferred, 1 is most preferred.

Examples of the hydrocarbon group for Ra ⁰⁶ include a chain hydrocarbon group or a cyclic hydrocarbon group, or a hydrocarbon group obtained by combining a chain and a cyclic.

As the chain hydrocarbon group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- Heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. are mentioned.

The cyclic hydrocarbon group may be an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

The alicyclic hydrocarbon group may be either monocyclic or polycyclic, and the monocyclic alicyclic hydrocarbon group may be, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a methylcyclohexyl group. And cycloalkyl groups such as dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cycloheptyl group and cyclodecyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1- (adamantan-1-yl) alkane-1-yl group, Norbornyl group, methyl norbornyl group, isobornyl group, etc. are mentioned.

As an aromatic hydrocarbon group, a phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert- butylphenyl group, p-adamantylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, non A phenyl group, phenanthryl group, 2, 6- diethylphenyl group, 2-methyl-6- ethylphenyl group, etc. are mentioned.

As Ra ⁰⁶ , in view of solubility in a developing solution, a chain hydrocarbon group is preferable, an alkyl group is more preferable, and a linear alkyl group is more preferable.

In said formula (a1-p1), _np0 is an integer of 1-6, the integer of 1-3 is preferable, 1 or 2 is more preferable, and 1 is more preferable.

Below, the specific example of the hydrocarbon group which has a polar group at least is shown.

Of the following formula, * is a bonding hand to combine, on a quaternary carbon atom (Ya ^0).

[Formula 7]

In the formula (a1-r2-r1), the number of hydrocarbon groups having at least a polar group in Ra ⁰³¹ , Ra ⁰³² and Ra ⁰³³ is one or more, but in consideration of the solubility in a developing solution at the time of forming a resist pattern What is necessary is just to determine suitably, For example, it is preferable that it is one or two of Ra ⁰³¹ , Ra ^032, and Ra ⁰³³ , Especially preferably, it is one.

The hydrocarbon group having at least the polar group may have a substituent other than the polar group. As this substituent, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.) and a C1-C5 halogenated alkyl group are mentioned, for example.

Equation (a1-r2-1) of, Ra ^'11 (Ra' ¹⁰ is an aliphatic cyclic group which forms together with the carbon atoms bonded) is that equation (a1-r-1) Ra ' of the ^third single ring or sentence in the Groups mentioned as aliphatic hydrocarbon groups that are li-groups are preferred.

Equation (a1-r2-2) of, Xa is the hydrocarbon group of the type with a ring wherein Ya is, the formula (a1-r-1) of the Ra '1 valent hydrocarbon of type rings in the ^third group (an aliphatic hydrocarbon And groups in which at least one hydrogen atom is further removed.

The cyclic hydrocarbon group which Xa forms with Ya may have a substituent. The substituent is, those similar to the substituent which may have a hydrocarbon cyclic in the Ra ^'3.

Equation (a1-r2-2) of, Ra ⁰¹ Ra ⁰³ ~, 1 divalent chained saturated hydrocarbon group of 1 to 10 carbon atoms in, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl group, heptyl group, octyl group, decyl group, etc. are mentioned.

As a C3-C20 monovalent aliphatic cyclic saturated hydrocarbon group in Ra <^01> -Ra <^03> , it is a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, cyclooxe, for example. Monocyclic aliphatic saturated hydrocarbon groups such as a methyl group, a cyclodecyl group, and a cyclododecyl group; Bicyclo [2.2.2] octanyl group, tricyclo [5.2.1.02,6] decanyl group, tricyclo [3.3.1.13,7] decanyl group, tetracyclo [6.2.1.13,6.02,7] dodecanyl group, Polycyclic type aliphatic saturated hydrocarbon groups, such as a danyl group, etc. are mentioned.

Among them, Ra ⁰¹ to Ra ⁰³ are preferably a hydrogen atom and a C1-C10 monovalent chain saturated hydrocarbon group from the viewpoint of the ease of synthesis of the monomer compound inducing the structural unit (a1), and among them, a hydrogen atom , Methyl group and ethyl group are more preferable, and a hydrogen atom is especially preferable.

As a substituent which the linear saturated hydrocarbon group or aliphatic cyclic saturated hydrocarbon group represented by said Ra ⁰¹ -Ra ⁰³ has, the same group as Ra ⁰⁵ mentioned above is mentioned, for example.

Examples of the group containing a carbon-carbon double bond generated by two or more of Ra ⁰¹ to Ra ⁰³ bonded to each other to form a cyclic structure include, for example, a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, A methyl cyclohexenyl group, a cyclopentylidene ethenyl group, a cyclohexylidene ethenyl group, etc. are mentioned. Among these, a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylidene ethenyl group are preferable from a viewpoint of the ease of synthesis of the monomer compound which induces a structural unit (a1).

In the formula (a1-r2-3), an aliphatic cyclic group formed by Xaa with Yaa is preferably a group selected as an aliphatic hydrocarbon group which is a monocyclic group or a polycyclic group of Ra ' ^{3 in} the formula (a1-r-1). Do.

Examples of the aromatic hydrocarbon group for Ra ⁰⁴ in formula (a1-r2-3) include groups in which at least one hydrogen atom is removed from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Especially, the group in which Ra ⁰⁴ removed one or more hydrogen atoms from the C6-C15 aromatic hydrocarbon ring is preferable, The group in which one or more hydrogen atoms were removed from benzene, naphthalene, anthracene or phenanthrene is more preferable, and benzene, Groups from which at least one hydrogen atom is removed from naphthalene or anthracene are more preferred, groups from which at least one hydrogen atom is removed from benzene or naphthalene are particularly preferred, and groups from which at least one hydrogen atom is removed from benzene are most preferred.

As a substituent which Ra ⁰⁴ in Formula (a1-r2-3) may have, a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, a halogen atom (fluorine atom, a chlorine atom, a bromine atom, etc.), Alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group etc.), an alkyloxycarbonyl group, etc. are mentioned.

In formula (a1-r2-4), Ra ^'12 and Ra' ¹³ are each independently a C1-C10 monovalent linear saturated hydrocarbon group or hydrogen atom. Ra 'in the ¹² and Ra'13, 1-valent chained saturated hydrocarbon group of 1 to 10 carbon atoms is in the ⁰¹ ~ Ra Ra ^03, the carbon number of 1 to 10 In the same divalent chained saturated hydrocarbon group of Can be. One part or all part of the hydrogen atom which this linear saturated hydrocarbon group has may be substituted.

Among them, Ra ^'12 and Ra' ¹³ are preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably a methyl group and an ethyl group, and particularly preferably a methyl group.

When the chain saturated hydrocarbon group represented by said Ra ^'12 and Ra' ¹³ is substituted, as the substituent, the group similar to Ra ⁰⁵ mentioned above is mentioned, for example.

, Ra ^'14 in the formula (a1-r2-4) is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group for Ra ′ ¹⁴ include a linear or branched alkyl group or a cyclic hydrocarbon group.

Ra 'alkyl group linear in ¹⁴ is preferably a carbon number of 1-5, and is one or more preferred, more preferred is 1 or 24. Specifically, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, etc. are mentioned. Among these, a methyl group, an ethyl group, or n-butyl group is preferable, and a methyl group or ethyl group is more preferable.

Ra 'alkyl group branched at the ^14, it is preferable that the carbon number is 3-10, more preferably 3-5. 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 preferable.

When the hydrocarbon groups of Ra ^'14 is annular, and the hydrocarbon group, aliphatic hydrocarbon contribution is contribution being an aromatic hydrocarbon, again, is the contribution polycyclic and monocyclic contribution.

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

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

Examples of the aromatic hydrocarbon group for Ra ′ ¹⁴ include the same aromatic hydrocarbon group for Ra ⁰⁴ . In particular, Ra ^'14 is, the removal of one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 group is preferable, and more preferable group is removed, the one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene, benzene More preferably, a group in which at least one hydrogen atom is removed from naphthalene or anthracene is particularly preferable, a group in which at least one hydrogen atom is removed from naphthalene or anthracene is particularly preferable, and a group in which at least one hydrogen atom is removed from naphthalene is most preferred.

Examples of the substituent which Ra ′ ¹⁴ may have include the same substituents as the substituent that Ra ⁰⁴ may have.

Wherein Ra ^'14 when a naphthyl group, the position in combination with a tertiary carbon atom in the formula (a1-r2-4), the first position or second position of the naphthyl group in (a1-r2-4) You can be anywhere.

Equation (a1-r2-4) of Ra ^'14 when the anthryl group, the position in combination with a tertiary carbon atom in the formula (a1-r2-4) is not 1-position of casting reel group, a 2-position Or any of nine positions.

The specific example of group represented by said formula (a1-r2-1) is given to the following.

[Formula 8]

[Formula 9]

[Formula 10]

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

[Formula 11]

[Formula 12]

[Formula 13]

The specific example of group represented by said formula (a1-r2-3) is given to the following.

[Formula 14]

The specific example of group represented by said formula (a1-r2-4) is given to the following.

[Formula 15]

Tertiary alkyloxycarbonyl acid dissociable groups:

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

[Formula 16]

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

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

Moreover, it is preferable that carbon number of the sum total of each alkyl group is 3-7, It is more preferable that it is C3-C5, It is most preferable that it is C3-C4.

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

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

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

[Formula 17]

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

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

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

In the 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 as the divalent hydrocarbon group in Va ¹ may be saturated or unsaturated, and is preferably saturated.

Specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group or an aliphatic hydrocarbon group containing a ring in its structure.

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

As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], and a trimethylene group [-( CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ], and the like.

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

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

Examples of the aliphatic hydrocarbon group containing a ring in the above structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) and an alicyclic hydrocarbon group bonded to a terminal of a linear or branched aliphatic hydrocarbon group. And groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. As said linear or branched aliphatic hydrocarbon group, the same thing as the said linear aliphatic hydrocarbon group or the said branched aliphatic hydrocarbon group is mentioned.

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

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

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

It is preferable that such aromatic hydrocarbon group has 3-30 carbon atoms, It is more preferable that it is 5-30, 5-20 are still more preferable, 6-15 are especially preferable, 6-12 are the most preferable. However, the carbon number does not include the carbon number in the substituent.

As an aromatic ring which an aromatic hydrocarbon group has, Specifically, aromatic hydrocarbon rings, such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene; And an aromatic hetero ring in which part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. As a hetero atom in an aromatic hetero ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned.

Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms are removed from the aromatic hydrocarbon ring (arylene group); Groups in which one of the hydrogen atoms of the group (aryl group) in which one hydrogen atom is removed from the aromatic hydrocarbon ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group And a group in which one hydrogen atom is further removed from an aryl group in an arylalkyl group such as 1-naphthylethyl group and 2-naphthylethyl group). It is preferable that it is 1-4, As for carbon number of the said alkylene group (alkyl chain in an arylalkyl group), it is more preferable that it is 1-2, It is especially preferable that it is one.

In said formula (a1-1), Ra <^1> is an acid dissociable group represented by said formula (a1-r-1) or (a1-r-2).

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

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

In said formula (a1-2), Ra <^2> is an acid dissociable group represented by said general formula (a1-r-1) or (a1-r-3).

The specific example of the structural unit represented by said formula (a1-1) is shown below. In each of the following formulas, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

The specific example of the structural unit represented by said formula (a1-2) is shown below.

[Formula 29]

1 type may be sufficient as the structural unit (a1) which (A1) component has, and 2 or more types may be sufficient as it.

As the structural unit (a1),

The structural unit represented by said formula (a1-1) is more preferable at the point which is easy to raise the characteristic (sensitivity, CDU, shape, etc.) in lithography by KrF.

Especially, as a structural unit (a1), it is especially preferable to include the structural unit represented with the following general formula (a1-1-1).

[Formula 30]

[In formula, Ra < ^{1 >>} is an acid dissociable group represented by general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4).]

In the formula (a1-1-1), R, Va n ¹ and _a1 is the same as R, ¹ and Va n _a1 in the formula (a1-1).

Description of the acid dissociable group represented by general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4) is as having mentioned above.

As for the ratio of the structural unit (a1) in (A1) component, 1-80 mol% is preferable with respect to the total (100 mol%) of all the structural units which comprise (A1) component, and 5-70 mol% is more Preferably, 10-60 mol% is more preferable.

By making ratio of a structural unit (a1) more than a lower limit, lithographic characteristics, such as a sensitivity, a resolution, and roughness improvement, improve. Moreover, if it is below an upper limit, it can balance with the other structural unit, and various lithographic characteristics become favorable.

`` Structural unit (a10) containing a hydroxystyrene skeleton ''

In addition to the structural unit (a1), the component (A1) preferably further has a structural unit (a10) containing a hydroxystyrene skeleton.

As such a structural unit (a10), the structural unit represented by the following general formula (a10-1) is mentioned preferably, for example.

[Formula 31]

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

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

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

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

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

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

Divalent hydrocarbon groups which may have a substituent:

When Ya ^x1 is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

Aliphatic hydrocarbon group at Ya ^x1

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

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

Linear or branched aliphatic hydrocarbon groups

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

As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], and a trimethylene group [-( CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ], and the like.

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

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

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

Aliphatic hydrocarbon groups containing rings in the structure

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

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

The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic alicyclic hydrocarbon group, a group in which two hydrogen atoms are removed from a monocycloalkane is preferable. As this monocycloalkane, a C3-C6 thing is preferable, A cyclopentane, a cyclohexane, etc. are mentioned specifically ,. As the polycyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a polycycloalkane is preferable, and as the polycycloalkane, one having 7 to 12 carbon atoms is preferable, specifically, adamantane, norbornane, Isobornane, tricyclodecane, tetracyclododecane and the like.

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

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

As an alkoxy group as said substituent, a C1-C5 alkoxy group is preferable, A methoxy group, an ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, tert-butoxy group are more preferable, Methoxy The period and ethoxy group are most preferred.

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

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

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

Aromatic hydrocarbon groups in Ya ^x1

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

The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 pi electrons, and may be monocyclic or polycyclic. It is preferable that carbon number of an aromatic ring is 5-30, C5-C20 is more preferable, C6-C15 is further more preferable, C6-C12 is especially preferable. However, the carbon number does not include the carbon number in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene and phenanthrene; And an aromatic hetero ring in which part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. As a hetero atom in an aromatic hetero ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Specific examples of the aromatic hetero ring include a pyridine ring and a thiophene ring.

Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms are removed from the aromatic hydrocarbon ring or the aromatic hetero ring (arylene group or heteroarylene group); A group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.); Groups in which one of the hydrogen atoms of a group (aryl group or heteroaryl group) having one hydrogen atom removed from the aromatic hydrocarbon ring or aromatic hetero ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naph And a group in which one hydrogen atom is further removed from an aryl group in an arylalkyl group such as a methylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, or 2-naphthylethyl group). It is preferable that carbon number of the alkylene group couple | bonded with the said aryl group or heteroaryl group is 1-4, It is more preferable that it is C1-C2, It is especially preferable that it is C1-C1.

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

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

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

Bivalent linkers containing hetero atoms:

When Ya ^x1 is a divalent linking group containing a hetero atom, preferred as the linking group are -O-, -C (= 0) -O-, -C (= 0)-,-OC (= 0) -O. -, -C (= O) -NH-, -NH-, -NH-C (= NH)-(H may be substituted with a substituent such as an alkyl group, acyl group), -S-, -S ( = O) _2- , -S (= O) ₂ -O-, general formula -Y ²¹ -OY ^22- , -Y ²¹ -O-, -Y ²¹ -C (= O) -O-, -C ( = O) -OY ²¹ -,-[Y ²¹ -C (= O) -O] _{m "} -Y ^22- , -Y ²¹ -OC (= O) -Y ²² -or -Y ²¹ -S (= O Group represented by _2- OY ^22- [wherein, Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m '' is an integer of 0 to 3). Etc. can be mentioned.

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

Formula -Y ²¹ -OY ^22- , -Y ²¹ -O-, -Y ²¹ -C (= O) -O-, -C (= O) -OY ²¹ -,-[Y ²¹ -C (= O ) -O] _{m "} -Y ^22- , -Y ²¹ -OC (= O) -Y ²² -or -Y ²¹ -S (= O) ₂ -OY ^22- , Y ²¹ and Y ²² are each independently The divalent hydrocarbon group may be the same as the divalent hydrocarbon group described in the above description of the divalent linking group (the divalent hydrocarbon group which may have a substituent).

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

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

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

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

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

_Examples of the aromatic hydrocarbon group for Wa ^x1 include groups in which (n _ax1 +1) hydrogen atoms have been removed from the aromatic ring. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 pi electrons, and may be monocyclic or polycyclic. It is preferable that carbon number of an aromatic ring is 5-30, C5-C20 is more preferable, C6-C15 is further more preferable, C6-C12 is especially preferable. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene and phenanthrene; And an aromatic hetero ring in which part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. As a hetero atom in an aromatic hetero ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned. Specific examples of the aromatic hetero ring include a pyridine ring and a thiophene ring.

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

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

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

[Formula 32]

The structural unit (a10) that the component (A1) has may be one type or two or more types.

The proportion of the structural unit (a10) in the component (A1) is, for example, 1 to 90 mol%, based on the total (100 mol%) of all the structural units constituting the component (A1), and 10 to 85 Mol% is preferable, 20-80 mol% is more preferable, 30-75 mol% is especially preferable.

By making ratio of a structural unit (a10) more than the lower limit of the said preferable range, lithographic characteristics, such as a sensitivity, resolution, and roughness improvement, improve. Moreover, if it is below an upper limit, it can balance with the other structural unit, and various lithographic characteristics become favorable.

`` Structural unit (a2) ''

In addition to the structural unit (a1), the component (A1) further comprises, in addition to the structural unit (a1), a structural unit (a2) containing a lactone-containing cyclic group, a -SO ₂ -containing cyclic group, or a carbonate-containing cyclic group (however, the structural unit (a1) You may have any).

The lactone-containing cyclic group, the -SO ₂ -containing cyclic group, or the carbonate-containing cyclic group in the structural unit (a2) is effective in enhancing the adhesion of the resist film to the substrate when the component (A1) is used for formation of the resist film. will be. Moreover, by having a structural unit (a2), an acid diffusion length is adjusted suitably, for example, the adhesiveness of a resist film to a board | substrate is improved, the solubility at the time of image development is adjusted suitably, and the effect of improving etching tolerance etc. And lithography characteristics become good.

A "lactone containing cyclic group" represents the cyclic group containing the ring (lactone ring) containing -O-C (= O)-in the ring skeleton. The lactone ring is counted as the first ring, and in the case of only the lactone ring, it is called a polycyclic group irrespective of its structure if it has a monocyclic group or another ring structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

As the lactone-containing cyclic group in the structural unit (a2), any one can be used without particular limitation. Specifically, the group represented by the following general formula (a2-r-1) (a2-r-7) is mentioned, respectively.

[Formula 33]

[Wherein, Ra ^'21 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR ", -OC (= O ) R", hydroxy group or cyano group; R ″ is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ₂ -containing cyclic group; A ″ may contain an oxygen atom (-O-) or a sulfur atom (-S-) Is an alkylene group having 1 to 5 carbon atoms, an oxygen atom or a sulfur atom, n 'is an integer of 0 to 2, and m' is 0 or 1.]

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

Ra 'The alkoxy group in ²¹ is preferably an alkoxy group having 1 to 6 carbon atoms. It is preferable that this alkoxy group is linear or branched chain form. Specific examples include an alkyl group and is either an oxygen atom (-O-) in the alkyl group as the Ra ^'21 is connected.

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

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

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

As an alkyl group in R ", any of a linear type, a branched chain type, and a cyclic type may be sufficient, and, as for carbon number, 1-15 are preferable.

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

When R "is a cyclic alkyl group, it is preferable that it is C3-C15, It is more preferable that it is C4-C12, Most preferably C5-C10. Specifically, Substitute | substituted by a fluorine atom or a fluorinated alkyl group. The group which removed 1 or more hydrogen atoms from the monocyclo alkan which may or may not be mentioned; The group etc. which removed 1 or more hydrogen atoms from polycyclo alkanes, such as a bicyclo alkan, tricyclo alkan, tetracyclo alkan, etc. are illustrated More specifically, the group which removed 1 or more hydrogen atoms from monocycloalkane, such as cyclopentane, cyclohexane, etc .; adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. The group etc. which removed 1 or more hydrogen atoms from polycycloalkane are mentioned.

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

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

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

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

In the general formulas (a2-r-2), (a2-r-3) and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A ″ may be linear or branched. The alkylene group of is preferable, and a methylene group, an ethylene group, n-propylene group, an isopropylene group, etc. are mentioned, When the alkylene group contains an oxygen atom or a sulfur atom, as the specific example, the alkylene group And groups in which -O- or -S- are interposed between the terminal or the carbon atom of, for example, -O-CH _2- , -CH ₂ -O-CH _2- , -S-CH _2- , -CH ₂ -S-CH ₂ -etc. As A ", a C1-C5 alkylene group or -O- is preferable, A C1-C5 alkylene group is more preferable, and a methylene group is the most preferable.

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

[Formula 34]

[Formula 35]

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

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

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

[Formula 36]

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

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

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

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

[Formula 37]

[Formula 38]

[Formula 39]

A "carbonate-containing cyclic group" represents 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 in the case of only the carbonate ring, the carbonate ring is referred to as a polycyclic group regardless of its structure. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group.

As the carbonate ring-containing cyclic group, any one can be used without particular limitation. Specifically, the group represented by the following general formula (ax3-r-1) (ax3-r-3)-is mentioned, respectively.

[Formula 40]

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

In General Formulas (ax3-r-2) to (ax3-r-3), A ″ is represented by General Formulas (a2-r-2), (a2-r-3), and (a2-r-5). It is the same as A "in.

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

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

[Formula 41]

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

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

[Formula 42]

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

In said formula (a2-1), R is the same as the above. As R, a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 fluorinated alkyl group is preferable, and a hydrogen atom or a methyl group is especially preferable from industrial ease of acquisition.

The formula (a2-1) of 2-valent connecting group Ya of ²¹ is not particularly limited, and may be preferably a divalent hydrocarbon group which may have a substituent, a divalent connecting group, such as containing a hetero atom. The description about the bivalent hydrocarbon group which may have a substituent in Ya ²¹ , and the bivalent coupling group containing a hetero atom may have a substituent in Ya ^x1 in general formula (a10-1) mentioned above. It is the same as that of the description of the bivalent hydrocarbon group and bivalent coupling group containing a hetero atom.

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

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

Examples of the lactone-containing cyclic group, the -SO ₂ -containing cyclic group, and the carbonate-containing cyclic group for Ra ²¹ include the groups represented by general formulas (a2-r-1) to (a2-r-7) described above, Groups represented by general formulas (a5-r-1) to (a5-r-4) and groups represented by general formulas (ax3-r-1) to (ax3-r-3), respectively, are preferable.

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

The structural unit (a2) which the (A1) component has may be 1 type or 2 or more types.

When (A1) component has a structural unit (a2), the ratio of a structural unit (a2) is 0-50 mol% with respect to the total (100 mol%) of all the structural units which comprise the said (A1) component. It is preferable, it is more preferable that it is 5-45 mol%, It is further more preferable that it is 10-40 mol%, 10-30 mol% is especially preferable.

By making ratio of a structural unit (a2) more than a preferable lower limit, the effect by containing a structural unit (a2) is fully acquired, and if it is below an upper limit, it can balance with another structural unit, and various lithographic characteristics It becomes good.

`` Structural unit (a3) ''

In addition to the structural unit (a1), the component (A1) further comprises a structural unit (a3) containing a polar group-containing aliphatic hydrocarbon group (except those corresponding to the structural unit (a1) and the structural unit (a2)). You may have it. When the component (A1) has a structural unit (a3), for example, the acid diffusion length is appropriately adjusted, the adhesion of the resist film to the substrate is increased, the solubility during development is appropriately adjusted, and the etching resistance is improved. By the effect, lithography characteristics and the like become good.

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

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

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

As the structural unit (a3), any one can be used without particular limitation as long as it contains a polar group-containing aliphatic hydrocarbon group.

As a structural unit (a3), the structural unit derived from the acrylate ester which the hydrogen atom couple | bonded with the carbon atom of the (alpha) position may be substituted by the substituent, and the structural unit containing a polar group containing aliphatic hydrocarbon group is preferable.

As a structural unit (a3), when the hydrocarbon group in a polar group containing aliphatic hydrocarbon group is a C1-C10 linear or branched hydrocarbon group, the structural unit derived from the hydroxyethyl ester of acrylic acid is preferable.

Moreover, as a structural unit (a3), when the hydrocarbon group in a polar group containing aliphatic hydrocarbon group is a polycyclic group, the structural unit represented by following formula (a3-1), the structural unit represented by a formula (a3-2), a formula ( The structural unit represented by a3-3) is mentioned as a preferable thing.

[Formula 43]

[Wherein, R is the same as above, j is an integer of 1 to 3, k is an integer of 1 to 3, t 'is an integer of 1 to 3, l is an integer of 1 to 5, s is It is an integer of 1-3.]

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

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

In formula (a3-2), it is preferable that k is 1. It is preferable that the cyano group couple | bonds with the 5-position or 6-position of a norbornyl group.

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

1 type may be sufficient as the structural unit (a3) which (A1) component has, and 2 or more types may be sufficient as it.

When (A1) component has a structural unit (a3), it is preferable that it is 1-40 mol% with respect to the total of all the structural units which comprise the said (A1) component, 2-30 mol% is more preferable, 5 25 mol% is more preferable, and 5-20 mol% is especially preferable.

By making ratio of a structural unit (a3) more than a preferable lower limit, the effect by containing a structural unit (a3) is fully acquired, if it is below an upper limit, it can balance with the other structural unit, and various lithographic characteristics It becomes good.

≪Composition unit (st) ≫

In addition to the structural unit (a1), the component (A1) may further have a structural unit (st) derived from styrene or a derivative thereof. "Styrene" is taken as the concept including what substituted the styrene and the hydrogen atom of the (alpha) position of styrene by substituents, such as an alkyl group and a halogenated alkyl group. The alkyl group as a substituent here includes an alkyl group of 1 to 5 carbon atoms, and the halogenated alkyl group as the substituent includes a halogenated alkyl group of 1 to 5 carbon atoms.

As a "styrene derivative", the thing by which the substituent couple | bonded with the benzene ring of styrene in which the hydrogen atom of the (alpha) position may be substituted by the substituent is mentioned.

In addition, an alpha position (carbon atom of an alpha position) means the carbon atom which the benzene ring couple | bonds unless there is particular notice.

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

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

When (A1) component has a structural unit (st), the ratio of a structural unit (st) is 1-50 mol% with respect to the total (100 mol%) of all the structural units which comprise the (A1) component. It is preferable, and it is more preferable that it is 3-40 mol%.

≪Other structural units≫

(A1) A component may have other structural units other than the structural unit (a1), structural unit (a10), structural unit (a2), structural unit (a3), and structural unit (st) which were mentioned above.

As another structural unit, For example, the structural unit (a9) represented by general formula (a9-1) mentioned later, the structural unit derived from styrene, and the structural unit derived from styrene derivative (however, to a structural unit (a10) The structural unit containing an acid non-aliphatic cyclic group etc. is mentioned, etc. are mentioned.

Constituent unit (a9):

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

[Formula 44]

[In formula, R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. Ya ⁹¹ is a single bond or a divalent linking group. Ya ⁹² is a bivalent coupler. R ⁹¹ is a hydrocarbon group which may have a substituent.]

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

As R, a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 fluorinated alkyl group is preferable, and a hydrogen atom or a methyl group is especially preferable from industrial ease of acquisition.

In the formula (a9-1), the divalent linking group of the Ya ^91, the description may be a general formula (a10-1) it is equal to that of the divalent connecting group in the Ya ^x1. Especially, as Ya ⁹¹ , it is preferable that it is a single bond.

In said formula (a9-1), the bivalent coupling group in Ya ⁹² is the same as the bivalent coupling group of Ya ^x1 in general formula (a10-1) mentioned above.

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

Moreover, in the bivalent coupling group in Ya ⁹² , as a bivalent coupling group containing a hetero atom, -O-, -C (= O) -O-, -C (= O)-, -OC (= O) -O-, -C (= O) -NH-, -NH-, -NH-C (= NH)-(H may be substituted by substituents, such as an alkyl group, an acyl group.), -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) A group represented by -Y ^22- [wherein, Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m 'is an integer of 0-3. Can be mentioned. Especially, -C (= O)-and -C (= S)-are preferable.

In said formula (a9-1), an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, an aralkyl group etc. are mentioned as a hydrocarbon group in R <^91> .

C1-C8 is preferable, C1-C6 is more preferable, C1-C4 is more preferable, A alkyl group in R <^91> may be linear or branched chain form may be sufficient as it. Specifically, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, etc. are mentioned as a preferable thing.

As for the monovalent alicyclic hydrocarbon group in R <^91> , C3-C20 is preferable, C3-C12 is more preferable, Polycyclic type or monocyclic type may be sufficient as it. As a monocyclic alicyclic hydrocarbon group, the group remove | excluding one or more hydrogen atoms from the monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclobutane, cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, the group remove | excluding one or more hydrogen atoms from polycycloalkane is preferable, As the polycycloalkane, a C7-12 thing is preferable, Specifically, adamantane, norbornane, Isobornane, tricyclodecane, tetracyclododecane and the like.

It is preferable that it is C6-C18, as for the aryl group in R <^91> , it is more preferable that it is C6-C10, and specifically, a phenyl group is especially preferable.

To an aralkyl group in R ⁹¹ is an "aryl group in R ^91," an aralkyl group is bonded alkylene group and the group having 1 to 8 carbon atoms is preferable, according to an alkylene group wherein the "R ⁹¹ having 1 to 6 carbon atoms and the aryl group "is an aralkyl group and more preferably bonded, are an aryl group, an aralkyl group" is bonded to an alkylene group in the "R ⁹¹ group having from 1 to 4 carbon atoms is particularly preferred.

It is preferable that one part or all part of the hydrogen atom of the said hydrocarbon group is substituted by the fluorine atom, and, as for the hydrocarbon group in R <^91> , it is more preferable that 30-100% of the hydrogen atoms of the said hydrocarbon group are substituted by the fluorine atom. Especially, it is especially preferable that all of the hydrogen atoms of the alkyl group mentioned above are a perfluoroalkyl group substituted by the fluorine atom.

The hydrocarbon group in R ⁹¹ may have a substituent. As a substituent, there may be mentioned a halogen atom, an oxo group (= O), hydroxyl (-OH), amino _{(-NH 2), -SO 2 -NH} 2 and the like. In addition, a part of the carbon atoms constituting the hydrocarbon group may be substituted with a substituent containing a hetero atom. As a substituent containing the hetero atom, -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 lactone-containing cyclic groups represented by General Formulas (a2-r-1) to (a2-r-7).

In addition, in R ^91, the hydrocarbon group has a substituent, the formula (a5-r-1) ~ -SO 2 each represent a (a5-r-4) - containing cyclic group; Substituted aryl group, monovalent heterocyclic group, etc. which are represented by a following formula are mentioned.

[Formula 45]

Among the structural units (a9), structural units represented by the following general formula (a9-1-1) are preferable.

[Formula 46]

[Wherein, R is the same as above, 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), Ya 91, R} 91, are the same as the description of the R. In addition, R ⁹² is an oxygen atom or a sulfur atom.

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

[Formula 47]

[Formula 48]

[Formula 49]

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

When (A1) component has a structural unit (a9), the ratio of a structural unit (a9) is 1-40 mol% with respect to the total (100 mol%) of all the structural units which comprise the (A1) component. It is preferable, 3-30 mol% is more preferable, 5-25 mol% is further more preferable, 10-20 mol% is especially preferable.

By making ratio of a structural unit (a9) more than a lower limit, for example, an acid diffusion length is adjusted suitably, the adhesiveness of a resist film to a board | substrate is improved, the solubility at the time of image development is adjusted suitably, an effect of improving etching tolerance, etc. Is obtained, the upper limit value or less can be balanced with other structural units, and various lithographic characteristics are good.

Constituent unit (a4):

Structural unit (a4) is a structural unit containing an acid non-aliphatic cyclic group. The component (A1) may further have a structural unit (a4) in addition to the structural unit (a1).

When the (A1) component has a structural unit (a4), the dry etching tolerance of the formed resist pattern improves. Moreover, the hydrophobicity of (A) component becomes high. It is thought that the improvement of hydrophobicity contributes to the improvement of resolution, the shape of a resist pattern, etc., especially in a solvent developing process.

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

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

Particularly, at least one selected from tricyclodecyl group, adamantyl group, tetracyclododecyl group, isobornyl group and norbornyl group is preferable in view of industrial availability. These polycyclic groups may have a C1-C5 linear or branched alkyl group as a substituent.

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

[Formula 50]

[Wherein, R ^α is the same as above.]

The structural unit (a4) which the (A1) component has may be 1 type or 2 or more types.

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

By making ratio of a structural unit (a4) more than a preferable lower limit, the effect by containing a structural unit (a4) is fully acquired, and setting it as the below preferable upper limit makes it easy to balance with another structural unit.

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

It is preferable that (A1) component contains the high molecular compound (A1-1) (henceforth "the (A1-1) component") which has a structural unit (a1).

As a preferable (A1-1) component, For example, the high molecular compound which has a repeating structure of a structural unit (a1) and a structural unit (a10), and the polymer which has a repeating structure of a structural unit (a1) and a structural unit (st) Compounds and the like.

In addition to the combination of the two respective structural units, as the third or three or more structural units, the above-described structural units may be appropriately combined according to the desired effect. As a combination of three or more structural units, the combination of a structural unit (a1), a structural unit (a10), and a structural unit (st) etc. are mentioned, for example.

Such a component (A1) dissolves the monomer which guides each structural unit in a polymerization solvent, for example, azobisisobutyronitrile (AIBN), azobisisobutyrate dimethyl (for example, V-601, etc.). It can manufacture by adding and superposing | polymerizing by radical polymerization initiators, such as). Or such (A1) component superposes | polymerizes the precursor (monomer in which the functional group of the monomer was protected) of the monomer which guide | induces a structural unit (a1), and the monomer which guides structural units other than a structural unit (a1) as needed. It can manufacture by melt | dissolving in a solvent, adding a radical polymerization initiator as mentioned above to this, and superposing | polymerizing, and then performing a deprotection reaction. In addition, during the polymerization, for _{example, HS-CH 2 -CH 2 -CH} 2 -C (CF 3) By using in combination a chain transfer agent such as ₂ -OH, -C (CF _{3) 2} -OH at the terminal You may introduce | transduce a group. Thus, the copolymer into which the hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group was substituted by the fluorine atom was introduce | transduced is effective in reducing a development defect and reducing LER (line edge roughness: uneven unevenness of a line side wall).

The mass average molecular weight (Mw) (polystyrene conversion basis by gel permeation chromatography (GPC)) of (A1) component is not specifically limited, 1000-50000 are preferable, 2000-30000 are more preferable, 3000 20000 is more preferable.

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

The dispersion degree (Mw / Mn) of (A1) component is not specifically limited, 1.0-4.0 are preferable, 1.0-3.0 are more preferable, 1.1-2.0 are especially preferable. In addition, Mn represents a number average molecular weight.

About (A2) component

The resist composition of this embodiment is a base material component (hereinafter referred to as "(A2) component") in which the solubility in a developing solution changes due to the action of an acid, which does not correspond to the component (A1), as the component (A). You may use together.

It does not specifically limit as (A2) component, What is necessary is just to select arbitrarily from the many thing conventionally known as a base component for chemically amplified resist compositions.

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

As for the ratio of the component (A1) in (A) component, 25 mass% or more is preferable with respect to the gross mass of (A) component, 50 mass% or more is more preferable, 75 mass% or more is more preferable, 100 Mass% may be sufficient. If the ratio is 25 mass% or more, the resist pattern which is excellent in various lithography characteristics, such as high sensitivity, resolution, and roughness improvement, will be formed easily.

In the resist composition of this embodiment, content of (A) component is 20 mass% or more. By making content of (A) component 20 mass% or more, when a resist composition is apply | coated to a board | substrate and a resist film is formed, it becomes possible to form a thick film resist film with a film thickness of 5 micrometers or more. 25 mass% or more is preferable, and, as for content of (A) component, 30 mass% or more is more preferable. By making content of (A) component in a resist composition higher, the resist composition which can form a resist film (for example, 8 micrometers or more) of a higher film thickness can be obtained.

Although the upper limit of content of (A) component will not be specifically limited if it is the density | concentration which can form a resist film, For example, it can be 50 mass% or less. The range of content of (A) component can be 20-50 mass%, for example, 25-45 mass% is preferable, and 30-40 mass% is more preferable.

What is necessary is just to adjust according to the resist film thickness etc. which are formed.

<(D0) component>

(D0) A component is a tertiary monoamine compound represented by the following general formula (d0). (D0) component acts as a quencher which traps the acid generate | occur | produced by exposure in a resist composition. The resist composition of the present embodiment contains 0.01 to 0.05 parts by mass of the (D0) component with respect to 100 parts by mass of the component (A), whereby lithography characteristics such as sensitivity and CDU are good, and a resist pattern having a good shape is formed. You can do it.

[Formula 51]

[Wherein, Rx ¹ to Rx ³ each independently represent a hydrocarbon group which may have a substituent. Two or more of Rx ¹ to Rx ³ may be bonded to each other to form a ring structure.]

The formula (d0) of, Rx ^1, Rx ² and Rx ³ are, each independently, a hydrocarbon group which may have a substituent.

The hydrocarbon group in Rx ¹ , Rx ² and Rx ³ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group as the hydrocarbon group in Rx ¹ , Rx ² and Rx ³ include a linear or branched alkyl group or a cyclic aliphatic hydrocarbon group.

The linear alkyl group preferably has 1 to 15 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 10 carbon atoms. As a specific example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n -An undecyl group, n-dodecyl group, etc. are mentioned.

The branched alkyl group preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms. Specifically, isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, etc. are mentioned.

The linear or branched alkyl group in Rx ¹ , Rx ² and Rx ³ may or may not have a substituent. As this substituent, a halogen atom, a hydroxyl group, an oxo group (= O), an ester bond [-C (= O) -O-], an ether bond (-O-), etc. are mentioned, for example. The ester bond and ether bond as a substituent are groups which substitute the methylene group which comprises an alkyl group. In addition, the linear or branched alkyl group in Rx ¹ , Rx ² and Rx ³ does not have an amino group as a substituent.

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

Especially as this substituent, a hydroxyl group is preferable.

The cyclic aliphatic hydrocarbon group in Rx ¹ , Rx ² and Rx ³ may be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, the group remove | excluding one hydrogen atom from monocycloalkane is preferable. As this monocycloalkane, a C3-C6 thing is preferable, A cyclopentane, a cyclohexane, etc. are mentioned specifically, A cyclopentane is especially preferable. As the polycyclic aliphatic hydrocarbon group, a group in which one hydrogen atom has been removed from a polycycloalkane is preferable, and as the polycycloalkane, one having 7 to 12 carbon atoms is preferable, and specifically, adamantane, norbornane and iso Bornan, tricyclodecane, tetracyclo dodecane, etc. are mentioned.

The cyclic aliphatic hydrocarbon group in Rx ¹ , Rx ² and Rx ³ may or may not have a substituent. As this substituent, a halogen atom, a hydroxyl group, an oxo group (= O), an alkyl group, ester bond [-C (= O) -O-], an ether bond (-O-), etc. are mentioned, for example. have. An ester bond and an ether bond as a substituent are groups which substitute the methylene group which comprises a cyclic aliphatic hydrocarbon group. In addition, the cyclic aliphatic hydrocarbon group in Rx ¹ , Rx ² and Rx ³ does not have an amino group as a substituent.

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

As an alkyl group as said substituent, a C1-C6 alkyl group is preferable. It is preferable that this alkyl group is a linear or branched chain type. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, etc. are mentioned. Among these, a methyl group or an ethyl group is preferable.

Especially as this substituent, a hydroxyl group or an alkyl group is preferable.

An aromatic hydrocarbon group as a hydrocarbon group in Rx ¹ , Rx ² and Rx ³ is a hydrocarbon group having at least one aromatic ring.

The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 pi electrons, and may be monocyclic or polycyclic. It is preferable that carbon number of an aromatic ring is 5-30, C5-20 is more preferable, 6-15 are still more preferable, 6-12 are especially preferable. As an aromatic ring, Specifically, aromatic hydrocarbon rings, such as benzene, naphthalene, anthracene, phenanthrene; And aromatic hetero rings in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom (except for nitrogen atoms). As a hetero atom in an aromatic hetero ring, an oxygen atom, a sulfur atom, etc. are mentioned. As an aromatic hetero ring, a furan ring, a thiophene ring, etc. are mentioned specifically ,.

As an aromatic hydrocarbon group in Rx ¹ , Rx ² and Rx ³ , specifically, a group (aryl group or heteroaryl group) in which one hydrogen atom is removed from the aromatic hydrocarbon ring or aromatic hetero ring; A group in which one hydrogen atom is removed from an aromatic compound (eg, biphenyl, fluorene, etc.) containing two or more aromatic rings; Groups in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic hetero ring is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2 And arylalkyl groups such as naphthylethyl group). It is preferable that carbon number of the alkylene group couple | bonded with the said aromatic hydrocarbon ring or aromatic heterocyclic ring is 1-4, It is more preferable that it is 1-2, It is especially preferable that it is one.

The aromatic hydrocarbon groups in Rx ¹ , Rx ² and Rx ³ may or may not have a substituent. As this substituent, a halogen atom, a hydroxyl group, an oxo group (= O), an alkyl group, etc. are mentioned. As a halogen atom and an alkyl group as a substituent, the thing similar to what was mentioned as a substituent of the said cyclic aliphatic hydrocarbon group is mentioned.

Especially as this substituent, a hydroxyl group or an alkyl group is preferable.

Rx ^1, Rx ² and Rx ³ are, or may by this combination of two or more to form a ring. The ring structure formed by two or more of such Rx ¹ , Rx ² and Rx ³ forms a ring structure together with the nitrogen atom in formula (d0). The ring structure may be an aliphatic heterocyclic ring containing a nitrogen atom in the ring structure or an aromatic heterocyclic ring. Moreover, the polycyclic structure which consists of ring structures other than this may be sufficient as this ring structure.

The aliphatic heterocyclic ring formed by two or more of Rx ¹ , Rx ² and Rx ³ may be polycyclic or monocyclic. As an aliphatic heterocyclic ring, a C3-C6 thing is preferable, Specifically, aziridine, azetidine, pyrrolidine, piperidine, etc. are mentioned.

The aromatic heterocyclic ring formed by two or more of Rx ¹ , Rx ² and Rx ³ may be polycyclic or monocyclic. As an aromatic hetero ring, a C3-C12 thing is preferable, Specifically, an aziline, an azet, a pyrrole, a pyridine, an azepine etc. are mentioned.

Rx ^1, Rx ^2, and ring structure of two or more of Rx ³ is formed by combining is, and may have a substituent, and does not have. As this substituent, a halogen atom, a hydroxyl group, an oxo group (= O), an alkyl group, etc. are mentioned, for example. The halogen atom and alkyl group as said substituent are the same as what was mentioned as a substituent in the said cyclic aliphatic hydrocarbon group.

With Rx ^1, Rx ² and the substituents in the ring structure formed by combining two or more of Rx ³ is, among others, alkyl groups are preferred.

Rx ^1, Rx ² and two ring structures or more is formed by the combination of Rx ³ is, it is more preferable to have a carbon atom in the substituent adjacent the nitrogen atom preferably has a substituent, and Formula (d0) .

As a preferable example of (D0) component, the compound represented by the following general formula (d0-1) or (d0-2) is mentioned.

[Formula 52]

[Formula (d0-1) of, Rx ¹¹ Rx ~ ¹³ are, each independently, it represents a group which may have a substituent group selected from the group of linear branched, or aromatic hydrocarbon. However, there is no case that all of the Rx ¹¹ Rx ~ ¹³ underlying an aromatic hydrocarbon. In formula (d0-2), Ry ¹ to Ry ³ represent a linear or branched alkyl group which may have a substituent. ny1 represents the integer of 0-3.]

Compound represented by formula (d0-1)

In the general formula (d0-1), Rx ¹¹ Rx ~ ¹³ are, each independently, it represents a group which may have a substituent group selected from the group of linear branched, or aromatic hydrocarbon. However, there is no case that all of the Rx ¹¹ Rx ~ ¹³ underlying an aromatic hydrocarbon.

The linear alkyl group in Rx ¹¹ , Rx ^12, and Rx ¹³ preferably has 1 to 15 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 12 carbon atoms, and 2 to 10 carbon atoms. Especially preferred. Specific examples are the formula (d0) can be given as in the linear alkyl group as the hydrocarbon group in Rx ^1, Rx ² and Rx ³ the same as all.

The branched alkyl group in Rx ¹¹ , Rx ¹² and Rx ¹³ preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms. Specific examples are the formula (d0) can be given as in the branched alkyl group as the hydrocarbon group in Rx ^1, Rx ² and Rx ³ the same as all.

The linear or branched alkyl group in Rx ¹¹ , Rx ¹² and Rx ¹³ may or may not have a substituent. The substituent has the formula (d0) can be given in the Rx ^1, Rx ² and as the substituent of the linear or branched alkyl group in Rx ³ the same as all. Especially as this substituent, a hydroxyl group is preferable.

The aromatic hydrocarbon group in Rx ¹¹ , Rx ¹² and Rx ¹³ may be monocyclic or polycyclic. It is preferable that carbon number of an aromatic ring is 5-30, 5-20 are more preferable, 6-15 are more preferable, and 6-12 are especially preferable. Specific examples are the formula (d0) can be given in an aromatic hydrocarbon group as the hydrocarbon group in Rx ^1, Rx ² and Rx ³ the same as all.

The groups Rx ^11, Rx ^12, and an aromatic hydrocarbon in the Rx ^13, need not, and may have a substituent, with. The substituent has the formula (d0) can be given as the substituent of the aromatic hydrocarbon group in the in Rx ^1, Rx ² and Rx ³ the same as all. Especially as this substituent, an alkyl group is preferable.

Rx ^11, Rx ¹² and Rx ¹³ is not the case that both, is an aromatic hydrocarbon group. If Rx ^11, Rx ¹² and Rx ¹³ of which one is an aromatic hydrocarbon group, and either one is the hydrocarbon group is preferably aromatic.

As a preferable example of a compound represented by the said general formula (d0-1), the compound represented by the following general formula (d0-1-1) or (d0-1-2) is mentioned.

[Formula 53]

Equation (d0-1-1) of, Rx Rx ¹¹¹ ~ ¹¹³ are, each independently represent a linear or branched alkyl group which may have a substituent. In formula (d0-1-2), Rx ¹²¹ to Rx ¹²³ each independently represent a linear or branched alkyl group which may have a substituent. nx1 represents the integer of 0-5.]

In General Formula (d0-1-1), Rx ¹¹¹ to Rx ¹¹³ each independently represent a linear or branched alkyl group which may have a substituent. As a linear or branched alkyl group in Rx ¹¹¹ , Rx ¹¹² and Rx ¹¹³ , a linear or branched alkyl group in Rx ¹ , Rx ² and Rx ³ in the general formula (d0). And the same thing as.

The linear or branched alkyl group in Rx ¹¹¹ , Rx ¹¹² and Rx ¹¹³ may or may not have a substituent. The substituent has the formula (d0) can be given in the Rx ^1, Rx ² and as the substituent of the linear or branched alkyl group in Rx ³ the same as all. Especially as this substituent, a hydroxyl group is preferable.

It is especially preferable that all of Rx ¹¹¹ -Rx ¹¹³ are the same group.

In the general formula ^{(d0-1-2), Rx 121, Rx} 122 and Rx ¹²³ are, each independently, represents a linear or branched alkyl group which may have a substituent.

As the linear or branched alkyl group for Rx ¹²¹ and Rx ¹²² , the same as the linear or branched alkyl group for Rx ¹ , Rx ² and Rx ³ in General Formula (d0). Can be mentioned.

The linear or branched alkyl group in Rx ¹²¹ and Rx ¹²² may or may not have a substituent. The substituent has the formula (d0) can be given in the Rx ^1, Rx ² and as the substituent of the linear or branched alkyl group in Rx ³ the same as all. Especially as this substituent, a hydroxyl group is preferable.

It is preferable that Rx ¹²¹ and Rx ¹²² are the same groups as each other.

It is preferable that a linear alkyl group in Rx ¹²³ is C1-C10, C1-C6 is more preferable, C1-C3 is still more preferable, C1-C2 is especially preferable. Specific examples are the above formula there may be mentioned (d0) of the Rx ^1, that either a specific example of the linear alkyl group according to the Rx ² and Rx ^3, among them, a methyl group or an ethyl group is preferred.

The branched alkyl group in Rx ¹²³ is preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms. Specific examples are the formula (d0) can be given in the Rx ^1, all the specific examples of branched alkyl groups in the Rx ² and Rx ^3. Especially, isopropyl group, isobutyl group, or tert- butyl group is preferable.

The linear or branched alkyl group in Rx ¹²³ may or may not have a substituent. The substituent has the formula (d0) can be given in the Rx ^1, Rx ² and as the substituent of the linear or branched alkyl group in Rx ³ the same as all.

Nx1 represents the integer of 0-5 in general formula (d0-1-2). 0-3 are preferable, as for nx1, 0-2 are more preferable, and 0 or 1 is more preferable.

The specific example of a compound represented by the said general formula (d0-1) is shown below.

[Formula 54]

In addition to the above examples, specific examples of the compound represented by the general formula (d0-1) include trimethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, and tri-n- Trialkylamines such as hexylamine, tri-n-heptylamine, tri-n-nonylamine and tri-n-dodecylamine; Trialkyl alcohol amines such as tri-n-octanol amine; Tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris [2- {2 -(2-hydroxyethoxy) ethoxy} ethyl] amine, triethanolamine triacetate, etc. are mentioned.

Compound represented by formula (d0-2)

In General Formula (d0-2), Ry ¹ , Ry ^2, and Ry ³ each independently represent a linear or branched alkyl group which may have a substituent.

The linear alkyl group in Ry ¹ and Ry ² is preferably 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms. Specific examples are the formula (d0) can be given in the Rx ^1, that either a specific example of the linear alkyl group according to the Rx ² and Rx ^3.

The branched alkyl group in Ry ¹ and Ry ² is preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms. Specific examples are the formula (d0) can be given in the Rx ^1, all the specific examples of branched alkyl groups in the Rx ² and Rx ^3. Especially, isopropyl group, isobutyl group, or tert- butyl group is preferable.

The linear or branched alkyl group in Ry ¹ and Ry ² may or may not have a substituent. The substituent has the formula (d0) can be given in the Rx ^1, Rx ² and as the substituent of the linear or branched alkyl group in Rx ³ the same as all.

Among them, Ry ¹ and Ry ² are preferably a branched alkyl group, more preferably a branched alkyl group having no substituent, and more preferably an isopropyl group, isobutyl group, or tert-butyl group. Ry ¹ and Ry ² are preferably identical group each other.

Alkyl group linear in Ry ³ is preferably a carbon number of 1 to 10 carbon atoms and 2 to 6 are more preferable, the carbon number is more preferably 2-4. Specific examples are the formula (d0) can be given in the Rx ^1, that either a specific example of the linear alkyl group according to the Rx ² and Rx ^3.

The branched alkyl group in Rx ¹²³ is preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms. Specific examples are the formula (d0) can be given in the Rx ^1, all the specific examples of branched alkyl groups in the Rx ² and Rx ^3.

The linear or branched alkyl group in Ry ¹ and Ry ² may or may not have a substituent. The substituent has the formula (d0) can be given in the Rx ^1, Rx ² and as the substituent of the linear or branched alkyl group in Rx ³ the same as all.

Ny1 is an integer of 0-3 in general formula (d0-2). It is preferable that ny1 is 0-2, It is more preferable that it is 0 or 1, It is further more preferable that it is 0.

The specific example of a compound represented by general formula (d0-2) is shown below.

[Formula 55]

As the component (D0), one type may be used alone, or two or more types may be used in combination.

In the resist composition of this embodiment, content of (D0) component is 0.01-0.05 mass parts with respect to 100 mass parts of (A) component. By making content of (D0) component into the said range, when forming a thick-film resist film with a film thickness of 5 micrometers or more, CDU can be improved while maintaining a high sensitivity, and the resist pattern of a favorable shape can be obtained. It is more preferable that it is 0.02-0.05 mass parts with respect to 100 mass parts of (A) component, and, as for content of (D0) component, it is still more preferable that it is 0.02-0.04 mass part.

<Optional component>

`` (B) Component: Acid Generator Component ''

It is preferable that the resist composition of this embodiment contains the acid generator component (component (B)) which generate | occur | produces an acid by exposure in addition to (A) component and (D0) component.

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

Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, and oxime sulfonate acid generators; Diazomethane-based acid generators such as bisalkyl or bisarylsulfonyldiazomethanes and poly (bissulfonyl) diazomethanes; Nitrobenzyl sulfonate-type acid generators, iminosulfonate-type acid generators, and disulfone-type acid generators are mentioned.

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

[Formula 56]

[In formula, R <^101> , R <^104> -R <^108> is respectively independently the cyclic group which may have a substituent, the chain alkyl group which may have a substituent, or the linear alkenyl group which may have a substituent. R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring. R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Y ¹⁰¹ is a divalent linking group containing a single bond or an oxygen atom. V ¹⁰¹ to V ¹⁰³ are each independently a single bond, an alkylene group, or a fluorinated alkylene group. L ¹⁰¹ to L ¹⁰² each independently represent a single bond or an oxygen atom. L ¹⁰³ to L ¹⁰⁵ are each independently a single bond, -CO-, or -SO _2- . m is an integer of 1 or more, and M ' ^{m +} is an onium cation of m value.]

{Noon}

Anion part of component (b-1)

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

Cyclic group which may have a substituent:

The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means the hydrocarbon group which does not have aromaticity. Moreover, it may be saturated or unsaturated may be sufficient as an aliphatic hydrocarbon group, and it is preferable that it is normally 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 3 to 30, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. . However, the carbon number does not include the carbon number in the substituent.

As an aromatic ring which an aromatic hydrocarbon group in R <^101> has, Specifically, the aromatic heterocyclic in which a part of the carbon atoms which comprise benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or these aromatic rings was substituted by the hetero atom Ring etc. are mentioned. As a hetero atom in an aromatic hetero ring, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned.

As an aromatic hydrocarbon group in R <^101> , the group (aryl group: For example, a phenyl group, a naphthyl group, etc.) which removed one hydrogen atom from the said aromatic ring specifically, one of the hydrogen atoms of the said aromatic ring is an alkylene group. Substituted group (For example, arylalkyl groups, such as a benzyl group, a phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.), etc. are mentioned. It is preferable that carbon number of the said alkylene group (alkyl chain in an arylalkyl group) is 1-4, C1-C2 is more preferable, C1-C is especially preferable.

^Examples of the cyclic aliphatic hydrocarbon group for R ¹⁰¹ include aliphatic hydrocarbon groups containing a ring in the structure.

The aliphatic hydrocarbon group containing a ring in this structure includes an alicyclic hydrocarbon group (a group in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring) and an alicyclic hydrocarbon group bonded to a terminal of a linear or branched aliphatic hydrocarbon group. And groups in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group.

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

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

Especially, as the cyclic aliphatic hydrocarbon group for R ¹⁰¹ , a group in which one or more hydrogen atoms are removed from a monocycloalkane or a polycycloalkane is preferable, and a group in which one hydrogen atom is removed from a polycycloalkane is more preferable, Particularly preferred are cyclic groups having an adamantyl group, norbornyl group and a steroid skeleton, and most preferred are cyclic groups having an adamantyl group and a steroid skeleton.

The linear or branched aliphatic hydrocarbon group which may be bonded to an alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and more preferably 1 carbon atom. 3 is especially preferable.

As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specifically, a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], and a trimethylene group [-( CH ₂ ) _3- ], tetramethylene group [-(CH ₂ ) _4- ], pentamethylene group [-(CH ₂ ) _5- ], and the like.

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

Moreover, the cyclic hydrocarbon group in R <^101> may contain a hetero atom like a heterocyclic ring. Specifically, the lactone-containing cyclic groups represented by general formulas (a2-r-1) to (a2-r-7), respectively, and the general formulas (a5-r-1) to (a5-r-4), respectively -SO ₂ represents-containing cyclic group, to the other can be a formula (r-hr-1) ~ a complex cyclic group represents respectively the (r-hr-16).

[Formula 57]

As a substituent in the cyclic group of R <^101> , an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, etc. are mentioned, for example.

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

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

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

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

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

Chain alkyl group which may have a substituent:

As a linear alkyl group of R <^101> , either linear or branched chain may be sufficient.

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

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

Chain alkenyl groups which may have a substituent:

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

As a linear alkenyl group, a linear alkenyl group is preferable among these, a vinyl group and a propenyl group are more preferable, and a vinyl group is especially preferable.

Of the substituents in groups alkyl or alkenyl chain of the R ¹⁰¹ is, e.g., an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a cyclic group etc. in the R ¹⁰¹ Can be.

Especially, R ¹⁰¹ is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, the group remove | excluding one or more hydrogen atoms from the phenyl group, naphthyl group, and polycycloalkane; Lactone-containing cyclic groups represented by general formulas (a2-r-1) and (a2-r-3) to (a2-r-7), respectively; Preferred are -SO ₂ -containing cyclic groups represented by general formulas (a5-r-1) to (a5-r-4).

In the formula (b-1), Y ¹⁰¹ is a divalent linking group comprising a single bond or an oxygen atom.

When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, the Y ¹⁰¹ may contain atoms other than an oxygen atom. As atoms other than an oxygen atom, a carbon atom, a hydrogen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example.

As a bivalent coupling group containing such an oxygen atom, the coupling group represented by the said general formula (y-al-1) (y-al-8), respectively is mentioned, for example.

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

In said formula (b-1), ^V101 is a single bond, an alkylene group, or a fluorinated alkylene group. Group is an alkylene group, a fluorinated alkylene group in V ^101, preferably having a carbon number of 1-4. A fluorinated alkylene group in the V ¹⁰¹ is, a part or all of the hydrogen atoms of the alkylene group of the ¹⁰¹ V may be substituted with a fluorine atom. Especially, it is preferable that V <^101> is a single bond or a C1-C4 fluorinated alkylene group.

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

As a specific example of the anion part of (b-1) component, for example, when ^Y101 becomes a single bond, fluorinated alkyl sulfo, such as a trifluoromethanesulfonate anion and a perfluorobutanesulfonate anion, for example. Nate anion; When ^Y101 is a bivalent coupling group containing an oxygen atom, the anion represented by either of following formula (an-1)-(an-3) is mentioned.

[Formula 58]

[Wherein, R ″ ¹⁰¹ may have an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group represented by the above formulas (r-hr-1) to (r-hr-6), or a substituent; A linear alkyl group. R ″ ¹⁰² is an aliphatic cyclic group which may have a substituent, and lactones represented by general formulas (a2-r-1) and (a2-r-3) to (a2-r-7), respectively. represented by containing cyclic group, or the formula (a5-r-1) ~ (a5-r-4) respectively, -SO ₂ - containing a cyclic group. R ″ ¹⁰³ is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent. V ″ ¹⁰¹ is a single bond or an alkyl having 1 to 4 carbons. Or a fluorinated alkylene group having 1 to 4 carbon atoms. R ¹⁰² is a fluorine atom or a C1-5 fluorinated alkyl group. v "are each independently an integer of 0-3, q" is each independently an integer of 1-20, and n "is 0 or 1.]

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

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

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

V ″ ¹⁰¹ is preferably a single bond or a fluorinated alkylene group, and more preferably a single bond or a fluorinated alkylene group having 1 to 3 carbon atoms. When V ″ ¹⁰¹ is a fluorinated alkylene group, -V ″ ¹⁰¹ -C (F V ″ ¹⁰¹ in) (R ″ ¹⁰² ) -SO ₃ ^- is -CF _2- , -CHF-, -CF ₂ CF _2- , -CHFCF _2- , -CF (CF ₃ ) CF ₂ -,- CH (CF ₃₎ CF ₂ - is preferable, and, -CF ₂ -, -CHF- is more preferable.

R ¹⁰² is a fluorine atom or a C1-5 fluorinated alkyl group. R ¹⁰² is preferably a fluorine atom or a C 1-5 perfluoroalkyl group, and more preferably a fluorine atom.

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

Anion part of component (b-2)

In formula (b-2), R <^104> , R <^105> is respectively independently the cyclic group which may have a substituent, the chain alkyl group which may have a substituent, or the linear alkenyl group which may have a substituent, The same thing as R <^101> in said Formula (b-1) is mentioned, respectively. However, R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring.

R ¹⁰⁴ and R ¹⁰⁵ are each preferably a linear alkyl group which may have a substituent, and more preferably a linear or branched alkyl group or a linear or branched fluorinated alkyl group.

It is preferable that carbon number of this linear alkyl group is 1-10, More preferably, it is C1-C7, More preferably, it is C1-C3. ^{Carbon number} of the chain alkyl group of R <^104> , R <^105> is so preferable that it is small, for the reason that the solubility to the solvent for resists is also good in the said carbon number range. Moreover, in the chain alkyl group of R <^104> , R <^105> , since the intensity | strength of an acid becomes stronger, the number of hydrogen atoms substituted with the fluorine atom becomes preferable, and it is preferable. The proportion of the fluorine atoms in the chain alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably, a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. to be.

In formula (b-2), V ¹⁰² and V ¹⁰³ are each independently a single bond, an alkylene group, or a fluorinated alkylene group, and examples thereof include the same as V ¹⁰¹ in formula (b-1).

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

Anion part of component (b-3)

In formula (b-3), R <^106> -R <^108> is respectively independently the cyclic group which may have a substituent, the linear alkyl group which may have a substituent, or the linear alkenyl group which may have a substituent, The same thing as R <^101> in Formula (b-1) is mentioned, respectively.

L ¹⁰³ to L ¹⁰⁵ are each independently a single bond, -CO-, or -SO _2- .

{Cateonbu}

In formulas (b-1), (b-2) and (b-3), m is an integer of 1 or more, M ' ^{m +} is m-valent onium cation, and sulfonium cation and iodonium cation are preferable. Examples thereof include organic cations represented by general formulas (ca-1) to (ca-4), for example.

[Formula 59]

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

As an aryl group in R <^201> -R <^207> and R <^211> -R <^212> , a C6-C20 aryl group is mentioned, A phenyl group and a naphthyl group are preferable.

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

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

Examples of the substituent which R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and the following general formula (ca-r-1) Groups represented by)-(ca-r-7) are mentioned, respectively.

[Formula 60]

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

R 'cyclic group which may have a substituent group ^201, a group the alkyl group of the chain which may be substituted, or alkenyl chain which may have a substituent, the same ones as in R ¹⁰¹ to be described later formula (b-1) In addition, the thing similar to the acid dissociable group represented by Formula (a1-r-2) mentioned above as a cyclic group which may have a substituent or the chain alkyl group which may have a substituent is mentioned.

When R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ , and R ²¹¹ to R ²¹² are bonded to each other to form a ring together with a sulfur atom in the formula, hetero atoms such as a sulfur atom, an oxygen atom, a nitrogen atom, a carbonyl group, Bonding through a functional group such as -SO-, -SO _2- , -SO _3- , -COO-, -CONH- or -N (R _N )-(wherein R _N is an alkyl group having 1 to 5 carbon atoms) You may also As a ring formed, it is preferable that one ring which contains the sulfur atom in a formula in the ring skeleton is a 3-10 membered ring including a sulfur atom, and it is especially preferable that it is a 5-7 membered ring. Specific examples of the ring to be formed include, for example, a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone Ring, thianthrene ring, phenoxatiin ring, tetrahydrothiophenium ring, tetrahydrothiopyranium ring and the like.

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

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

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

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

As an alkenyl group in R <^210> , it is preferable that carbon number is 2-10. -SO ₂ that is, may have a substituent in R ²¹⁰ - by-containing cyclic group "-SO ₂ - containing the cyclic group" is preferable, and more preferably groups represented by the above-mentioned formula (a5-r-1) Do.

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

Arylene groups of the Y ^201, may be mentioned a group removed a hydrogen atom from the aryl groups exemplified as the aromatic hydrocarbon group in R ¹⁰¹ to be described later of the formula (b-1).

Examples of the alkylene group and the alkenylene group for Y ²⁰¹ include groups in which one hydrogen atom is removed from a group exemplified as a chain alkyl group and a chain alkenyl group in R ¹⁰¹ in formula (b-1) described later. have.

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

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

As the divalent linking group for W ²⁰¹ , a divalent hydrocarbon group which may have a substituent is preferable, and the divalent hydrocarbon group which may have the same substituent as Ya ²¹ in General Formula (a2-1) described above will be exemplified. Can be. The divalent linking group for W ²⁰¹ may be any of linear, branched, and cyclic, and is preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of the arylene group is preferable. As an arylene group, a phenylene group, a naphthylene group, etc. are mentioned, A phenylene group is especially preferable.

Connection of the trivalent group is ²⁰¹ W, and ²⁰¹ W the group 1 to remove the hydrogen atom from the divalent linking group in, in addition to the divalent linking group, and the like which combines the divalent connecting group. As the trivalent linking group for W ²⁰¹ , a group in which two carbonyl groups are bonded to an arylene group is preferable.

Specifically as a preferable cation represented by said formula (ca-1), the following general formula (ca-1-1)-(ca-1-78), (ca-1-101)-(ca-1-149) The cation shown by each is mentioned.

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

[Formula 61]

[Formula 62]

[Formula 63]

[Formula 64]

[Formula 65]

[Formula 66]

[Formula 67]

[Formula 68]

[Formula 69]

[Formula 70]

[Wherein, R ″ ²⁰¹ is a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group and a cyan, which are mentioned as substituents which R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² may have. And a group represented by a no group, an amino group, an aryl group, and general formulas (ca-r-1) to (ca-r-7).]

Specifically as a preferable cation represented by said formula (ca-2), the cation represented by the following formula (ca-2-1)-(ca-2-3), diphenyl iodonium cation, bis (4) -tert- butylphenyl) iodonium cation.

[Formula 71]

Specifically as a preferable cation represented by said formula (ca-3), the cation shown by the following formula (ca-3-1)-(ca-3-7) is mentioned, respectively.

[Formula 72]

As a preferable cation represented by said Formula (ca-4), the cation shown by the following formula (ca-4-1)-(ca-4-2) is mentioned specifically ,.

[Formula 73]

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

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

When a resist composition contains (B) component, 50 mass parts or less are preferable with respect to 100 mass parts of (A) component, and, as for content of (B) component, in a resist composition, 1-40 mass parts is more preferable. , 1-30 mass parts is more preferable, and 1-20 mass parts is especially preferable.

Pattern formation is fully performed by making content of (B) component into the said range.

When the resist composition contains the component (B), the molar ratio with the component (D0) is preferably (D0) component / (B) component = 0.01 to 0.09, and (D0) component / (B) component = It is more preferable that it is 0.02-0.09, and it is further more preferable that it is (D0) component / (B) component = 0.02-0.05. By using such a molar ratio, when a thick film resist film having a film thickness of 5 µm or more is formed, the balance between the acid generated from the component (B) by exposure and the acid trapped by the component (D0) becomes good, thereby maintaining the CDU while maintaining high sensitivity. Can be improved.

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

(D) component acts as a quencher (acid diffusion control agent) which traps the acid generate | occur | produced by exposure in a resist composition. The resist composition of this embodiment may further contain acid diffusion control components other than the above-mentioned (D0) component as (D) component in the range which does not impair the effect of this invention.

As (D) component other than (D0) component, it is the photo-degradable base (D1) which decomposes | disassembles by exposure and loses acid diffusion controllability (henceforth "a component (D1)."), A nitrogen-containing organic compound (D2) (henceforth "(D2) component") which does not correspond to a (D1) component and the said (D0) component, etc. are mentioned.

About (D1) component

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

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

[Formula 74]

[Wherein, Rd ¹ to Rd ⁴ are a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. However, it is assumed that a fluorine atom is not bonded to a carbon atom adjacent to the S atom in Rd ² in General 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 m-valent onium cation.]

{(d1-1) component}

Noonbu

In formula (d1-1), Rd ¹ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, respectively, in said Formula (b1) It is the same as Rx ¹ Rx ~ ^4.

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

As said aromatic hydrocarbon group, the polycyclic structure (for example, the polycyclic structure which consists of a ring structure of bicyclooctane skeleton and ring structures other than this, etc.) containing a phenyl group, a naphthyl group, and a bicyclooctane skeleton is mentioned preferably. Can be.

As said aliphatic cyclic group, it is more preferable that 1 or more hydrogen atoms were removed from polycycloalkane, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

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

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

As Rd ¹ , it is preferable that some or all of the hydrogen atoms constituting the linear alkyl group are fluorinated alkyl groups substituted with fluorine atoms, and all of the hydrogen atoms constituting the linear alkyl groups are substituted with fluorine atoms. It is especially preferable that it is (a linear perfluoroalkyl group).

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

[Formula 75]

Cation part

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

As onium cation of M'm ⁺ , the thing similar to the cation represented by the said General formula (ca-1)-(ca-4), respectively is mentioned preferably, The cation represented by the said General formula (ca-1) More preferably, the cations represented by the formulas (ca-1-1) to (ca-1-78) and (ca-1-101) to (ca-1-149) are more preferable.

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

{(d1-2) component}

Noonbu

In formula (d1-2), Rd ² is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and Rx in said Formula (b1) as Rx ¹ ~ ⁴ are the same.

However, it is assumed that a fluorine atom is not bonded (not substituted with fluorine) to a carbon atom adjacent to the S atom in Rd ² . Thereby, the anion of the component (d1-2) becomes a suitable weak acid anion, and the quenching ability as the component (D1) is improved.

Roneun Rd ^2, is preferably brought to an alkyl group, or a substituent of the type chain which may have a substituent is also an aliphatic cyclic group which. As a linear alkyl group, it is preferable that it is C1-C10, and it is more preferable that it is 3-10. As an aliphatic cyclic group, group (substituent group) remove | excluding one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclo dodecane, etc .; It is more preferable that it is group which removed 1 or more hydrogen atoms from camphor etc.

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

The preferable specific example of the anion part of a component (d1-2) is shown below.

[Formula 76]

Cation part

In formula (d1-2), M'm ⁺ is m-valent onium cation, and is the same as M'm ⁺ in said formula (d1-1).

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

{(d1-3) component}

Noonbu

Formula (d1-3) of, Rd is ³ Rx ¹ in the cyclic group which may have a substituent, an alkenyl group which may have a chain-like alkyl group, or a substituent of the type chain which may have a substituent, the formula (b1) Rx ~ ⁴ as can be exemplified by the same, it is preferred that cyclic group containing a fluorine atom, an alkyl group of chain-like, or alkenyl group of chain-like. Among them, a fluorinated alkyl group and more preferably the same as that of the fluorinated alkyl group Rd ^1.

In formula (d1-3), Rd ⁴ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and Rx in said Formula (b1) as Rx ¹ ~ ⁴ are the same.

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

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

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

Examples of the alkenyl group in Rd ⁴ include the same as those of Rx ¹ to Rx ⁴ in the formula (b1), and a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group and a 2-methylpropenyl group are preferable. Do. These groups may also have a C1-C5 alkyl group or a C1-C5 halogenated alkyl group as a substituent.

Examples of the cyclic group in Rd ⁴ include the same as those of Rx ¹ to Rx ⁴ in the formula (b1), and include cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane and tetra The alicyclic group which removed 1 or more hydrogen atoms from cycloalkane, such as cyclododecane, or aromatic groups, such as a phenyl group and a naphthyl group, is preferable. In the case where Rd ⁴ is an alicyclic group, the resist composition is satisfactorily dissolved in an organic solvent, whereby lithographic characteristics are improved.

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

Group connection divalent in Yd ¹ is not particularly limited, there may be mentioned a divalent hydrocarbon group which may have a substituent (the aliphatic hydrocarbon group, an aromatic hydrocarbon group), a divalent connecting group, such as containing a hetero atom. They can be given, respectively, the formula (a10-1) and in the same Ya ^x1 way, two-valent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom from the description of the divalent connecting group in the.

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

The preferable specific example of the anion part of a component (d1-3) is shown below.

[Formula 77]

[Formula 78]

Cation part

In formula (d1-3), M'm ⁺ is m-valent onium cation, and is the same as M'm ⁺ in said formula (d1-1).

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

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

When a resist composition contains (D1) component, 0.5-35 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content of (D1) component, in a resist composition, 1-25 mass parts is more preferable. , 2-20 mass parts is more preferable, and 3-15 mass parts is especially preferable.

When content of (D1) component is more than a preferable minimum, especially favorable lithography characteristic and resist pattern shape are easy to be obtained. On the other hand, if it is below an upper limit, it can balance with another component, and various lithographic characteristics become favorable.

Preparation method of the component (D1):

The manufacturing method of the said (d1-1) component and (d1-2) component is not specifically limited, It can manufacture by a well-known method.

In addition, the manufacturing method of (d1-3) component is not specifically limited, For example, it is manufactured similarly to the method of US2012-0149916.

About (D2) component

The component (D2) is a base component and is a nitrogen-containing organic compound component (except those corresponding to the component (D0) and the component (D1)), which act as an acid diffusion control agent in the resist composition.

The component (D2) is not particularly limited as long as it acts as an acid diffusion control agent and does not correspond to the component (D0) and the component (D1). For example, a compound comprising an anion part and a cation part, Primary aliphatic amine, secondary aliphatic amine, etc. are mentioned.

As a compound which consists of an anion part and a cation part in (D2) component, what made the cation part in said (d1-1)-(d1-3) components the ammonium cation. The ammonium cation here is, NH ₄ ^+, or the H which binds to the nitrogen atom, a substituted hydrocarbon group which may have a heteroatom cation (first to a quaternary ammonium cation), or together with the nitrogen atom And cyclic cation forming a ring.

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

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

Specific examples of the alkylamine and the alkyl alcohol amine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine and n-decylamine; Dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine and dicyclohexylamine; Alkyl alcohol amines, such as diethanolamine, diisopropanolamine, and di-n-octanolamine, are mentioned.

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

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

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

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

Examples of the aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, and 2,6-diisopropylaniline.

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

When the resist composition contains the component (D2), the component (D2) is usually used in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the component (A). By setting it as said range, it can balance with the other component, and various lithographic characteristics become favorable.

It is preferable that the resist composition of this embodiment does not contain the (D1) component and the (D2) component.

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

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

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

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

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

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

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

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

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

When a resist composition contains (E) component, content of (E) component is normally used in 0.01-5 mass parts with respect to 100 mass parts of (A) component.

≪ (F) component: Fluorine additive component≫

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

As (F) component, Unexamined-Japanese-Patent No. 2010-002870, Unexamined-Japanese-Patent No. 2010-032994, Unexamined-Japanese-Patent No. 2010-277043, Unexamined-Japanese-Patent No. 2011-13569, Japan Unexamined-Japanese-Patent The fluorine-containing polymer compound described in publication 2011-128226 can be used.

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

[Formula 79]

[Wherein, R is the same as described above, Rf ¹⁰² and Rf ¹⁰³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Rf ¹⁰² and Rf ¹⁰³ are the same; You may or may differ. nf ¹ is an integer of 1 to 5, and Rf ¹⁰¹ is an organic group containing a fluorine atom.]

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

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

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

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

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

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

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

1000-50000 are preferable, as for the mass mean molecular weight (Mw) (polystyrene conversion basis by gel permeation chromatography) of (F) component, 5000-40000 are more preferable, and 10000-30000 are the most preferable. If it is below the upper limit of this range, there exists sufficient solubility to a resist solvent in using as a resist, and if it is more than the lower limit of this range, dry etching resistance and a resist pattern cross-sectional shape are favorable.

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

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

When a resist composition contains (F) component, content of (F) component is normally used in the ratio of 0.5-10 mass parts with respect to 100 mass parts of (A) component.

`` (S) Component: Organic Solvent Component ''

The resist composition of this embodiment can be manufactured by melt | dissolving a resist material in the organic solvent component (henceforth "(S) component").

As (S) component, what is necessary is just to melt | dissolve each component to be used and it can be set as a uniform solution, and conventionally, arbitrary things can be suitably selected and used from what is known as a solvent of a chemically amplified resist composition.

As (S) component, For example, lactones, such as (gamma) -butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; Monomethyl ether, monoethyl ether of a compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, the polyhydric alcohol or the compound having the ester bond, Derivatives of polyhydric alcohols such as monoalkyl ethers such as monopropyl ether and monobutyl ether or compounds having ether bonds such as monophenyl ether [In these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferable]; Cyclic ethers such as dioxane, esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate; Anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phentol, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, isopropyl benzene, toluene, xylene, cymene, mesitylene Aromatic organic solvents, such as dimethyl sulfoxide (DMSO), etc. are mentioned.

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

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

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

More specifically, when mix | blending EL or cyclohexanone as a polar solvent, the mass ratio of PGMEA: EL or cyclohexanone becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8. : 2 Moreover, when mix | blending PGME as a polar solvent, the mass ratio of PGMEA: PGME becomes like this. Preferably it is 1: 9-9: 1, More preferably, it is 2: 8-8: 2, More preferably, it is 3: 7- 7: 3: Moreover, the mixed solvent of PGMEA, PGME, and cyclohexanone is also preferable.

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

Since the resist composition of this embodiment is 20 mass% or more of (A) component concentration, (S) component is used by the usage-amount which becomes 20 mass% or more of (A) component concentration of a resist composition.

The resist composition of the present embodiment may be suitably further prepared with miscible additives such as additional resins, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, etc., for improving the performance of the resist film as desired. It can be added and contained.

The resist composition of this embodiment demonstrated above contains (A) component and the tertiary monoamine compound (D0) represented by general formula (d0). Moreover, in the resist composition of this embodiment, content of the said (A) component is 20 mass% or more, and content of the said compound (D0) is 0.01-0.05 mass parts with respect to 100 mass parts of said (A) component.

Since the resist composition of this embodiment has 20 mass% or more of content of (A) component, when it apply | coats to a board | substrate and forms a resist film, a thick-film resist film with a film thickness of 5 micrometers or more is formed. In such a thick film resist film, light hardly reaches the bottom part at the time of exposure, and there exists a tendency for a sensitivity to fall. On the other hand, if the amount of the acid diffusion control agent is reduced in order to maintain the sensitivity, the pattern dimension in-plane uniformity (CDU) is deteriorated, so it is difficult to improve the CDU while maintaining good sensitivity. In addition, in the thick film resist film, since light hardly reaches the bottom, a resist pattern having a good shape is hardly formed.

When compound (D0) has a specific structure (tertiary monoamine represented by general formula (d0)), when applied to the resist composition which forms a thick film resist film, it has moderate acid diffusion controllability. This is presumably because nucleophilicity is moderately inhibited by steric hindrance resulting from atomic arrangement around nitrogen atoms. It is estimated that the resist composition of this embodiment can improve CDU with a small content of a specific range by using the compound (D0) which has such a structure as an acid diffusion control agent. Moreover, since it is a small content of the said specific range, it is guessed that deterioration of a sensitivity can be suppressed.

In addition, by using the compound (D0) in the above specific range, the acid diffusion controllability in the downward direction in the thick film resist film is appropriately controlled at the time of exposure, so that a resist pattern having a good shape can be formed. I guess.

By the above operation, in the resist composition of the present embodiment, when a thick film resist film having a thickness of 5 µm or more is formed, lithography characteristics such as CDU can be improved while maintaining a good sensitivity, and a resist pattern having a good shape can be formed. I guess it is.

(Resist pattern formation method)

The resist pattern formation method which concerns on the 2nd aspect of this invention is a process (i) of forming a resist film using the resist composition of above-mentioned embodiment on a support body, the process (ii) of exposing the said resist film, and the said It is a method which has a process (iii) of developing the resist film after exposure and forming a resist pattern.

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

Process (i):

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

Process (ii):

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

Process (iii):

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

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

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

After the development treatment or the rinse treatment, drying is performed. In some cases, after the developing treatment, a bake treatment (post bake) may be performed.

In this way, a resist pattern can be formed.

Hereinafter, the detail of the resist pattern formation method of this embodiment is demonstrated.

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

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

Here, the multilayer resist method forms at least one layer organic film (lower layer organic film) and at least one layer resist film (upper layer resist film) on a board | substrate, and uses the resist pattern formed in the upper layer resist film as a mask It is a method of patterning an organic film, and it is supposed that the pattern of a Gore-spectrum ratio can be formed. That is, according to the multilayer resist method, since a required thickness can be ensured by an underlayer organic film, a resist film can be thinned and fine pattern formation of a Gore aspect ratio is attained.

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

Since the resist pattern formation method of this embodiment forms a resist film using the resist composition of embodiment mentioned above, the film thickness of the resist film formed in process (i) becomes 5 micrometers or more. The film thickness of the resist film formed in process (i) becomes like this. Preferably it is 7 micrometers or more. The upper limit of the film thickness of the resist film is substantially 30 µm or less. As a range of the film thickness of the resist film formed in a process (i), 5-30 micrometers is illustrated, for example, 7-20 micrometers is preferable, 7-15 micrometers is more preferable, 8-10 micrometers is More preferred.

The film thickness of a resist film can be adjusted with content of (A) component in the resist composition used at a process (i). That is, the higher the content of the component (A) in the resist composition, the higher the thickness of the resist film can be formed.

The wavelength used for exposure is not specifically limited, ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, etc. It can be done using radiation. The resist composition has high utility for KrF excimer laser, ArF excimer laser, EB or EUV, higher utility for KrF excimer laser, ArF excimer laser, and particularly high usefulness for KrF excimer laser. That is, the resist pattern formation method of this embodiment is a method especially useful when the process of exposing a resist film includes the operation which exposes a KrF excimer laser beam to the said resist film.

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

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

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

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

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

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

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

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

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

As an organic solvent which the organic developing solution used for image development processing in a solvent image development process contains, it should just be able to melt | dissolve component (A) (component (A) before exposure), and it can select suitably from well-known organic solvents. Specific examples thereof include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents and ether solvents, and hydrocarbon solvents.

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

Among the organic solvents, organic solvents containing plural kinds of functional groups for characterizing the respective solvents are present in the structure, but in this case, it is assumed that they correspond to any solvent species containing the functional groups of the organic solvent. For example, diethylene glycol monomethyl ether shall correspond to any of the alcohol solvent and the ether solvent in the said classification | combination.

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

As an organic solvent which an organic developing solution contains, a polar solvent is preferable among the above, and a ketone solvent, an ester solvent, a nitrile solvent, etc. are preferable.

As a ketone solvent, it is 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl, for example. Ketones, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, Isophorone, propylene carbonate, γ-butyrolactone, methyl amyl ketone (2-heptanone) and the like. Among these, methyl amyl ketone (2-heptanone) is preferable as a ketone solvent.

As an ester solvent, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoam acetate, methoxy acetate, ethyl ethoxy acetate, propylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3 Metok Cybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate , Propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, propionate Ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3- Oxypropionate, propyl-3-methoxypropionate, and the like. Among these, butyl acetate is preferable as an ester solvent.

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

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

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

The developing treatment can be carried out by a known developing method, for example, a method of immersing a support in a developer for a certain time (dip method), a method of raising the developer on the surface of the support by surface tension and stopping for a certain time (puddle). Method), a method of spraying a developer onto the surface of a support (spray method), a method of continuously deriving a developer while scanning a developer extracting nozzle at a constant speed on a support rotated at a constant speed, and the like (dynamic dispensing method). .

As the organic solvent contained in the rinse liquid used for the rinse treatment after the developing treatment in the solvent developing process, for example, an organic solvent used as the organic solvent used in the organic developer may be appropriately selected and used that is difficult to dissolve the resist pattern. Can be. Usually, at least 1 type of solvent chosen from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is used. Among these, at least one kind selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent and an amide solvent is preferable, and at least one kind selected from an alcohol solvent and an ester solvent is more preferable. Alcoholic solvents are particularly preferred.

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

These organic solvents may be used individually by 1 type, and may use 2 or more types together. Moreover, you may mix and use with the organic solvent and water of that excepting the above. However, considering the development characteristics, the blending amount of water in the rinse liquid is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and 3% by mass relative to the total amount of the rinse liquid. % Or less is especially preferable.

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

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

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

In the resist pattern forming method of the present embodiment described above, since the resist composition according to the first embodiment described above is used, when forming a resist pattern, it is possible to achieve better lithography characteristics (CDU improvement, etc.) with high sensitivity. A resist pattern can be formed. Moreover, according to such a resist pattern formation method, the resist pattern of a favorable shape is formed.

Such a resist pattern formation method is useful for manufacture of a three-dimensional structure device, and is a preferable method for the use (overlapping etc.) of processing a multistage staircase structure. By applying the resist pattern forming method of the present invention, stacking of a memory film (three-dimensionalization, production of a large capacity memory) can be realized with high accuracy.

Example

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

<Preparation of a resist composition>

Each component shown in Table 1 was mixed, and it melt | dissolved and prepared the resist composition (content of both and (A) component: 35 mass%) of each case, respectively.

In Table 1, each symbol has the following meanings, respectively. The numerical value in [] is a compounding quantity (mass part).

(A) -1: A high molecular compound represented by the following general formula (A-1). This polymer compound (A) -1 was obtained by radically polymerizing using the monomer which guide | induces the structural unit which comprises this polymer compound in predetermined molar ratio. About this high molecular compound (A) -1, the mass mean molecular weight (Mw) of the standard polystyrene conversion calculated | required by GPC measurement is 10000, and molecular weight dispersion degree (Mw / Mn) is about 2.0. ^The copolymerization composition ratio (proportion (molar ratio) of each structural unit in the structural formula) determined by ¹³ C-NMR was l / m / n = 1 / 0.6 / 0.4.

[Formula 80]

(B) -1: The acid generator which consists of the following compound (B-1).

(B) -2: The acid generator which consists of the following compound (B-2).

[Formula 81]

(D0) -1: Acid diffusion control agent which consists of a compound represented by following General formula (D0-1).

(D0) -2: Acid diffusion control agent which consists of a compound represented by following General formula (D0-2).

[Formula 82]

(D) -1: Acid diffusion control agent which consists of a compound represented by following General formula (D2-1).

(D) -2: Acid diffusion control agent which consists of a compound represented by following General formula (D2-2).

[Formula 83]

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

<Formation method of resist pattern>

Process (i):

On each 8-inch silicon wafer, the resist composition of each example was apply | coated using a coater, and it pre-baked (PAB) treatment for 120 second at 140 degreeC on a hotplate, and dried, and it was made into a film thickness of 8 micrometers. A resist film was formed.

Process (ii):

Subsequently, KrF excimer laser (248 nm) was subjected to a mask pattern (6% halftone) by KrF exposure apparatus NSR-S203B (manufactured by Nikon Corporation; NA (number of apertures) = 0.60, sigma = 0.68) with respect to the resist film. Was selectively investigated.

Subsequently, post exposure bake (PEB) treatment was performed at 110 ° C. for 90 seconds.

Process (iii):

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

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

As a result, an isolated line pattern (hereinafter referred to as "IS pattern") having a space width of 3 µm and a pitch of 15 µm was formed.

[Sensitivity]

In the formation method of the resist pattern mentioned above, the optimal exposure amount Eop (mJ / cm <2>) in which the resist pattern made into a target is formed was calculated | required, and it was set as the sensitivity. This was shown in Table 2 as "sensitivity (mJ / cm <2>)".

[Dimension Uniformity (CDU) in Wafer Surface (Shot)]]

About the IS pattern formed by the formation method of the resist pattern mentioned above, the IS pattern (7 by scanning electron microscope, scanning voltage 300V, brand name: S-9380, the Hitachi High-Technologies Corporation). X 15 shots) was observed from above, and the space width of the IS pattern (38 points in the shot) was measured. The triple value (3σ) of the standard deviation (σ) calculated from the measurement result was calculated | required. The smaller the value of 3σ obtained in this way, the higher the dimension (CD) uniformity of the space width formed in the resist film. The results are shown in Table 2 as "CDU (nm)".

[Shape of Resist Pattern]

The shape of the IS pattern formed by the formation method of the resist pattern mentioned above was observed by length measurement SEM (scanning electron microscope, acceleration voltage 800V, brand name: SU-8000, the Hitachi High-Technologies company make), and the following evaluation criteria According to this, the evaluation result was shown in Table 2 as "shape."

Evaluation standard

○: The pattern side wall is inclined linearly.

(Triangle | delta): There exists expansion in the inclination of the pattern side wall.

×: top-round shape, pattern sidewall is dug

From the results shown in Table 2, in the resist compositions of Examples 1 to 7 to which the present invention was applied, it was confirmed that the CDU performance was improved and exhibited high sensitivity as compared with the resist compositions of Comparative Examples 1 to 4. Moreover, in Examples 1-7, the resist pattern shape was also favorable compared with Comparative Examples 1-4.

Claims (5)

As a resist composition which generate | occur | produces an acid by exposure and changes solubility to a developing solution by the action of an acid,
Base component (A) whose solubility with respect to a developing solution changes by the action of an acid,
Tertiary monoamine compound (D0) represented by the following general formula (d0)
Containing,
Content of the said base material component (A) is 20 mass% or more,
The resist composition whose content of the said compound (D0) is 0.01-0.05 mass parts with respect to 100 mass parts of said base material components (A).

[Wherein, Rx ¹ to Rx ³ each independently represent a hydrocarbon group which may have a substituent. Two or more of Rx ¹ to Rx ³ may be bonded to each other to form a ring structure.] The method of claim 1,
The resist composition whose said compound (D0) is a compound represented by the following general formula (d0-1) or (d0-2).

[Formula (d0-1) of, Rx ¹¹ Rx ~ ¹³ are, each independently, it represents a group which may have a substituent group selected from the group of linear branched, or aromatic hydrocarbon. However, there is no case that all of the Rx ¹¹ Rx ~ ¹³ underlying an aromatic hydrocarbon. In formula (d0-2), Ry ¹ to Ry ³ represent a linear or branched alkyl group which may have a substituent. nx1 represents the integer of 0-3.] The method of claim 1,
Furthermore, the resist composition containing the acid generator component (B) which generate | occur | produces an acid by exposure. Process (i) of forming a resist film using the resist composition of any one of Claims 1-3 on the support body, process (ii) of exposing the said resist film, and developing the resist film after exposure, and developing a resist The resist pattern formation method which has a process (iii) of forming a pattern. The method of claim 4, wherein
The resist pattern formation method whose film thickness of the resist film formed in the said process (i) is 5 micrometers or more.