# Patent

## Title
Positive resist composition and method of forming resist pattern

## Abstract

A positive resist composition including a resin component (A1) having a structural unit (a1) derived from an acrylate ester which may have an atom other than hydrogen or a group bonded to the carbon atom on the α position and containing an acid dissociable, dissolution inhibiting group, and a structural unit (a0) containing an —SO2— containing cyclic group; a compound (C1) represented by general formula (c1) shown below; and an acid-generator component (B) which generates acid upon exposure, wherein R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; Y1 represents a divalent aliphatic hydrocarbon group; R1 represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorinated alkyl group; p represents an integer of 1 to 10; and A+ represents an organic cation.

## Background
TECHNICAL FIELD
The present invention relates to a positive resist composition and a method of forming a resist pattern.
Priority is claimed on Japanese Patent Application No. 2010-155701, filed Jul. 8, 2010, the content of which is incorporated herein by reference.
BACKGROUND ART
In lithography techniques, for example, a resist film composed of a resist material is formed on a substrate, and the resist film is subjected to selective exposure of radial rays such as light or electron beam through a mask having a predetermined pattern, followed by development, thereby forming a resist pattern having a predetermined shape on the resist film.
A resist material in which the exposed portions become soluble in a developing solution is called a positive-type, and a resist material in which the exposed portions become insoluble in a developing solution is called a negative-type.
In recent years, in the production of semiconductor elements and liquid crystal display elements, advances in lithography techniques have lead to rapid progress in the field of pattern miniaturization.
Typically, these miniaturization techniques involve shortening the wavelength (increasing the energy) of the exposure light source. Conventionally, ultraviolet radiation typified by g-line and i-line radiation has been used, but nowadays KrF excimer lasers and ArF excimer lasers are starting to be introduced in mass production. Furthermore, research is also being conducted into lithography techniques that use an exposure light source having a wavelength shorter (energy higher) than these excimer lasers, such as electron beam, extreme ultraviolet radiation (EUV), and X ray.
Resist materials for use with these types of exposure light sources require lithography properties such as a high resolution capable of reproducing patterns of minute dimensions, and a high level of sensitivity to these types of exposure light sources.
As a resist material that satisfies these conditions, a chemically amplified composition is used, which includes a base material component that exhibits a changed solubility in an alkali developing solution under the action of acid and an acid-generator component that generates acid upon exposure.
For example, a chemically amplified positive resist contains, as a base component (base resin), a resin which exhibits increased solubility in an alkali developing solution under action of acid, and an acid generator is typically used. If the resist film formed using the resist composition is selectively exposed during formation of a resist pattern, then within the exposed portions, acid is generated from the acid-generator component, and the action of this acid causes an increase in the solubility of the resin component in an alkali developing solution, making the exposed portions soluble in the alkali developing solution.
Currently, resins that contain structural units derived from (meth)acrylate esters within the main chain (acrylic resins) are now widely used as base resins for resist compositions that use ArF excimer laser lithography, as they exhibit excellent transparency in the vicinity of 193 nm (for example, see Patent Document 1).
Especially, in order to improve various lithography properties, a base resin having a plurality of structural units is currently used for a chemically amplified resist composition. For example, in the case of a chemically amplified positive resist composition, a resin containing a structural unit having an acid dissociable, dissolution inhibiting group that is dissociated by the action of acid generated from the acid generator, a structural unit having a polar group such as a hydroxyl group, a structural unit having a lactone structure, and the like is typically used.
Further, in order to improve various lithography properties such as resolution, exposure latitude (EL margin) and mask reproducibility, a resin having a structural unit containing an —SO2— containing cyclic group has been used (for example, see Patent Document 2).
An “—SO2— containing cyclic group” refers to a cyclic group having a ring containing —SO2— within the ring skeleton thereof, i.e., a cyclic group in which the sulfur atom (S) within —SO2— forms part of the ring skeleton of the cyclic group.
On the other hand, as acid generators usable in a chemically amplified resist composition, various types have been proposed including, for example, onium salt acid generators such as iodonium salts and sulfonium salts; oxime sulfonate acid generators; diazomethane acid generators; nitrobenzylsulfonate acid generators; iminosulfonate acid generators; and disulfone acid generators.
Among these, currently, as acid generators, onium salt acid generators having an onium ion such as triphenylsulfonium as the cation moiety are particularly used. As the anion moiety for onium salt acid generators, an alkylsulfonate ion or a fluorinated alkylsulfonate ion in which part or all of the hydrogen atoms within the aforementioned alkylsulfonate ion has been substituted with fluorine atoms is typically used (for example, see Patent Document 3).
DOCUMENTS OF RELATED ART
Patent Document


    [Patent Document 1] Japanese Unexamined Patent Application, First Publication No. 2003-241385
    [Patent Document 2] Japanese Unexamined Patent Application, First Publication No. 2010-134417
    [Patent Document 3] Japanese Unexamined Patent Application, First Publication No. 2005-037888


SUMMARY OF THE INVENTION
As further progress is made in lithography techniques and the application field for lithography techniques expands, especially as the size of the pattern is miniaturized, further improvement in resist pattern shape and various lithography properties will be demanded in resist materials.
In an attempt to solve these problems, in a conventional positive-type chemically amplified resist composition, as described above, a polymeric compound having a structural unit containing an acid dissociable, dissolution inhibiting group and a structural unit having an —SO2— containing cyclic group is used as a base resin, and the base resin is used in combination with an onium salt acid generator to improve lithography properties. However, in the formation of an extremely fine semiconductor device, further more improvement has been demanded especially in the reduction of the roughness of the resist pattern.
The present invention takes the above circumstances into consideration, with an object of providing a positive resist composition which enables formation of a resist pattern with reduced roughness and having an excellent shape, and a method of forming a resist pattern.
For solving the above-mentioned problems, the present invention employs the following aspects.
Specifically, a first aspect of the present invention is a positive resist composition including a resin component (A1) having a structural unit (a1) derived from an acrylate ester which may have an atom other than hydrogen or a group bonded to the carbon atom on the α position and containing an acid dissociable, dissolution inhibiting group, and a structural unit (a0) derived from an acrylate ester which may have an atom other than hydrogen or a group bonded to the carbon atom on the α position and containing an —SO2— containing cyclic group; a compound (C1) represented by general formula (c1) shown below; and an acid-generator component (B) (excluding the compound (C1)) which generates acid upon exposure.




In the formula, R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; Y1 represents a divalent aliphatic hydrocarbon group; R1 represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorinated alkyl group; p represents an integer of 1 to 10; and A+ represents an organic cation.

A second aspect of the present invention is a method of forming a resist pattern, including using a positive resist composition according to the first aspect to form a resist film on a substrate, subjecting the resist film to exposure, and subjecting the resist film to alkali developing to form a resist pattern.
In the present description and claims, an “alkyl group” includes linear, branched or cyclic, monovalent saturated hydrocarbon, unless otherwise specified.
The term “alkylene group” includes linear, branched or cyclic divalent saturated hydrocarbon, unless otherwise specified.
A “lower alkyl group” is an alkyl group of 1 to 5 carbon atoms.
A “halogenated alkyl group” is a group in which part or all of the hydrogen atoms of an alkyl group is substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The term “aliphatic” is a relative concept used in relation to the term “aromatic”, and defines a group or compound that has no aromaticity.
The term “structural unit” refers to a monomer unit that contributes to the formation of a polymeric compound (polymer, copolymer).
The term “exposure” is used as a general concept that includes irradiation with any form of radiation.
The term “(meth)acrylic acid” is a generic term that includes either or both of acrylic acid having a hydrogen atom bonded to the α-position and methacrylic acid having a methyl group bonded to the α-position.
The term “(meth)acrylate ester” is a generic term that includes either or both of the acrylate ester having a hydrogen atom bonded to the α-position and the methacrylate ester having a methyl group bonded to the α-position.
The term “(meth)acrylate” is a generic term that includes either or both of the acrylate having a hydrogen atom bonded to the α-position and the methacrylate having a methyl group bonded to the α-position.
According to the present invention, there are provided a positive resist composition which enables formation of a resist pattern with reduced roughness and having an excellent shape, and a method of forming a resist pattern.


DETAILED DESCRIPTION OF THE INVENTION
Positive Resist Composition
The positive resist composition according to the first aspect of the present invention includes a resin component (A) which exhibits increased solubility in an alkali developing solution under action of acid (hereafter, referred to as “component (A)”), a compound (C1) represented by the aforementioned general formula (c1) (hereafter, referred to as “component (C1)”) and an acid-generator component (B) which generates acid upon exposure (hereafter, referred to as “component (B)”) (provided that the component (B) excludes the component (C1)).
In the positive resist composition, when radial rays are irradiated (when exposure is conducted), acid is generated from the component (B), and the solubility of the component (A) in an alkali developing solution is increased by the action of the generated acid. Therefore, in the formation of a resist pattern, by conducting selective exposure of a resist film formed by using the positive resist composition of the present invention, the solubility of the exposed portions in an alkali developing solution is increased, whereas the solubility of the unexposed portions in an alkali developing solution is unchanged, and hence, a resist pattern can be formed by alkali developing.
<Component (A)>
In the present invention, the component (A) includes a resin component (A1) (hereafter, referred to as “component (A1)”) having a structural unit (a1) derived from an acrylate ester which may have an atom other than hydrogen or a group bonded to the carbon atom on the α position and containing an acid dissociable, dissolution inhibiting group, and a structural unit (a0) derived from an acrylate ester which may have an atom other than hydrogen or a group bonded to the carbon atom on the α position and containing an —SO2— containing cyclic group.
In the present descriptions and the claims, the expression “structural unit derived from an acrylate ester” refers to a structural unit that is formed by the cleavage of the ethylenic double bond of an acrylate ester.
An “acrylate ester” refers to an acrylate ester having a hydrogen atom bonded to the carbon atom on the α position.
With respect to the “acrylate ester which may have an atom other than hydrogen or a substituent bonded to the carbon atom on the α position”, examples of the atom other than hydrogen include a halogen atom, and examples of the substituent include an alkyl group of 1 to 5 carbon atoms and a halogenated alkyl group of 1 to 5 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
With respect to the “structural unit derived from an acrylate ester”, the “α-position (the carbon atom on the α-position)” refers to the carbon atom having the carbonyl group bonded thereto, unless specified otherwise.
Specific examples of the alkyl group of 1 to 5 carbon atoms for the substituent which may be bonded to the carbon atom on the α-position include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group and a neopentyl group.
Specific examples of the halogenated alkyl group of 1 to 5 carbon atoms for the substituent include groups in which part or all of the hydrogen atoms of the aforementioned “alkyl group of 1 to 5 carbon atoms for the substituent” are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly desirable.
In the present invention, it is preferable that a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms is bonded to the carbon atom on the α-position, a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a fluorinated alkyl group of 1 to 5 carbon atoms is more preferable, and in terms of industrial availability, a hydrogen atom or a methyl group is the most desirable.
[Component (A1)]
The component (A1) has the aforementioned structural unit (a1) and the aforementioned structural unit (a0).
Further, it is preferable that the component (A1) has a structural unit (a5) represented by general formula (a5-1) described later, as well as the structural units (a1) and (a0).
Furthermore, the component (A1) may have a structural unit other than the structural unit (a5), as well as the structural units (a1) and (a0).
(Structural Unit (a1))
The structural unit (a1) is a structural unit derived from an acrylate ester which may have an atom other than hydrogen or a substituent bonded to the carbon atom on the α position and contains an acid dissociable, dissolution inhibiting group.
As the acid dissociable, dissolution inhibiting group in the structural unit (a1), any of the groups that have been proposed as acid dissociable, dissolution inhibiting groups for the base resins of chemically amplified resists can be used, provided the group has an alkali dissolution-inhibiting effect that renders the entire component (A1) insoluble in an alkali developing solution prior to dissociation, and then following dissociation by action of acid, increases the solubility of the entire component (A1) in the alkali developing solution. Generally, groups that form either a cyclic or chain-like tertiary alkyl ester with the carboxyl group of the (meth)acrylic acid, and acetal-type acid dissociable, dissolution inhibiting groups such as alkoxyalkyl groups are widely known.
Here, a tertiary alkyl ester describes a structure in which an ester is formed by substituting the hydrogen atom of a carboxyl group with a chain-like or cyclic tertiary alkyl group, and a tertiary carbon atom within the chain-like or cyclic tertiary alkyl group is bonded to the oxygen atom at the terminal of the carbonyloxy group (—C(═O)—O—). In this tertiary alkyl ester, the action of acid causes cleavage of the bond between the oxygen atom and the tertiary carbon atom.
The chain-like or cyclic alkyl group may have a substituent.
Hereafter, for the sake of simplicity, groups that exhibit acid dissociability as a result of the formation of a tertiary alkyl ester with a carboxyl group are referred to as “tertiary alkyl ester-type acid dissociable, dissolution inhibiting groups”.
Examples of tertiary alkyl ester-type acid dissociable, dissolution inhibiting groups include aliphatic branched, acid dissociable, dissolution inhibiting groups and aliphatic cyclic group-containing acid dissociable, dissolution inhibiting groups.
In the present description and claims, the term “aliphatic branched” refers to a branched structure having no aromaticity.
The “aliphatic branched, acid dissociable, dissolution inhibiting group” is not limited to be constituted of only carbon atoms and hydrogen atoms (not limited to hydrocarbon groups), but is preferably a hydrocarbon group.
Further, the “hydrocarbon group” may be either saturated or unsaturated, but is preferably saturated.
Examples of aliphatic branched, acid dissociable, dissolution inhibiting groups include tertiary alkyl groups of 4 to 8 carbon atoms, and specific examples include a tert-butyl group, tert-pentyl group and tert-heptyl group.
The term “aliphatic cyclic group” refers to a monocyclic group or polycyclic group that has no aromaticity.
The “aliphatic cyclic group” within the structural unit (a1) may or may not have a substituent. Examples of substituents include lower alkyl groups of 1 to 5 carbon atoms, lower alkoxy groups of 1 to 5 carbon atoms, fluorine atom, fluorinated lower alkyl groups of 1 to 5 carbon atoms, and oxygen atom (═O).
The basic ring of the “aliphatic cyclic group” exclusive of substituents is not limited to be constituted from only carbon and hydrogen (not limited to hydrocarbon groups), but is preferably a hydrocarbon group.
Further, the “hydrocarbon group” may be either saturated or unsaturated, but is preferably saturated. Furthermore, the “aliphatic cyclic group” is preferably a polycyclic group.
As such aliphatic cyclic groups, groups in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane which may or may not be substituted with a lower alkyl group, a fluorine atom or a fluorinated alkyl group, may be used. Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane and cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
As the aliphatic cyclic group-containing acid dissociable, dissolution inhibiting group, for example, a group which has a tertiary carbon atom on the ring structure of the cycloalkyl group can be used. Specific examples include 2-methyl-2-adamantyl group and a 2-ethyl-2-adamantyl group. Further, groups having an aliphatic cyclic group such as an adamantyl group, cyclohexyl group, cyclopentyl group, norbornyl group, tricyclodecyl group or tetracyclododecyl group, and a branched alkylene group having a tertiary carbon atom bonded thereto, as the groups bonded to the oxygen atom of the carbonyl group (—C(O)—O—) within the structural units represented by general formulas (a1′′-1) to (a1′′-6) shown below, can be used.







In the formulas, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; and R15 and R16 each independently represent an alkyl group (which may be linear or branched, and preferably has 1 to 5 carbon atoms).

In general formulas (a1′′-1) to (a1′′-6) above, the lower alkyl group or halogenated lower alkyl group for R are the same as the alkyl group of 1 to 5 carbon atoms or halogenated alkyl group of 1 to 5 carbon atoms which can be bonded to the α-position of the aforementioned acrylate ester.
An “acetal-type acid dissociable, dissolution inhibiting group” generally substitutes a hydrogen atom at the terminal of an alkali-soluble group such as a carboxy group or hydroxyl group, so as to be bonded with an oxygen atom. When acid is generated upon exposure, the generated acid acts to break the bond between the acetal-type acid dissociable, dissolution inhibiting group and the oxygen atom to which the acetal-type, acid dissociable, dissolution inhibiting group is bonded.
Examples of acetal-type acid dissociable, dissolution inhibiting groups include groups represented by general formula (p1) shown below.




In the formula, R1′ and R2′ each independently represent a hydrogen atom or a lower alkyl group; n represents an integer of 0 to 3; and Y represents a lower alkyl group or an aliphatic cyclic group.

In general formula (p1) above, n is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 0.
As the lower alkyl group for R1′ and R2′, the same lower alkyl groups as those described above for R can be used, although a methyl group or ethyl group is preferable, and a methyl group is particularly desirable.
In the present invention, it is preferable that at least one of R1′′ and R2′ be a hydrogen atom. That is, it is preferable that the acid dissociable, dissolution inhibiting group (p1) is a group represented by general formula (p1-1) shown below.




In the formula, R1′, n and Y are the same as defined above.

As the lower alkyl group for Y, the same as the lower alkyl groups for R above can be used.
As the aliphatic cyclic group for Y, any of the aliphatic monocyclic/polycyclic groups which have been proposed for conventional ArF resists and the like can be appropriately selected for use. For example, the same groups described above in connection with the “aliphatic cyclic group” can be used.
Further, as the acetal-type, acid dissociable, dissolution inhibiting group, groups represented by general formula (p2) shown below can also be used.




In the formula, R17 and R18 each independently represent a linear or branched alkyl group or a hydrogen atom; and R19 represents a linear, branched or cyclic alkyl group; or R17 and R19 each independently represents a linear or branched alkylene group, and the terminal of R17 is bonded to the terminal of R19 to form a ring.

The alkyl group for R17 and R18 preferably has 1 to 15 carbon atoms, and may be either linear or branched. As the alkyl group, an ethyl group or a methyl group is preferable, and a methyl group is most preferable.
It is particularly desirable that either one of R17 and R18 be a hydrogen atom, and the other be a methyl group.
R19 represents a linear, branched or cyclic alkyl group which preferably has 1 to 15 carbon atoms, and may be any of linear, branched or cyclic.
When R19 represents a linear or branched alkyl group, it is preferably an alkyl group of 1 to 5 carbon atoms, more preferably an ethyl group or methyl group, and most preferably an ethyl group.
When R19 represents a cycloalkyl group, it preferably has 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. As examples of the cycloalkyl group, groups in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, may be used. Examples of such groups include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane. Among these, a group in which one or more hydrogen atoms have been removed from adamantane is preferable.
In general formula (p2) above, R17 and R19 may each independently represent a linear or branched alkylene group (preferably an alkylene group of 1 to 5 carbon atoms), and the terminal of R19 may be bonded to the terminal of R17.
In such a case, a cyclic group is formed by R17, R19, the oxygen atom having R19 bonded thereto, and the carbon atom having the oxygen atom and R17 bonded thereto. Such a cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include tetrahydropyranyl group and tetrahydrofuranyl group.
As the structural unit (a1), it is preferable to use at least one member selected from the group consisting of structural units represented by formula (a1-0-1) shown below and structural units represented by formula (a1-0-2) shown below.




In the formula, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; and X1 represents an acid dissociable, dissolution inhibiting group.





In the formula, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; X2 represents an acid dissociable, dissolution inhibiting group; and Y2 represents a divalent linking group.

In general formula (a1-0-1) above, the lower alkyl group or halogenated lower alkyl group for R are the same as the alkyl group of 1 to 5 carbon atoms or halogenated alkyl group of 1 to 5 carbon atoms which can be bonded to the α-position of the aforementioned acrylate ester.
X1 is not particularly limited as long as it is an acid dissociable, dissolution inhibiting group. Examples thereof include the aforementioned tertiary alkyl ester-type acid dissociable, dissolution inhibiting groups and acetal-type acid dissociable, dissolution inhibiting groups, and tertiary alkyl ester-type acid dissociable, dissolution inhibiting groups are preferable.
In general formula (a1-0-2), R is the same as defined above.
X2 is the same as defined for X1 in general formula (a1-0-1).
As the divalent linking group for Y2, an alkylene group, a divalent aliphatic cyclic group or a divalent linking group containing a hetero atom can be mentioned.
As the aliphatic cyclic group, the same as those used above in connection with the explanation of “aliphatic cyclic group” can be used, except that two hydrogen atoms have been removed therefrom.
When Y2 represents an alkylene group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 6, still more preferably 1 to 4, and most preferably 1 to 3.
When Y2 represents a divalent aliphatic cyclic group, it is particularly desirable that the divalent aliphatic cyclic group be a group in which two or more hydrogen atoms have been removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane or tetracyclododecane.
When Y2 represents a divalent linking group containing a hetero atom, examples thereof include —O—, —C(═O)—O—, —C(═O)—, —O—C(═O)—O—, —C(═O)—NH—, —NH— (H may be substituted with a substituent such as an alkyl group or an acyl group), —S—, —S(═O)2—, —S(═O)2—O—, and “-A-O-B- (wherein O is an oxygen atom, and each of A and B independently represents a divalent hydrocarbon group which may have a substituent)”.
When Y2 represents a divalent linking group —NH— and the H in the formula is replaced with a substituent such as an alkyl group or an acyl group, the substituent preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 5 carbon atoms.
When Y2 is “A-O-B”, each of A and B independently represents a divalent hydrocarbon group which may have a substituent.
A hydrocarbon “has a substituent” means that part or all of the hydrogen atoms within the hydrocarbon group is substituted with groups or atoms other than hydrogen atom.
The hydrocarbon group for A may be either an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. An “aliphatic hydrocarbon group” refers to a hydrocarbon group that has no aromaticity.
The aliphatic hydrocarbon group for A may be either saturated or unsaturated. In general, the aliphatic hydrocarbon group is preferably saturated.
As specific examples of the aliphatic hydrocarbon group for A, a linear or branched aliphatic hydrocarbon group, and an aliphatic hydrocarbon group having a ring in the structure thereof can be given.
The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, still more preferably 2 to 5, and most preferably 2.
As a linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specific examples include a methylene group, an ethylene group [—(CH2)2—], a trimethylene group [—(CH2)3—], a tetramethylene group [—(CH2)4—] and a pentamethylene group [—(CH2)5—].
As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples include alkylalkylene groups, e.g., alkylmethylene groups such as —CH(CH3)—, —CH(CH2CH3)—, —C(CH3)2—, —C(CH3)(CH2CH3)—, —C(CH3)(CH2CH2CH3)— and —C(CH2CH3)2—; alkylethylene groups such as —CH(CH3)CH2—, —CH(CH3)CH(CH3)—, —C(CH3)2CH2— and —CH(CH2CH3)CH2—; alkyltrimethylene groups such as —CH(CH3)CH2CH2— and —CH2CH(CH3)CH2—; and alkyltetramethylene groups such as —CH(CH3)CH2CH2CH2— and —CH2CH(CH3)CH2CH2—. As the alkyl group within the alkylalkylene group, a linear alkyl group of 1 to 5 carbon atoms is preferable.
The linear or branched aliphatic hydrocarbon group (chain-like aliphatic hydrocarbon group) may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated lower alkyl group of 1 to 5 carbon atoms, and an oxygen atom (═O).
As examples of the hydrocarbon group containing a ring, a cyclic aliphatic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), and a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of the aforementioned chain-like aliphatic hydrocarbon group or interposed within the aforementioned chain-like aliphatic hydrocarbon group, can be given.
The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The cyclic aliphatic hydrocarbon group may be either a polycyclic group or a monocyclic group. As the monocyclic group, a group in which two hydrogen atoms have been removed from a monocycloalkane of 3 to 6 carbon atoms is preferable. Examples of the monocycloalkane include cyclopentane and cyclohexane.
As the polycyclic group, a group in which two hydrogen atoms have been removed from a polycycloalkane of 7 to 12 carbon atoms is preferable. Examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a lower alkyl group of 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group of 1 to 5 carbon atoms, and an oxygen atom (═O).
As A, a linear aliphatic hydrocarbon group is preferable, more preferably a linear alkylene group, still more preferably a linear alkylene group of 2 to 5 carbon atoms, and most preferably an ethylene group.
Examples of the hydrocarbon group for A include a divalent aromatic hydrocarbon group in which one hydrogen atom has been removed from a benzene ring of a monovalent aromatic hydrocarbon group such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group or a phenanthryl group; an aromatic hydrocarbon group in which part of the carbon atoms constituting the ring of the aforementioned divalent aromatic hydrocarbon group has been substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom; and an aromatic hydrocarbon group in which one hydrogen atom has been removed from a benzene ring of an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group or a 2-naphthylethyl group.
The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group of 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group of 1 to 5 carbon atoms, and an oxygen atom (═O).
As the hydrocarbon group for B, the same divalent hydrocarbon groups as those described above for A can be used.
As B, a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group or an alkylmethylene group is particularly desirable.
The alkyl group within the alkyl methylene group is preferably a linear alkyl group of 1 to 5 carbon atoms, more preferably a linear alkyl group of 1 to 3 carbon atoms, and most preferably a methyl group.
Specific examples of the structural unit (a1) include structural units represented by general formulas (a1-1) to (a1-4) shown below.




In the formulas, X′ represents a tertiary alkyl ester-type acid dissociable, dissolution inhibiting group; Y represents a lower alkyl group of 1 to 5 carbon atoms or an aliphatic cyclic group; n represents an integer of 0 to 3; Y2 represents a divalent linking group; R is the same as defined above; and each of R1′ and R2′ independently represents a hydrogen atom or a lower alkyl group of 1 to 5 carbon atoms.

Examples of the tertiary alkyl ester-type acid dissociable, dissolution inhibiting group for X′ include the same tertiary alkyl ester-type acid dissociable, dissolution inhibiting groups as those described above for X1.
As R1′, R2′, n and Y are respectively the same as defined for R1′, R2′, n and Y in general formula (p1) described above in connection with the “acetal-type acid dissociable, dissolution inhibiting group”.
As examples of Y2, the same groups as those described above for Y2 in general formula (a1-0-2) can be given.
Specific examples of structural units represented by general formula (a1-1) to (a1-4) are shown below.
In the formulas shown below, Rα represents a hydrogen atom, a methyl group or a trifluoromethyl group.















































































As the structural unit (a1), one type of structural unit may be used alone, or two or more types of structural units may be used in combination.
Among these, structural units represented by general formula (a1-1) or (a1-3) are preferable. More specifically, at least one structural unit selected from the group consisting of structural units represented by formulas (a1-1-1) to (a-1-1-4), (a1-1-16), (a1-1-17), (a1-1-20) to (a1-1-23), (a1-1-26), (a1-1-32), (a1-1-33) and (a1-3-25) to (a1-3-28) is more preferable.
Further, as the structural unit (a1), structural units represented by general formula (a1-1-01) shown below which includes the structural units represented by formulas (a1-1-1) to (a1-1-3) and (a1-1-26), structural units represented by general formula (a1-1-02) shown below which includes the structural units represented by formulas (a1-1-16), (a1-1-17), (a1-1-20) to (a1-1-23), (a1-1-32) and (a1-1-33), structural units represented by general formula (a1-3-01) shown below which include the structural units represented by formulas (a1-3-25) and (a1-3-26), structural units represented by general formula (a1-3-02) shown below which include the structural units represented by formulas (a1-3-27) and (a1-3-28), structural units represented by general formula (a1-3-03-1) shown below which include the structural units represented by formulas (a1-3-29) and (a1-3-31), and structural units represented by general formula (a1-3-03-2) shown below which include the structural units represented by formulas (a1-3-30) and (a1-3-32) are also preferable.




In the formula, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; and R11 represents a lower alkyl group. R12 represents a lower alkyl group. n′ represents an integer of 1 to 6.

In general formula (a1-1-01), R is the same as defined above.
The lower alkyl group for R11 is the same as defined for the lower alkyl group for R above, a linear or branched alkyl group is preferable, and a methyl group, an ethyl group or an isopropyl group is particularly desirable.
In general formula (a1-1-02), R is the same as defined above.
The lower alkyl group for R12 is the same as defined for the lower alkyl group for R above, a linear or branched alkyl group is preferable, and a methyl group or an ethyl group is particularly desirable.
n′ is preferably 1 or 2.




In the formula, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; R14 represents a lower alkyl group; R13 represents a hydrogen atom or a methyl group; and y represents an integer of 1 to 10.





In the formula, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; R14 represents a lower alkyl group; R13 represents a hydrogen atom or a methyl group; y represents an integer of 1 to 10; and n′ represents an integer of 1 to 6.

In general formulas (a1-3-01) and (a1-3-02), R is the same as defined above.
R13 is preferably a hydrogen atom.
The lower alkyl group for R14 is the same as the lower alkyl group for R, and is preferably a methyl group or an ethyl group.
y is preferably an integer of 1 to 8, more preferably an integer of 2 to 5, and most preferably 2.




In the formulas, R and R14 are the same as defined above; v represents an integer of 1 to 10; w represents an integer of 1 to 10; and t represents an integer of 0 to 3.

v is preferably an integer of 1 to 5, and most preferably 1 or 2.
w is preferably an integer of 1 to 5, and most preferably 1 or 2.
t is preferably an integer of 1 to 3, and most preferably 1 or 2.
In the component (A1), the amount of the structural unit (a1) based on the combined total of all structural units constituting the component (A1) is preferably 10 to 80 mol %, more preferably 20 to 70 mol %, and still more preferably 25 to 50 mol %. When the amount of the structural unit (a1) is at least as large as the lower limit of the above-mentioned range, a pattern can be easily formed using a resist composition prepared from the component (A1). On the other hand, when the amount of the structural unit (a1) is no more than the upper limit of the above-mentioned range, a good balance can be achieved with the other structural units.
(Structural Unit (a0))
The structural unit (a0) is a structural unit derived from an acrylate ester which may have an atom other than hydrogen or a substituent bonded to the carbon atom on the α position and contains an —SO2— group containing cyclic group.
By virtue of the structural unit (a0) containing a —SO2— containing cyclic group, a positive resist composition containing the component (A1) including the structural unit (a0) is capable of improving the adhesion of a resist film to a substrate
Further, the structural unit (a0) contributes to improvement in various lithography properties such as sensitivity, resolution, exposure latitude (EL margin), line width roughness (LWR) and mask reproducibility.
Here, an “—SO2— containing cyclic group” refers to a cyclic group having a ring containing —SO2— within the ring structure thereof, i.e., a cyclic group in which the sulfur atom (S) within —SO2— forms part of the ring skeleton of the cyclic group.
In the —SO2— containing cyclic group, the ring containing —SO2— within the ring skeleton thereof is counted as the first ring. A cyclic group in which the only ring structure is the ring that contains —SO2— in the ring skeleton thereof is referred to as a monocyclic group, and a group containing other ring structures is described as a polycyclic group regardless of the structure of the other rings.
The —SO2— containing cyclic group may be either a monocyclic group or a polycyclic group.
As the —SO2— containing cyclic group, a cyclic group containing —O—SO2— within the ring skeleton thereof, i.e., a cyclic group containing a sultone ring in which —O—S— within the —O—SO2— group forms part of the ring skeleton thereof is particularly desirable.
The —SO2— containing cyclic group preferably has 3 to 30 carbon atoms, more preferably 4 to 20, still more preferably 4 to 15, and most preferably 4 to 12. Herein, the number of carbon atoms refers to the number of carbon atoms constituting the ring skeleton, excluding the number of carbon atoms within a substituent.
The —SO2— containing cyclic group may be either a —SO2— containing aliphatic cyclic group or a —SO2— containing aromatic cyclic group. A —SO2— containing aliphatic cyclic group is preferable.
Examples of the —SO2— containing aliphatic cyclic group include aliphatic cyclic groups in which part of the carbon atoms constituting the ring skeleton has been substituted with a —SO2— group or a —O—SO2— group and has at least one hydrogen atom removed from the aliphatic hydrocarbon ring. Specific examples include an aliphatic hydrocarbon ring in which a —CH2— group constituting the ring skeleton thereof has been substituted with a —SO2— group and has at least one hydrogen atom removed therefrom; and an aliphatic hydrocarbon ring in which a —CH2—CH2— group constituting the ring skeleton has been substituted with a —O—SO2— group and has at least one hydrogen atom removed therefrom.
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 either a monocyclic group or a polycyclic group. As the monocyclic group, a group in which two hydrogen atoms have been removed from a monocycloalkane of 3 to 6 carbon atoms is preferable. Examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic group, a group in which two hydrogen atoms have been removed from a polycycloalkane of 7 to 12 carbon atoms is preferable. Examples of the polycycloalkane include adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane.
The —SO2— containing cyclic group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxy group, an oxygen atom (═O), —COOR′′, —OC(═O)R′′, a hydroxyalkyl group and a cyano group (wherein R′′ represents a hydrogen atom or an alkyl group).
The alkyl group for the substituent is preferably an alkyl group of 1 to 6 carbon atoms. Further, the alkyl group is preferably a linear alkyl group or a branched alkyl group. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and a hexyl group. Among these, a methyl group or ethyl group is preferable, and a methyl group is particularly desirable.
As the alkoxy group for the substituent, an alkoxy group of 1 to 6 carbon atoms is preferable. Further, the alkoxy group is preferably a linear alkoxy group or a branched alkyl group. Specific examples of the alkoxy group include the aforementioned alkyl groups for the substituent having an oxygen atom (—O—) bonded thereto.
Examples of the halogen atom for the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group for the substituent include groups in which part or all of the hydrogen atoms within the aforementioned alkyl groups has been substituted with the aforementioned halogen atoms.
As examples of the halogenated lower alkyl group for the substituent, groups in which part or all of the hydrogen atoms of the aforementioned alkyl groups for the substituent have been substituted with the aforementioned halogen atoms can be given. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly desirable.
In the —COOR′′ group and the —OC(═O)R′′ group, R′′ preferably represents a hydrogen atom or a linear, branched or cyclic alkyl group of 1 to 15 carbon atoms.
When R′′ represents a linear or branched alkyl group, it is preferably an alkyl group of 1 to 10 carbon atoms, more preferably an alkyl group of 1 to 5 carbon atoms, and most preferably a methyl group or an ethyl group.
When R′′ is a cyclic alkyl group (cycloalkyl group), it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. As examples of the cycloalkyl group, groups in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, may be used. Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane and cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
The hydroxyalkyl group for the substituent preferably has 1 to 6 carbon atoms, and specific examples thereof include the aforementioned alkyl groups for the substituent in which at least one hydrogen atom has been substituted with a hydroxy group.
More specific examples of the —SO2— containing cyclic group include groups represented by general formulas (3-1) to (3-4) shown below.




In the formulas, A′ represents an oxygen atom, a sulfur atom or an alkylene group of 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom; z represents an integer of 0 to 2; and R6 represents an alkyl group, an alkoxy group, a halogenated alkyl group, a hydroxyl group, —COOR′′, —OC(═O)R′′, a hydroxyalkyl group or a cyano group, wherein R′′ represents a hydrogen atom or an alkyl group.

In general formulas (3-1) to (3-4) above, A′ represents an oxygen atom (—O—), a sulfur atom (—S—) or an alkylene group of 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom.
As the alkylene group of 1 to 5 carbon atoms represented by A′, a linear or branched alkylene group is preferable, and examples thereof include a methylene group, an ethylene group, an n-propylene group and an isopropylene group.
Examples of alkylene groups that contain an oxygen atom or a sulfur atom include the aforementioned alkylene groups in which —O— or —S— is bonded to the terminal of the alkylene group or present between the carbon atoms of the alkylene group. Specific examples of such alkylene groups include —O—CH2—, —CH2—O—CH2—, —S—CH2—, —CH2—S—CH2—.
As A′, an alkylene group of 1 to 5 carbon atoms or —O— is preferable, more preferably an alkylene group of 1 to 5 carbon atoms, and most preferably a methylene group.
z represents an integer of 0 to 2, and is most preferably 0.
When z is 2, the plurality of R6 may be the same or different from each other.
As the alkyl group, alkoxy group, halogenated alkyl group, —COOR′′, —OC(═O)R′′ and hydroxyalkyl group for R6, the same alkyl groups, alkoxy groups, halogenated alkyl groups, —COOR′′, —OC(═O)R′′ and hydroxyalkyl groups as those described above as the substituent for the —SO2— containing cyclic group can be mentioned.
Specific examples of the cyclic groups represented by general formulas (3-1) to (3-4) are shown below. In the formulas shown below, “Ac” represents an acetyl group.
















As the —SO2— containing cyclic group, a group represented by the aforementioned general formula (3-1) is preferable, at least one member selected from the group consisting of groups represented by the aforementioned chemical formulas (3-1-1), (3-1-18), (3-3-1) and (3-4-1) is more preferable, and a group represented by chemical formula (3-1-1) is most preferable.
More specifically, examples of the structural unit (a0) include structural units represented by general formula (a0-0) shown below.




In the formula, R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; R3 represents a —SO2— containing cyclic group; and R29′ represents a single bond or a divalent linking group.

In general formula (a0-0), R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms.
As the alkyl group for R, a linear or branched alkyl group of 1 to 5 carbon atoms is preferable, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group and a neopentyl group.
The halogenated alkyl group for R is a group in which part or all of the hydrogen atoms of the aforementioned alkyl group has been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly desirable.
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 particularly desirable in terms of industrial availability.
In formula (a0-0), R3 is the same as defined for the aforementioned —SO2— containing group.
R29′ may be a single bond or a divalent linking group. In terms of the effects of the present invention, a divalent linking group is preferable.
As the divalent linking group for R29′, an alkylene group, a divalent alicyclic hydrocarbon group or a divalent linking group containing a hetero atom is preferable. Among these, an alkylene group or a divalent linking group containing a hetero atom is more preferable.
When R29′ represents an alkylene group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 6, still more preferably 1 to 4, and most preferably 1 to 3.
When R29′ represents a divalent alicyclic hydrocarbon group, it is particularly desirable that the alicyclic hydrocarbon group be a group in which two or more hydrogen atoms have been removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane or tetracyclododecane.
When R29′ represents a divalent linking group containing a hetero atom, preferable examples of the linking group include —O—, —C(═O)—O—, —C(═O)—, —O—C(═O)—O—, —C(═O)—NH—, —NH— (H may be substituted with a substituent such as an alkyl group or an acyl group), —S—, —S(═O)2—, —S(═O)2—O— and a group represented by general formula -A-O-B-, [A-C(═O)—O]m′—B— or -A-O-C(═O)—B— [in the formulas, each of A and B independently represents a divalent hydrocarbon group which may have a substituent, O represents an oxygen atom, and m′ represents an integer of 0 to 3].
When R29′ represents —NH—, H may be substituted with a substituent such as an alkyl group, an aryl group (an aromatic group) or the like. The substituent (an alkyl group, an aryl group or the like) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and most preferably 1 to 5.
In the group represented by the formula -A-O-B-, [A-C(═O)—O]m′—B— or -A-O-C(═O)—B—, each of A and B independently represents a divalent hydrocarbon group which may have a substituent.
As A, a linear aliphatic hydrocarbon group is preferable, more preferably a linear alkylene group, still more preferably a linear alkylene group of 1 to 5 carbon atoms, and a methylene group or an ethylene group is particularly desirable.
As B, a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkylmethylene group is more preferable. The alkyl group within the alkylmethylene group is preferably a linear alkyl group of 1 to 5 carbon atoms, more preferably a linear alkyl group of 1 to 3 carbon atoms, and most preferably a methyl group.
In the group represented by the formula [A-C(═O)—O]m′—B—, m represents an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1. Namely, it is particularly desirable that the group represented by the formula -[A-C(═O)—O]m′—B— is a group represented by the formula -A-C(═O)—O—B—. Among these, a group represented by the formula —(CH2)a′—C(═O)—O—(CH2)b′— is preferable. In the formula, a′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. b′ is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1.
Among these, as the divalent linking group for R29′, a linear group containing oxygen as a hetero atom e.g., a divalent linking group containing an ether bond or an ester bond with an alkylene group is preferable. In particular, a group represented by a general formula: —R4—C(═O)—O—[in the formula, R4 represents a divalent linking group] is preferable.
Namely, the structural unit (a0) is preferably a structural unit represented by general formula (a0-0-1) shown below.




In the formula, R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; R4 represents a divalent linking group; and R3 represents an —SO2— containing cyclic group.

R is the same as defined for R in the aforementioned formula (a0-0).
R4 is not particularly limited. For example, the same divalent linking groups as those described for R29′ in general formula (a0-0) can be mentioned.
As the divalent linking group for R4, an alkylene group, a divalent alicyclic hydrocarbon group or a divalent linking group containing a hetero atom is preferable.
As the linear or branched alkylene group, the divalent alicyclic hydrocarbon group and the divalent linking group containing a hetero atom, the same linear or branched alkylene group, divalent alicyclic hydrocarbon group and divalent linking group containing a hetero atom as those described above as preferable examples of R29′ can be mentioned.
Among these, as R4, a linear or branched alkylene group or a divalent linking group containing oxygen as a hetero atom is preferable, and a linear or branched alkylene group is more preferable.
As the linear alkylene group, a methylene group or an ethylene group is preferable, and a methylene group is particularly desirable.
As the branched alkylene group, an alkylmethylene group or an alkylethylene group is preferable, and —CH(CH3)—, —C(CH3)2— or —C(CH3)2CH2— is particularly desirable.
As the divalent linking group containing a hetero atom, a divalent linking group containing an ether bond or an ester bond is preferable, and a group represented by the aforementioned formula -A-O-B-, -[A-C(═O)—O]m′—B— or -A-O-C(═O)—B— is more preferable. m′ represents an integer of 0 to 3.
Among these, a group represented by the formula -A-O—C(═O)—B— is preferable, and a group represented by the formula: —(CH2)c′-O—C(═O)—(CH2)d′— is particularly desirable. c′ represents an integer of 1 to 5, and preferably 1 or 2. d′ represents an integer of 1 to 5, and preferably 1 or 2.
In particular, as the structural unit (a0), a structural unit represented by general formula (a0-0-11) or (a0-0-12) shown below is preferable, and a structural unit represented by general formula (a0-0-12) is more preferable.




In the formulas, R, A′, R6, z and R4 are the same as defined above.

In general formula (a0-0-11), A′ is preferably a methylene group, an ethylene group, an oxygen atom (—O—) or a sulfur atom (—S—).
As R4, a linear or branched alkylene group or a divalent linking group containing an oxygen atom is preferable. As the linear or branched alkylene group and the divalent linking group containing an oxygen atom represented by R4, the same linear or branched alkylene groups and the divalent linking groups containing an oxygen atom as those described above can be mentioned.
As the structural unit represented by general formula (a0-0-12), a structural unit represented by general formula (a0-0-12a) or (a0-0-12b) shown below is particularly desirable.




In the formulas, R and A′ are the same as defined above; and each of c′ to e′ independently represents an integer of 1 to 5.

As the structural unit (a0), one type of structural unit may be used alone, or two or more types of structural units may be used in combination.
In terms of achieving an excellent shape for a resist pattern formed using a positive resist composition containing the component (A1) and excellent lithography properties such as EL margin, LWR and mask reproducibility, the amount of the structural unit (a0) within the component (A1), based on the combined total of all structural units constituting the component (A1) is preferably 1 to 60 mol %, more preferably 3 to 55 mol %, still more preferably 5 to 50 mol %, and most preferably 5 to 45 mol %.
(Structural Unit (a5))
The structural unit (a5) is a structural unit represented by general formula (a5-1) shown below.
The structural unit (a5) exhibits high affinity for various organic solvents. Therefore, by including the structural unit (a5), the solubility of the component (A1) in an organic solvent can be improved. In particular, a component (A1) including the structural unit (a5) exhibits excellent solubility in an alcohol solvent.




In the formula, R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; Y5 represents an aliphatic hydrocarbon group which may have a substituent: Z represents a monovalent organic group; a represents an integer of 1 to 3, and b represents an integer of 0 to 2, provided that a+b=1 to 3; and each of c, d and e independently represents an integer of 0 to 3.
In formula (a5-1), R is the same as defined above for R in the structural unit (a1). Of the various possibilities, R is preferably a hydrogen atom or a methyl group.
In formula (a5-1), Y5 represents an aliphatic hydrocarbon group which may have a substituent.
The aliphatic hydrocarbon group for Y5 may be either a saturated aliphatic hydrocarbon group, or an unsaturated aliphatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be linear, branched or cyclic.
In the present description and claims, an “aliphatic hydrocarbon group” refers to an aliphatic hydrocarbon group that has no aromaticity.
Further, the expression “may have a substituent” means that part of the carbon atoms constituting the aliphatic hydrocarbon group may be substituted with a substituent group containing a hetero atom, or part or all of the hydrogen atoms constituting the aliphatic hydrocarbon group may be substituted with a substituent group containing a hetero atom.
As the “hetero atom” for Y5, there is no particular limitation as long as it is an atom other than carbon and hydrogen, and examples thereof include a halogen atom, an oxygen atom, a sulfur atom and a nitrogen atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom.
The substituent group containing a hetero atom may consist of a hetero atom, or may be a group containing a hetero atom and a group or atom other than a hetero atom. Specific examples thereof include —O—, —C(═O)—O—, —C(═O)—, —O—C(═O)—O—, —C(═O)—NH—, —NH— (the H may be replaced with a substituent such as an alkyl group or an acyl group), —S—, —S(═O)2— and —S(═O)2—O—. When the aliphatic hydrocarbon group is cyclic, the aliphatic hydrocarbon group may contain any of these substituent groups in the ring structure.
Examples of the substituent group for substituting part or all of the hydrogen atoms constituting the aliphatic hydrocarbon group include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (═O), a cyano group and an alkyl group.
The aforementioned alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group or tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
Examples of the aforementioned halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
Example of the aforementioned halogenated alkyl group includes a group in which part or all of the hydrogen atoms within an alkyl group of 1 to 5 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group) have been substituted with the aforementioned halogen atoms.
Examples of the alkyl group include alkyl groups of 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group.
When Y5 represents a linear or branched aliphatic hydrocarbon group, the linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and most preferably 1 to 3. Specific examples of preferable linear or branched aliphatic hydrocarbon group include chain-like alkylene groups.
When Y5 represents a cyclic aliphatic hydrocarbon group (aliphatic cyclic group), the basic ring of the “aliphatic cyclic group” exclusive of substituents (aliphatic ring) is not limited to be constituted from only carbon and hydrogen (not limited to hydrocarbon rings), and the ring (aliphatic ring) may contain a hetero atom (e.g., an oxygen atom or the like) in the structure thereof. Further, the “hydrocarbon ring” may be either saturated or unsaturated, but is preferably saturated.
The aliphatic cyclic group may be either a polycyclic group or a monocyclic group. Examples of aliphatic cyclic groups include groups in which two or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane which may or may not be substituted with a lower alkyl group, a fluorine atom or a fluorinated alkyl group. Specific examples include groups in which two or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
Further examples of the aliphatic cyclic group include groups in which two or more hydrogen atoms have been removed from tetrahydrofuran or tetrahydropyran which may or may not be substituted with a lower alkyl group, a fluorine atom or a fluorinated alkyl group.
The aliphatic cyclic group within the structural unit (a5) is preferably a polycyclic group, and a group in which two or more hydrogen atoms have been removed from adamantane is particularly desirable.
In general formula (a5-1), Z represents a monovalent organic group.
In the present description and claims, the term “organic group” refers to a group containing a carbon atom, and may include atoms other than carbon (e.g., a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (such as a fluorine atom and a chlorine atom) and the like).
Examples of the organic group for Z include an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and a group represented by the formula -Q5-R5 (in the formula, Q5 represents a divalent linking group, and R5 represents an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent).
Examples of the aliphatic hydrocarbon group for the organic group represented by Z include a linear, branched or cyclic, saturated hydrocarbon group of 1 to 20 carbon atoms, and a linear or branched, aliphatic unsaturated hydrocarbon group of 2 to 20 carbon atoms.
Examples of the linear, saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group.
Examples of the branched, saturated hydrocarbon group include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group and a 4-methylpentyl group.
The linear or branched alkyl group may have a substituent. Examples of the substituent include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (═O), a cyano group and a carboxy group.
The alkoxy group as the substituent for the linear or branched alkyl group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
Examples of the halogen atom as the substituent for the linear or branched alkyl group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
Examples of the halogenated alkyl group as a substituent include groups in which part or all of the hydrogen atoms within an alkyl group of 1 to 5 carbon atoms (preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group, or the like) have been substituted with the aforementioned halogen atoms.
The cyclic, saturated hydrocarbon group may be either a polycyclic group or a monocyclic group. Examples thereof include cyclic, saturated hydrocarbon groups of 3 to 20 carbon atoms, such as groups in which one hydrogen atom has been removed from a monocycloalkane or a polycycloalkane (e.g., a bicycloalkane, a tricycloalkane or a tetracycloalkane). More specific examples include groups in which one hydrogen atom has been removed from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane or cyclooctane; and groups in which one hydrogen atom has been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
The cyclic alkyl group may have a substituent. For example, part of the carbon atoms constituting the ring within the cyclic alkyl group may be substituted with a hetero atom, or a hydrogen atom bonded to the ring within the cyclic alkyl group may be substituted with a substituent.
In the former example, a heterocycloalkane in which part of the carbon atoms constituting the ring within the aforementioned monocycloalkane or polycycloalkane has been substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, and one hydrogen atom has been removed therefrom, can be used. Further, the ring may contain an ester bond (—C(═O)—O—). More specific examples include a lactone-containing monocyclic group, such as a group in which one hydrogen atom has been removed from γ-butyrolactone; and a lactone-containing polycyclic group, such as a group in which one hydrogen atom has been removed from a bicycloalkane, tricycloalkane or tetracycloalkane containing a lactone ring.
In the latter example, as the substituent, the same substituent groups as those for the aforementioned linear or branched alkyl group, or an alkyl group of 1 to 5 carbon atoms can be used.
Examples of linear unsaturated hydrocarbon groups include a vinyl group, a propenyl group (an allyl group) and a butynyl group.
Examples of branched unsaturated hydrocarbon groups include a 1-methylpropenyl group and a 2-methylpropenyl group.
The aforementioned linear or branched, unsaturated hydrocarbon group may have a substituent. Examples of substituents include the same substituents as those which the aforementioned linear or branched alkyl group may have.
The aromatic hydrocarbon group as the organic group for Z is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon ring preferably has 3 to 30 carbon atoms, more preferably 5 to 30, still more preferably 5 to 20, still more preferably 6 to 15, and most preferably 6 to 12.
Here, the number of carbon atoms within a substituent(s) is not included in the number of carbon atoms of the aromatic hydrocarbon group.
The aromatic hydrocarbon group may be either a group including an aromatic hydrocarbon ring in which the ring skeleton of the aromatic ring is constituted of only carbon atoms, or a group including an aromatic hetero ring in which the ring skeleton of the aromatic ring contains not only carbon atoms but also a hetero atom.
Examples of the aromatic hydrocarbon group include an aryl group which is an aromatic hydrocarbon ring having one hydrogen atom removed therefrom, such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group or a phenanthryl group; a heteroaryl group in which part of the carbon atoms constituting the aforementioned aryl group has been substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom; and an arylalkyl group, such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group or a 2-naphthylethyl group. The alkyl chain within the arylalkyl group preferably has 1 to 4 carbon atom, more preferably 1 or 2, and most preferably 1.
The aromatic hydrocarbon group may have a substituent. For example, part of the carbon atoms constituting the aromatic ring within the aromatic hydrocarbon group may be substituted with a hetero atom, or a hydrogen atom bonded to the aromatic ring within the aromatic hydrocarbon group may be substituted with a substituent.
In the former example, a heteroaryl group in which part of the carbon atoms constituting the ring within the aforementioned aryl group has been substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, and a heteroarylalkyl group in which part of the carbon atoms constituting the ring of the aforementioned arylalkyl group has been substituted with the aforementioned heteroatom can be used.
In the latter example, as the substituent for the aromatic group, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (═O), an acetyl group or the like can be used.
Examples of the alkyl group, alkoxy group, halogen atom and halogenated alkyl group as the substituent for the aromatic group include the same substituent groups as those for the aforementioned linear or branched alkyl group, and an alkyl group of 1 to 5 carbon atoms.
In the group represented by the formula -Q5-R5, Q5 represents a divalent linking group, and R5 represents an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent.
As examples of the divalent linking group for Q5, the same groups as those described above in the explanation of Y2 in formula (a1-0-2) can be mentioned.
As examples of R5, the same aliphatic hydrocarbon groups and aromatic hydrocarbon groups as those described above for Z can be mentioned.
Among these examples, as the organic group for Z, in consideration of the improvement in solubility in an organic solvent when blended within a resist composition, a group containing an aliphatic hydrocarbon group which may have a substituent is preferable, and a group represented by the formula -Q5-R8′ (in the formula, Q5 represents a divalent linking group, and R8′ represents an aliphatic hydrocarbon group which may have a substituent) is more preferable. Specific examples of preferable organic groups include a tertiary alkyl group-containing group and an alkoxyalkyl group.
(Tertiary Alkyl Group-Containing Group)
In the present description and the claims, the term “tertiary alkyl group” refers to an alkyl group having a tertiary carbon atom. As mentioned above, the term “alkyl group” refers to a monovalent saturated hydrocarbon group, and includes chain-like (linear or branched) alkyl groups and cyclic alkyl groups.
The term “tertiary alkyl group-containing group” refers to a group which includes a tertiary alkyl group in the structure thereof. The tertiary alkyl group-containing group may be either constituted of only a tertiary alkyl group, or constituted of a tertiary alkyl group and an atom or group other than a tertiary alkyl group.
Examples of the “atom or group other than a tertiary alkyl group” which constitutes the tertiary alkyl group-containing group with a tertiary alkyl group include a carbonyloxy group, a carbonyl group, an alkylene group and an oxygen atom.
As the tertiary alkyl group-containing group for Z, a tertiary alkyl group-containing group which does not have a ring structure, and a tertiary alkyl group-containing group which has a ring structure can be mentioned.
A tertiary alkyl group-containing group which does not have a ring structure is a group which has a branched tertiary alkyl group as the tertiary alkyl group, and has no ring in the structure thereof.
As the branched tertiary alkyl group, for example, a group represented by general formula (I) shown below can be mentioned.




In formula (I), each of R21 to R23 independently represents a linear or branched alkyl group. The number of carbon atoms within the alkyl group is preferably from 1 to 5, and more preferably from 1 to 3.
Further, in the group represented by general formula (I), the total number of carbon atoms is preferably from 4 to 7, more preferably from 4 to 6, and most preferably 4 or 5.
Preferable examples of the group represented by general formula (I) include a tert-butyl group and a tert-pentyl group, and a tert-butyl group is more preferable.
Examples of tertiary alkyl group-containing groups which do not have a ring structure include the aforementioned branched tertiary alkyl group; a tertiary alkyl group-containing, chain-like alkyl group in which the aforementioned branched tertiary alkyl group is bonded to a linear or branched alkylene group; a tertiary alkyloxycarbonyl group which has the aforementioned branched tertiary alkyl group as the tertiary alkyl group; and a tertiary alkyloxycarbonylalkyl group which has the aforementioned branched tertiary alkyl group as the tertiary alkyl group.
As the alkylene group within the tertiary alkyl group-containing, chain-like alkyl group, an alkylene group of 1 to 5 carbon atoms is preferable, an alkylene group of 1 to 4 carbon atoms is more preferable, and an alkylene group of 1 or 2 carbon atoms is the most desirable.
As a chain-like tertiary alkyloxycarbonyl group, for example, a group represented by general formula (II) shown below can be mentioned. In general formula (II), R21 to R23 are the same as defined for R21 to R23 in general formula (I). As the chain-like tertiary alkyloxycarbonyl group, a tert-butyloxycarbonyl group (t-boc) and a tert-pentyloxycarbonyl group are preferable.




As a chain-like tertiary alkyloxycarbonylalkyl group, for example, a group represented by general formula (III) shown below can be mentioned. In general formula (III), R21 to R23 are the same as defined for R21 to R23 in general formula (I). f represents an integer of 1 to 3, and is preferably 1 or 2. As the chain-like tertiary alkyloxycarbonylalkyl group, a tert-butyloxycarbonylmethyl group and a tert-butyloxycarbonylethyl group are preferable.
Among these, as the tertiary alkyl group-containing group which does not have a ring structure, a tertiary alkyloxycarbonyl group or a tertiary alkyloxycarbonylalkyl group is preferable, a tertiary alkyloxycarbonyl group is more preferable, and a tert-butyloxycarbonyl group (t-boc) is most preferable.




A tertiary alkyl group-containing group which has a ring structure is a group which contains a tertiary carbon atom and a ring in the structure thereof.
In the tertiary alkyl group-containing group which has a ring structure, the ring structure preferably has 4 to 12 carbon atoms which constitute the ring, more preferably 5 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. As the ring structure, for example, groups in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane can be mentioned. Preferable examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
As the tertiary alkyl group-containing group which has a ring structure, for example, a group having the following group (1) or (2) as the tertiary alkyl group can be mentioned.
(1) A group in which a linear or branched alkyl group is bonded to a carbon atom which constitutes the ring of a cyclic alkyl group (cycloalkyl group), so that the carbon atom becomes a tertiary carbon atom.
(2) A group in which an alkylene group (branched alkylene group) having a tertiary carbon atom is bonded to a carbon atom constituting the ring of a cycloalkyl group.
In the aforementioned group (1), the linear or branched alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.
Examples of the group (1) include a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 1-methyl-1-cycloalkyl group and a 1-ethyl-1-cycloalkyl group.
In the aforementioned group (2), the cycloalkyl group having a branched alkylene group bonded thereto may have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group of 1 to 5 carbon atoms, and an oxygen atom (═O).
As an example of the group (2), a group represented by general formula (IV) shown below can be given.




In general formula (IV), R24 represents a cycloalkyl group which may or may not have a substituent. Examples of the substituent which the cycloalkyl group may have include a fluorine atom, a fluorinated alkyl group of 1 to 5 carbon atoms, and an oxygen atom (═O).
Each of R25 and R26 independently represents a linear or branched alkyl group. As the alkyl group, the same alkyl groups as those described above for R21 to R23 in general formula (I) may be mentioned.
(Alkoxyalkyl Group)
As the alkoxyalkyl group for Z, for example, a group represented by general formula (V) shown below can be mentioned.
[Chemical Formula 36.]

—R42—O—R41  (v)

In formula (V), R41 represents a linear, branched or cyclic alkyl group.
When R41 represents a linear or branched alkyl group, it is preferably an alkyl group of 1 to 5 carbon atoms, more preferably an ethyl group or a methyl group, and an ethyl group is particularly desirable.
When R41 represents a cyclic alkyl group, it preferably has 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. As examples of the cyclic alkyl group, groups in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane, and which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, may be mentioned. Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane. Among these, a group in which one or more hydrogen atoms have been removed from adamantane is preferable.
R42 represents a linear or branched alkylene group. The alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and most preferably 1 or 2 carbon atoms.
As the alkoxyalkyl group for Z, a group represented by general formula (VI) shown below is particularly desirable.




In general formula (VI), R41 is the same as defined above, and each of R43 and R44 independently represents a linear or branched alkyl group or a hydrogen atom.
With respect to R43 and R44, the alkyl group preferably has 1 to 15 carbon atoms, and may be either linear or branched. As the alkyl group, an ethyl group or a methyl group is preferable, and a methyl group is most preferable.
It is particularly desirable that either one of R43 and R44 be a hydrogen atom, and the other be a methyl group.
Among the above-mentioned examples, as Z, a tertiary alkyl group-containing group is preferable, a group represented by general formula (II) above is more preferable, and a tert-butyloxycarbonyl group (t-boc) is most preferable.
In general formula (a5-1), a represents an integer of 1 to 3, and b represents an integer of 0 to 2, with the provision that a+b=1 to 3.
a is preferably 1.
b is preferably 0.
a+b is preferably 1.
c represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
d represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
e represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
As the structural unit (a5), a structural unit represented by general formula (a5-1-1) or (a5-1-2) shown below is particularly desirable.




In the formula, R, Z, b, c, d and e are the same as defined above.





In the formula, R, Z, a, b, c, d and e are respectively the same as defined above, and c′′ represents an integer of 1 to 3.

In formula (a5-1-2), c′′ represents an integer of 1 to 3, preferably 1 or 2, and still more preferably 1.
When c represents 0 in formula (a5-1-2), the oxygen atom on the terminal of the carbonyloxy group within the acrylate ester is preferably not bonded to the carbon atom which is bonded to the oxygen atom within the cyclic group. That is, when c represents 0, it is preferable that there are at least two carbon atoms present between the terminal oxygen atom and the oxygen atom within the cyclic group (excluding the case where the number of such carbon atom is one (i.e., the case where an acetal bond is formed)).
A monomer for deriving the structural unit (a5) can be synthesized, for example, by protecting part or all of the hydroxyl groups within a compound represented by general formula (a5-1′) shown below (namely, an acrylate ester containing an aliphatic cyclic group having 1 to 3 alcoholic hydroxyl groups) with organic groups (preferably tertiary alkyl group-containing groups or alkoxyalkyl groups) by a conventional method.




In the formula, R, Y5, a, b, c, d and e are respectively the same as defined above.

As the structural unit (a5), one type of structural unit may be used alone, or two or more types of structural units may be used in combination.
The amount of the structural unit (a5) within the component (A1) based on the combined total of all structural units constituting the component (A1) is preferably 1 to 45 mol %, more preferably 5 to 45 mol %, still more preferably 5 to 40 mol %, and most preferably 5 to 35 mol %. When the amount of the structural unit (a5) is at least as large as the lower limit of the above-mentioned range, the solubility of the component (A1) in an organic solvent (S) is improved. On the other hand, when the amount of the structural unit (a5) is no more than the upper limit of the above-mentioned range, a good balance can be achieved with the other structural units.
(Other Structural Units)
The component (A1) may also have a structural unit other than the above-mentioned structural units (a1), (a0) and (a5), as long as the effects of the present invention are not impaired.
As such a structural unit, any other structural unit which cannot be classified as one of the above structural units (a1), (a0) and (a5) can be used without any particular limitation, and any of the multitude of conventional structural units used within resist resins for ArF excimer lasers or KrF excimer lasers (and particularly for ArF excimer lasers) can be used.
Examples of other structural units include a structural unit (a2), a structural unit (a6), a structural unit (a3) and a structural unit (a4) which are described below.
Structural Unit (a2)
The structural unit (a2) is a structural unit derived from an acrylate ester which may have an atom other than hydrogen or a substituent bonded to the carbon atom on the α position and contains a lactone-containing cyclic group.
The term “lactone-containing cyclic group” refers to a cyclic group including one ring containing a —O—C(═O)— structure (lactone ring). The term “lactone ring” refers to a single ring containing a —O—C(O)— structure, and this ring is counted as the first ring. A lactone-containing cyclic group in which the only ring structure is the lactone ring is referred to as a monocyclic group, and groups containing other ring structures are described as polycyclic groups regardless of the structure of the other rings.
When the component (A1) is used for forming a resist film, the lactone-containing cyclic group of the structural unit (a2) is effective in improving the adhesion between the resist film and the substrate, and increasing the compatibility with the developing solution containing water.
As the structural unit (a2), there is no particular limitation, and an arbitrary structural unit may be used.
Specific examples of lactone-containing monocyclic groups include a group in which one hydrogen atom has been removed from a 4- to 6-membered lactone ring, such as a group in which one hydrogen atom has been removed from β-propionolatone, a group in which one hydrogen atom has been removed from γ-butyrolactone, and a group in which one hydrogen atom has been removed from δ-valerolactone. Further, specific examples of lactone-containing polycyclic groups include groups in which one hydrogen atom has been removed from a lactone ring-containing bicycloalkane, tricycloalkane or tetracycloalkane.
More specifically, examples of the structural unit (a2) include structural units represented by general formulas (a2-1) to (a2-5) shown below.




In the formulas, R represents a hydrogen atom, a lower alkyl group or a halogenated lower alkyl group; each R′ independently represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms or —COOR′′, wherein R′′ represents a hydrogen atom or an alkyl group; R29 represents a single bond or a divalent linking group; s′′ represents an integer of 0 to 2; A′′ represents an oxygen atom, a sulfur atom or an alkylene group of 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom; and m represents 0 or 1.

In general formulas (a2-1) to (a2-5), R is the same as defined for R in the structural unit (a1).
Examples of the alkyl group of 1 to 5 carbon atoms for R′ include a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group.
Examples of the alkoxy group of 1 to 5 carbon atoms for R′ include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and a tert-butoxy group
In terms of industrial availability, R′ is preferably a hydrogen atom.
R′′ preferably represents a hydrogen atom or a linear, branched or cyclic alkyl group of 1 to 15 carbon atoms.
When R′′ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
When R′′ is a cyclic alkyl group (cycloalkyl group), it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. As examples of the cycloalkyl group, groups in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, may be used. Examples of such groups include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
As A′′, an alkylene group of 1 to 5 carbon atoms or —O— is preferable, more preferably an alkylene group of 1 to 5 carbon atoms, and most preferably a methylene group.
R29 represents a single bond or a divalent linking group. Examples of divalent linking groups include the same divalent linking groups as those described above for Y2 in general formula (a1-0-2). Among these, an alkylene group, an ester bond (—C(═O)—O—) or a combination thereof is preferable. The alkylene group as a divalent linking group for R29 is preferably a linear or branched alkylene group. Specific examples include the same linear alkylene groups and branched alkylene groups as those described above for the aliphatic cyclic group A in Y2.
s′′ is preferably 1 or 2.
Specific examples of structural units represented by general formulas (a2-1) to (a2-5) are shown below.
In the formulas shown below, Rα represents a hydrogen atom, a methyl group or a trifluoromethyl group.





































In the component (A1), as the structural unit (a2), one type of structural unit may be used, or two or more types may be used in combination.
As the structural unit (a2), at least one structural unit selected from the group consisting of formulas (a2-1) to (a2-5) is preferable, and at least one structural unit selected from the group consisting of formulas (a2-1) to (a2-3) is more preferable. Of these, it is preferable to use at least one structural unit selected from the group consisting of structural units represented by formulas (a2-1-1), (a2-1-2), (a2-2-1), (a2-2-7), (a2-3-1) and (a2-3-5).
In the component (A1), the amount of the structural unit (a2) based on the combined total of all structural units constituting the component (A1) is preferably 5 to 60 mol %, more preferably 10 to 50 mol %, and still more preferably 20 to 50 mol %. When the amount of the structural unit (a2) is at least as large as the lower limit of the above-mentioned range, the effect of using the structural unit (a2) can be satisfactorily achieved. On the other hand, when the amount of the structural unit (a2) is no more than the upper limit of the above-mentioned range, a good balance can be achieved with the other structural units.
Structural Unit (a6)
The structural unit (a6) is a structural unit represented by general formula (a6-1) shown below.




In general formula (a6-1), R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; Y3 represents an alkylene group or an aliphatic cyclic group; each of g and h independently represents an integer of 0 to 3; and i represents an integer of 1 to 3.

In general formula (a6-1), R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms. R is the same as defined for R in the aforementioned structural unit (a1). Of the various possibilities, R is preferably a hydrogen atom or a methyl group.
Y3 represents an alkylene group or an aliphatic cyclic group.
As the alkylene group for Y3, an alkylene group of 1 to 10 carbon atoms can be used.
As the aliphatic cyclic group for Y3, the same groups as those described above for the aliphatic cyclic group for Y5 in general formula (a5-1) can be mentioned. It is preferable that the structure of the basic ring (aliphatic ring) in Y3 be the same as that in Y5.
g represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
h represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
i represents an integer of 1 to 3, and is most preferably 1.
As the structural unit (a6), a structural unit represented by general formula (a6-1-1) shown below is preferable, and a structural unit in which one of the “i” groups of —(CH2)h—OH is bonded to the 3rd position of the 1-adamantyl group is particularly desirable.




In the formula, R, g, h and i are respectively the same as defined above.

As the structural unit (a6), one type of structural unit may be used alone, or two or more types of structural units may be used in combination.
The amount of the structural unit (a6) within the component (A1) based on the combined total of all structural units constituting the component (A1) is preferably 1 to 40 mol %, more preferably 1 to 35 mol %, still more preferably 5 to 30 mol %, and most preferably 5 to 25 mol %. When the amount of the structural unit (a3) is at least as large as the lower limit of the above-mentioned range, the rectangularity of the cross-sectional shape of the resist pattern is improved, and hence, a resist pattern having an excellent shape can be formed. On the other hand, when the amount of the structural unit (a3) is no more than the upper limit of the above-mentioned range, a good balance can be achieved with the other structural units.
Structural Unit (a3)
The structural unit (a3) is a structural unit derived from an acrylate ester which may have an atom other than hydrogen or a substituent bonded to the carbon atom on the a position and contains a polar group-containing aliphatic hydrocarbon group (provided that the structural unit (a3) excludes the aforementioned structural units (a5) and (a6)).
When the component (A1) includes the structural unit (a3), the hydrophilicity of the component (A) is improved, and hence, the compatibility of the component (A) with the developing solution is improved. As a result, the alkali solubility of the exposed portions improves, which contributes to favorable improvements in the resolution.
Examples of the polar group include a hydroxyl group, cyano group, carboxyl group, or hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group have been substituted with fluorine atoms, although a hydroxyl group is particularly desirable.
Examples of the aliphatic hydrocarbon group include linear or branched hydrocarbon groups (preferably alkylene groups) of 1 to 10 carbon atoms, and cyclic aliphatic hydrocarbon groups (cyclic groups). These cyclic groups can be selected appropriately from the multitude of groups that have been proposed for the resins of resist compositions designed for use with ArF excimer lasers. The cyclic group is preferably a polycyclic group, more preferably a polycyclic group of 7 to 30 carbon atoms.
Of the various possibilities, structural units derived from an acrylate ester that include an aliphatic polycyclic group that contains a hydroxyl group, cyano group, carboxyl group or a hydroxyalkyl group in which part of the hydrogen atoms of the alkyl group have been substituted with fluorine atoms are particularly desirable. Examples of the polycyclic group include groups in which two or more hydrogen atoms have been removed from a bicycloalkane, tricycloalkane, tetracycloalkane or the like. Specific examples include groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane. Of these polycyclic groups, groups in which two or more hydrogen atoms have been removed from adamantane, norbornane or tetracyclododecane are preferred industrially.
When the aliphatic hydrocarbon group within the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group of 1 to 10 carbon atoms, the structural unit (a3) is preferably a structural unit derived from a hydroxyethyl ester of acrylic acid. On the other hand, when the hydrocarbon group is a polycyclic group, structural units represented by formulas (a3-1) and (a3-2) shown below are preferable.




In the formulas, R is the same as defined above; k is an integer of 1 to 3; t′ is an integer of 1 to 3; l is an integer of 1 to 5; and s is an integer of 1 to 3.

In general formula (a3-1), k is preferably 1. The cyano group is preferably bonded to the 5th or 6th position of the norbornyl group.
In formula (a3-2), t′ is preferably 1. l is preferably 1. s is preferably 1. Further, it is preferable that a 2-norbornyl group or 3-norbornyl group be bonded to the terminal of the carboxy group of the acrylic acid. The fluorinated alkyl alcohol is preferably bonded to the 5th or 6th position of the norbornyl group.
As the structural unit (a3), one type of structural unit may be used, or two or more types may be used in combination.
The amount of the structural unit (a3) within the component (A1) based on the combined total of all structural units constituting the component (A1) is preferably 5 to 50 mol %, more preferably 5 to 40 mol %, and still more preferably 5 to 25 mol %. When the amount of the structural unit (a3) is at least as large as the lower limit of the above-mentioned range, the effect of using the structural unit (a3) can be satisfactorily achieved. On the other hand, when the amount of the structural unit (a3) is no more than the upper limit of the above-mentioned range, a good balance can be achieved with the other structural units.
Structural Unit (a4)
The structural unit (a2) is a structural unit derived from an acylate ester which may have an atom other than hydrogen or a substituent bonded to the carbon atom on the α position and contains an acid non-dissociable aliphatic polycyclic group.
In the structural unit (a4), examples of this polycyclic group include the same groups as those described above in relation to the aforementioned structural unit (a1), and any of the multitude of conventional polycyclic groups used within the resin component of resist compositions for ArF excimer lasers or KrF excimer lasers (and particularly for ArF excimer lasers) can be used.
In consideration of industrial availability and the like, at least one polycyclic group selected from amongst a tricyclodecyl group, adamantyl group, tetracyclododecyl group, isobornyl group, and norbornyl group is particularly desirable. These polycyclic groups may be substituted with a linear or branched alkyl group of 1 to 5 carbon atoms.
Specific examples of the structural unit (a4) include units with structures represented by general formulas (a4-1) to (a4-5) shown below.




In the formulas, R is the same as defined above.

When the structural unit (a4) is included in the component (A1), the amount of the structural unit (a4) based on the combined total of all the structural units that constitute the component (A1) is preferably within the range from 1 to 30 mol %, and more preferably from 10 to 20 mol %.
In the positive resist composition of the present invention, the component (A1) includes the structural unit (a1) and the structural unit (a0), and specific examples thereof include a copolymer having the structural unit (a1) and the structural unit (a0).
As preferable examples of the component (A1), a copolymer having the structural units (a1), (a0) and (a2); a copolymer having the structural units (a1), (a0) and (a6); and a copolymer having the structural units (a1), (a0), (a2) and (a6) can be mentioned, as these copolymers exhibit improved lithography properties such as roughness when used in combination with the component (C1) described later.
Further, as preferable examples of the component (A1), a copolymer having the structural units (a1), (a0) and (a5); a copolymer having the structural units (a1), (a0), (a5) and (a2); and a copolymer having the structural units (a1), (a0), (a5), (a2) and (a6) can be mentioned, as these copolymers exhibit high solubility in an alcohol solvent, and can be preferably used a resist composition for the second pattering in a double pattering process.
In the component (A), as the component (A1), one type may be used alone, or two or more types may be used in combination.
In the present invention, as the component (A1), a polymeric compound that includes a combination of structural units such as that shown below is particularly desirable.




In the formulas, R, R4, A′ and R11 are the same as defined above; and the plurality of R may be the same or different from each other; R21 to R23 are the same as defined for R21 to R23 in formula (II) above; and e is the same as defined for e in formula (a5-1) above.





In the formula, R, R4, A′, R11 and R12 are the same as defined above; and the plurality of R may be the same or different from each other; R21 to R23 are respectively the same as defined for R21 to R23 in the aforementioned formula (II); and e is the same as defined for e in the aforementioned formula (a5-1).

The component (A1) can be obtained, for example, by a conventional radical polymerization or the like of the monomers corresponding with each of the structural units, using a radical polymerization initiator such as azobisisobutyronitrile (AIBN).
Furthermore, in the component (A1), by using a chain transfer agent such as HS—CH2—CH2—CH2—C(CF3)2—OH, a —C(CF3)2—OH group can be introduced at the terminals of the component (A1). Such a copolymer having introduced a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms is effective in reducing developing defects and LER (line edge roughness: unevenness of the side walls of a line pattern).
The weight average molecular weight (Mw) (the polystyrene equivalent value determined by gel permeation chromatography) of the component (A1) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 1,500 to 30,000, and most preferably 2,500 to 20,000. When the weight average molecular weight is no more than the upper limit of the above-mentioned range, the resist composition exhibits a satisfactory solubility in a resist solvent. On the other hand, when the weight average molecular weight is at least as large as the lower limit of the above-mentioned range, dry etching resistance and the cross-sectional shape of the resist pattern becomes satisfactory.
Further, the dispersity (Mw/Mn) of the component (A1) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5. Here, Mn is the number average molecular weight.
In the positive resist composition of the present invention, as the component (A), “a resin component (A2) which exhibits increased solubility in an alkali developing solution under action of acid” other than the component (A1) (hereafter, referred to as “component (A2)”) may be used in combination.
As the component (A2), any of the multitude of conventional base resins used within chemically amplified positive resist compositions can be arbitrarily selected for use.
Specifically, as the component (A2), a polymeric compound having the aforementioned structural unit (a1) is preferable. Further, it is preferable that the component (A2) has the aforementioned structural unit (a2), as well as the structural unit (a1). Furthermore, it is preferable that the component (A2) has the aforementioned structural unit (a3) or the aforementioned structural unit (a6), as well as the structural unit (a1) or the structural units (a1) and (a2).
Moreover, the component (A2) may include a structural unit other than the aforementioned structural units (a2), (a3) and (a6), such as the aforementioned structural unit (a4), as well as the structural unit (a1).
Examples of the component (A2) include a copolymer consisting of the structural units (a1), (a2) and (a6), and a copolymer consisting of the structural units (a1), (a2), (a6) and (a4). In addition, novolak resins and polyhydroxystyrene (PHS) resins can also be given as examples.
The weight average molecular weight (Mw) (the polystyrene equivalent value determined by gel permeation chromatography) of the component (A2) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 1,500 to 30,000, and most preferably 2,500 to 20,000. When the weight average molecular weight is no more than the upper limit of the above-mentioned range, the resist composition exhibits a satisfactory solubility in a resist solvent. On the other hand, when the weight average molecular weight is at least as large as the lower limit of the above-mentioned range, dry etching resistance and the cross-sectional shape of the resist pattern becomes satisfactory.
Further, the dispersity (Mw/Mn) of the component (A2) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5.
In the positive resist composition of the present invention, in addition to the component (A1), if desired, a low molecular weight compound component which exhibits increased solubility in an alkali developing solution under action of acid may be used in combination.
Examples of the low molecular weight component include low molecular weight compounds that have a molecular weight of at least 500 and less than 2,000, contains a hydrophilic group, and also contains an acid dissociable, dissolution inhibiting group described above in connection with the component (A1). Specific examples of the low molecular weight compound include compounds containing a plurality of phenol skeletons in which a part of the hydrogen atoms within hydroxyl groups have been substituted with the aforementioned acid dissociable, dissolution inhibiting groups.
In the component (A), the amount of the component (A1) based on the total weight of the component (A) is preferably 25% by weight or more, more preferably 50% by weight or more, still more preferably 75% by weight or more, and may be even 100% by weight. When the amount of the component (A1) is 25% by weight or more, an excellent resist pattern exhibiting a high resolution with reduced roughness can be formed.
In the resist composition of the present invention, the amount of the component (A) can be appropriately adjusted depending on the thickness of the resist film to be formed, and the like.
<Component (C1)>
The positive resist composition of the present invention includes a compound (C1) represented by general formula (c1) shown below.




In the formula, R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; Y1 represents a divalent aliphatic hydrocarbon group; R1 represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorinated alkyl group; p represents an integer of 1 to 10; and A+ represents an organic cation.

In formula (c1), R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms.
As the alkyl group of 1 to 5 carbon atoms for R, a linear or branched alkyl group of 1 to 5 carbon atoms is preferable, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group and a neopentyl group.
The halogenated alkyl group for R is a group in which part or all of the hydrogen atoms of the aforementioned alkyl group of 1 to 5 carbon atoms has been substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly desirable.
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 particularly desirable in terms of industrial availability.
In formula (c1), Y1 represents a divalent aliphatic hydrocarbon group, and preferable examples thereof include an alkylene group and a divalent aliphatic cyclic group.
When Y2 represents an alkylene group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 6, still more preferably 1 to 4, and most preferably 2 or 3.
In the divalent aliphatic cyclic group for Y1, the “aliphatic cyclic group” may or may not have a substituent. Examples of the substituent include an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group of 1 to 5 carbon atoms, and an oxygen atom (═O).
The basic ring of the “aliphatic cyclic group” exclusive of substituents is not limited to be constituted from only carbon and hydrogen (not limited to hydrocarbon groups), but is preferably a hydrocarbon group.
Further, the “hydrocarbon group” may be either saturated or unsaturated, but is preferably saturated. The “aliphatic cyclic group” may be either a monocyclic group or a polycyclic group, but is preferably a polycyclic group.
As the aliphatic cyclic group, for example, a group in which two or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane such as a bicycloalkane, a tricycloalkane or a tetracycloalkane which may or may not be substituted with the aforementioned substituent can be used.
Specific examples include groups in which two or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which two or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
In formula (c1), R1 represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorinated alkyl group. In particular, when R1 represents a fluorine atom or a fluorinated alkyl group, the strength (acidity) of the acid generated from the component (C1) is enhanced (although the acidity is weak), and the balance between ease in the salt exchange with the acid generated from the component (B) upon exposure and maintaining the countercation of the component (C1) prior to exposure becomes excellent.
The alkyl group for R1 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
Examples of the fluorinated alkyl group for R1 include groups in which part or all of the hydrogen atoms within the alkyl group for R1 has been substituted with a fluorine atom.
The fluorination ratio (percentage (%) of the number of fluorine atoms, base on the total number of fluorine atoms and hydrogen atoms) is preferably 50 to 100%, more preferably 80 to 100%, and still more preferably 85 to 100%.
The alkyl group or fluorinated alkyl group for R1 may have a substituent. Examples of substituents include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group and an oxygen atom (═O).
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group or tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
Examples of the halogen atom as the substituent include a chlorine atom, a bromine atom and an iodine atom.
Examples of the halogenated alkyl group as the substituent include groups in which part or all of the hydrogen atoms within the aforementioned alkyl groups of 1 to 5 carbon atoms has been substituted with the aforementioned halogen atoms (chlorine atoms, bromine atoms or iodine atoms).
In formula (c1), p represents an integer of 1 to 10. p is preferably an integer of 1 to 4, and 1 or 2 is particularly desirable.
The skeleton “R1—(CF2)p—SO2—” in which p represents an integer of 1 to 4 exhibits excellent decomposability as compared to a perfluoroalkyl chain of 6 to 10 carbon atoms which is hardly decomposable, and bioaccumulation can be minimized to improve ease in handling. Furthermore, the fluorinated alkyl group is preferable in that the acid-generator component (B) can be uniformly distributed within a resist film.
In formula (c1), A+ represents an organic cation.
As the organic cation for A+, there is no particular limitation, and any of those conventionally known as cation moiety for an onium salt acid generator can be appropriately selected for use.
Specifically, an organic cation represented by general formula (b′-1), (b′-2), (b-5) or (b-6) shown below can be preferably used.




In the formulas, each of R1′′ to R3′′, R5′′ and R6′′ independently represents an aryl group or an alkyl group; two of R1′′ to R3′′ may be mutually bonded to form a ring with the sulfur atom; at least one of R1′′ to R3′′ represents an aryl group, and at least one of R5′′ and R6′′ represents an aryl group.

In formula (b′-1), R1′′ to R3′′ each independently represents an aryl group or an alkyl group. In formula (I-1), two of R1′′ to R3′′ may be bonded to each other to form a ring with the sulfur atom.
Further, among R1′′ to R3′′, at least one group represents an aryl group. Among R1′′ to R3′′, two or more groups are preferably aryl groups, and it is particularly desirable that all of R1′′ to R3′′ are aryl groups.
The aryl group for R1′′ to R3′′ is not particularly limited. Examples thereof include an unsubstituted aryl group having 6 to 20 carbon atoms, a substituted aryl group in which part or all of the hydrogen atoms of the aforementioned unsubstituted aryl group has been substituted with alkyl groups, alkoxy groups, alkoxyalkyloxy groups, alkoxycarbonylalkyloxy groups, halogen atoms or hydroxyl groups, and a group represented by the formula —(R4′)—C(═O)—R5′. R4′ represents an alkylene group of 1 to 5 carbon atoms. R5′ represents an aryl group. As the aryl group for R5′, the same aryl groups as those described above for R1′′ to R3′′ can be used.
The unsubstituted aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples thereof include a phenyl group and a naphthyl group.
The alkyl group as the substituent for the substituted aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group is particularly desirable.
The alkoxy group as the substituent for the substituted aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group is particularly desirable.
The halogen atom as the substituent for the substituted aryl group is preferably a fluorine atom.
Examples of the alkoxyalkyloxy group as the substituent for the substituted aryl group include a group represented by a general formula —O—C(R47)(R48)—O—R49 (in the formula, each of R47 and R48 independently represent a hydrogen atom or a linear or branched alkyl group; and R49 represents an alkyl group).
The alkyl group for R47 and R48 preferably has 1 to 5 carbon atoms, and may be either linear or branched. As the alkyl group, an ethyl group or a methyl group is preferable, and a methyl group is most preferable.
It is preferable that at least one of R47 and R48 be a hydrogen atom. It is particularly desirable that at least one of R47 and R48 be a hydrogen atom, and the other be a hydrogen atom or a methyl group.
The alkyl group for R49 preferably has 1 to 15 carbon atoms, and may be linear, branched or cyclic.
The linear or branched alkyl group for R49 preferably has 1 to 5 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group.
The cyclic alkyl group for R49 preferably has 4 to 15 carbon atoms, more preferably 4 to 12, and most preferably 5 to 10. Specific examples thereof include groups in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane, and which may or may not be substituted with an alkyl group of 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group. Examples of the monocycloalkane include cyclopentane and cyclohexane. Examples of polycycloalkanes include adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane. Among these, a group in which one or more hydrogen atoms have been removed from adamantane is preferable.
An example of the alkoxycarbonylalkyloxy group as the substituent for the substituted aryl group includes a group represented by a general formula —O—R50—C(═O)—O—R51 (in the formula, R50 represents a linear or branched alkylene group; and R51 represents a tertiary alkyl group.)
The linear or branched alkylene group for R50 preferably has 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group and a 1,1-dimethylethylene group.
Examples of the tertiary alkyl group for R51 include a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 1-methyl-1-cyclopentyl group, a 1-ethyl-1-cyclopentyl group, a 1-methyl-1-cyclohexyl group, a 1-ethyl-1-cyclohexyl group, a 1-(1-adamantyl)-1-methylethyl group, a 1-(1-adamantyl)-1-methylpropyl group, a 1-(1-adamantyl)-1-methylbutyl group, a 1-(1-adamantyl)-1-methylpentyl group, a 1-(1-cyclopentyl)-1-methylethyl group, a 1-(1-cyclopentyl)-1-methylpropyl group, a 1-(1-cyclopentyl)-1-methylbutyl group, a 1-(1-cyclopentyl)-1-methylpentyl group, a 1-(1-cyclohexyl)-1-methylethyl group, a 1-(1-cyclohexyl)-1-methylpropyl group, a 1-(1-cyclohexyl)-1-methylbutyl group, a 1-(1-cyclohexyl)-1-methylpentyl group, a tert-butyl group, a tert-pentyl group and a tert-hexyl group.
The aryl group for each of R1′′ to R3′′ is preferably a phenyl group or a naphthyl group.
The alkyl group for R1′′ to R3′′ is not particularly limited and includes, for example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. In terms of achieving excellent resolution, the alkyl group preferably has 1 to 5 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, and a decyl group, and a methyl group is most preferable because it is excellent in resolution and can be synthesized at a low cost.
When two of R1′′ to R3′′ are bonded to each other to form a ring with the sulfur atom, it is preferable that the two of R1′′ to R3′′ form a 3 to 10-membered ring including the sulfur atom, and it is particularly desirable that the two of R1′′ to R3′′ form a 5 to 7-membered ring including the sulfur atom.
When two of R1′′ to R3′′ are bonded to each other to form a ring with the sulfur atom, the remaining one of R1′′ to R3′′ is preferably an aryl group. As examples of the aryl group, the same aryl groups as those described above for R1′′ to R3′′ can be mentioned.
Specific examples of the organic cation represented by general formula (b′-1) include triphenylsulfonium, (3,5-dimethylphenyl)diphenylsulfonium,

    (4-(2-adamantoxymethyloxy)-3,5-dimethylphenyl)diphenylsulfonium,
    (4-(2-adamantoxymethyloxy)phenyl)diphenylsulfonium,
    (4-(tert-butoxycarbonylmethyloxy)phenyl)diphenylsulfonium,
    (4-(tert-butoxycarbonylmethyloxy)-3,5-dimethylphenyl)diphenylsulfonium,
    (4-(2-methyl-2-adamantyloxycarbonylmethyloxy)phenyl)diphenylsulfonium,
    (4-(2-methyl-2-adamantyloxycarbonylmethyloxy)-3,5-dimethylphenyl)diphenylsulfonium,
    tri(4-methylphenyl)sulfonium,
    dimethyl(4-hydroxynaphthyl)sulfonium, monophenyldimethylsulfonium,
    diphenylmonomethylsulfonium, (4-methylphenyl)diphenylsulfonium,
    (4-methoxyphenyl)diphenylsulfonium, tri(4-tert-butyl)phenylsulfonium,
    diphenyl(1-(4-methoxy)naphthyl)sulfonium, di(1-naphthyl)phenylsulfonium,
    1-phenyltetrahydrothiophenium, 1-(4-methylphenyl)tetrahydrothiophenium,
    1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium,
    1-(4-methoxynaphthalene-1-yl)tetrahydrothiophenium,
    1-(4-ethoxynaphthalene-1-yl)tetrahydrothiophenium,
    1-(4-n-butoxynaphthalene-1-yl)tetrahydrothiophenium, 1-phenyltetrahydrothiopyranium,
    1-(4-hydroxyphenyl)tetrahydrothiopyranium,
    1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiopyranium and
    1-(4-methylphenyl)tetrahydrothiopyranium.


In formula (b′-2), R5′′ and R6′′ each independently represent an aryl group or alkyl group. At least one of R5′′ and R6′′ represents an aryl group. It is preferable that both of R5′′ and R6′′ represent an aryl group.
As the aryl group for R5′′ and R6′′, the same as the aryl groups for R1′′ to R3′′ can be used.
As the alkyl group for R5′′ and R6′′, the same as the alkyl groups for R1′′ to R3′′ can be used.
It is particularly desirable that both of R5′′ and R6′′ represents a phenyl group.
Specific examples of the organic cation represented by general formula (b-2) include diphenyliodonium and bis(4-tert-butylphenyl)iodonium.




In the formulas, R80 represents a hydrogen atom or an alkyl group; R81 represents an alkyl group, an acetyl group, a carboxy group or a hydroxyalkyl group; each of R82 to R86 independently represents an alkyl group, an acetyl group, an alkoxy group, a carboxy group, or a hydroxyalkyl group; each of n0 to n5 independently represents an integer of 0 to 3, with the provision that n0+n1 is 5 or less; and n6 represents an integer of 0 to 2.

In general formulas (b-5) and (b-6), with respect to R80 to R86, the alkyl group is preferably an alkyl group of 1 to 5 carbon atoms, more preferably a linear or branched alkyl group, and most preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group or a tert butyl group.
The alkoxy group is preferably an alkoxy group of 1 to 5 carbon atoms, more preferably a linear or branched alkoxy group, and most preferably a methoxy group or ethoxy group.
The hydroxyalkyl group is preferably the aforementioned alkyl group in which one or more hydrogen atoms have been substituted with hydroxy groups, and examples thereof include a hydroxymethyl group, a hydroxyethyl group and a hydroxypropyl group.
n0 is preferably 0 or 1.
n1 is preferably 0 to 2.
It is preferable that n2 and n3 each independently represent 0 or 1, and more preferably 0.
n4 is preferably 0 to 2, and more preferably 0 or 1.
n5 is preferably 0 or 1, and more preferably 0.
n6 is preferably 0 or 1.
In the present invention, as A+, an organic cation represented by formula (b′-1) or (b-5) is preferable, an organic cation represented by any one of general formulas (b′-1-1) to (b′-1-8) and (b-5-1) to (b-5-4) is more preferable, and an organic cation having a triphenyl skeleton such as those represented by formulas (b′-1-1) to (b′-1-8) is particularly desirable.










Alternatively, as the organic cation for A+, an organic cation represented by general formula (b-7) or (b-8) shown below may be preferably used.
In formulas (b-7) and (b-8) shown below, each of R8 and R9 independently represents a phenyl group or naphthyl group which may have a substituent, an alkyl group of 1 to 5 carbon atoms, an alkoxy group or a hydroxyl group.
u is an integer of 1 to 3, and most preferably 1 or 2.




As the component (C1), in terms of improvement in the lithography properties such as roughness and the shape of the resist pattern, a compound represented by general formula (c1-1) shown below is particularly desirable.




In the formula, R1′′ to R3′′, R1 and p are the same as defined above; q represents an integer of 1 to 10; and R0 represents a hydrogen atom or a methyl group.

In the formula above, q is preferably an integer of 1 to 6, more preferably an integer of 1 to 4, still more preferably an integer of 1 to 3, and most preferably 2.
As the component (C1), one type of compound may be used, or two or more types of compounds may be used in combination.
In the positive resist composition of the present invention, the amount of the component (C1) relative to 100 parts by weight of the component (A1) is preferably within the range of 0.5 to 10 parts by weight, more preferably 1.3 to 8.5 parts by weight, still more preferably 1.5 to 7 parts by weight, and most preferably 2.5 to 6 parts by weight.
When the amount of the component (C1) is at least as large as the lower limit of the above-mentioned range, various lithography properties (such as roughness) of the positive resist composition are improved by using in combination with the component (A1). Further, a resist pattern having an excellent shape can be obtained. On the other hand, when the amount of the component (C1) is no more than the upper limit of the above-mentioned range, sensitivity can be maintained at a satisfactory level, and through-top becomes excellent.
<Component (B)>
In the present invention, as the component (B), there is no particular limitation, and any of the known acid generators used in conventional chemically amplified resist compositions can be used.
Examples of these acid generators are numerous, and include onium salt acid generators such as iodonium salts and sulfonium salts; oxime sulfonate acid generators; diazomethane acid generators such as bisalkyl or bisaryl sulfonyl diazomethanes and poly(bis-sulfonyl)diazomethanes; nitrobenzylsulfonate acid generators; iminosulfonate acid generators; and disulfone acid generators.
As an onium salt acid generator, a compound represented by general formula (b-1) or (b-2) shown below can be used.




In formula (b-1), each of R1′′ to R3′′ independently represents an aryl group, alkyl group or alkenyl group which may have a substituent, provided that at least one of R1′′ to R3′′ represents an aryl group, and two of R1′′ to R3′′ may be bonded to each other to form a ring with the sulfur atom. In formula (b-2), R5′′ and R6′′ each independently represent an aryl group, alkyl group or alkenyl group which may have a substituent, provided that and at least one of R5′′ and R6′′ represents an aryl group. R4′′ represents a halogenated alkyl group, an aryl group or an alkenyl group which may have a substituent.

In general formula (b-1), R1′′ to R3′′ are respectively the same as defined for R1′′ to R3′′ in general formula (b′-1).
In general formula (b-2), R5′′ and R6′′ are respectively the same as defined for R5′′ and R6′′ in general formula (b′-2).
In formulas (b-1) and (b-2), R4′′ represents a halogenated alkyl group, an aryl group or an alkenyl group which may have a substituent.
As an example of the halogenated alkyl group for R4′′, a group in which part of or all of the hydrogen atoms of a linear, branched or cyclic alkyl group have been substituted with halogen atoms can be given. Examples of the aforementioned halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
When the alkyl group within the halogenated alkyl group is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. On the other hand, when the alkyl group within the halogenated alkyl group is a cyclic alkyl group, it preferably has 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.
In the halogenated alkyl group, the percentage of the number of halogen atoms based on the total number of halogen atoms and hydrogen atoms (halogenation ratio (%)) is preferably 10 to 100%, more preferably 50 to 100%, and most preferably 100%. Higher halogenation ratios are preferable, as they result in increased acid strength.
The aryl group for R4′′ is preferably an aryl group of 6 to 20 carbon atoms.
The alkenyl group for R4′′ is preferably an alkenyl group of 2 to 10 carbon atoms.
With respect to R4′′, the expression “may have a substituent” means that part of or all of the hydrogen atoms within the aforementioned linear, branched or cyclic alkyl group, halogenated alkyl group, aryl group or alkenyl group may be substituted with substituents (atoms other than hydrogen atoms, or groups).
R4′′ may have one substituent, or two or more substituents.
Examples of the substituent include a halogen atom, a hetero atom, an alkyl group, and a group represented by the formula X-Q2- (in the formula, Q2 represents a divalent linking group containing an oxygen atom; and X represents a hydrocarbon group of 3 to 30 carbon atoms which may have a substituent).
Examples of halogen atoms and alkyl groups as substituents for R4′′ include the same halogen atoms and alkyl groups as those described above with respect to the halogenated alkyl group for R4′′.
Examples of hetero atoms include an oxygen atom, a nitrogen atom, and a sulfur atom.
In the group represented by formula X-Q2-, Q2 represents a divalent linking group containing an oxygen atom.
Q2 may contain an atom other than an oxygen atom. Examples of atoms other than oxygen include a carbon atom, a hydrogen atom, a sulfur atom and a nitrogen atom.
Examples of divalent linking groups containing an oxygen atom include non-hydrocarbon, oxygen atom-containing linking groups such as an oxygen atom (an ether bond; —O—), an ester bond (—C(═O)—O—), an amido bond (—C(═O)—NH—), a carbonyl group (—C(═O)—) and a carbonate bond (—O—C(═O)—O—); and combinations of the aforementioned non-hydrocarbon, hetero atom-containing linking groups with an alkylene group.
Specific examples of the combinations of the aforementioned non-hydrocarbon, hetero atom-containing linking groups and an alkylene group include —R91—O—, —R92—O—C(═O)—, —C(═O)—O—R93—O—C(═O)— (in the formulas, each of R91 to R93 independently represents an alkylene group).
The alkylene group for R91 to R93 is preferably a linear or branched alkylene group, and preferably has 1 to 12 carbon atoms, more preferably 1 to 5, and most preferably 1 to 3.
Specific examples of alkylene groups include a methylene group [—CH2—]; alkylmethylene groups such as —CH(CH3)—, —CH(CH2CH3)—, —C(CH3)2—, —C(CH3)(CH2CH3)—, —C(CH3)(CH2CH2CH3)— and —C(CH2CH3)2—; an ethylene group [—CH2CH2—]; alkylethylene groups such as —CH(CH3)CH2—, —CH(CH3)CH(CH3)—, —C(CH3)2CH2— and —CH(CH2CH3)CH2—; a trimethylene group (n-propylene group) [—CH2CH2CH2—]; alkyltrimethylene groups such as —CH(CH3)CH2CH2— and —CH2CH(CH3)CH2—; a tetramethylene group [—CH2CH2CH2CH2—]; alkyltetramethylene groups such as —CH(CH3)CH2CH2CH2— and —CH2CH(CH3)CH2CH2—; and a pentamethylene group [—CH2CH2CH2CH2CH2—].
As Q2, a divalent linking group containing an ester bond or an ether bond is preferable, and —R91—O—, —R92—O—C(═O)— or —C(═O)—O—R93—O—C(═O)— is more preferable.
In the group represented by the formula X-Q2-, the hydrocarbon group for X may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
The aliphatic hydrocarbon group for X may be either a saturated aliphatic hydrocarbon group, or an unsaturated aliphatic hydrocarbon group. Further, the aliphatic hydrocarbon group for X may be linear, branched or cyclic.
In the aliphatic hydrocarbon group for X, part of the carbon atoms constituting the aliphatic hydrocarbon group may be substituted with a substituent group containing a hetero atom, or part or all of the hydrogen atoms constituting the aliphatic hydrocarbon group may be substituted with a substituent group containing a hetero atom.
As the “hetero atom”, there is no particular limitation as long as it is an atom other than carbon atom and hydrogen, and examples thereof include a halogen atom, an oxygen atom, a sulfur atom and a nitrogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom.
The substituent group containing a hetero atom may consist of a hetero atom, or may be a group containing a group or atom other than a hetero atom.
Specific examples of the substituent group for substituting part of the carbon atoms include —O—, —C(═O)—O—, —C(═O)—, —O—C(═O)—O—, —C(═O)—NH—, —NH— (in the formula, the H may be replaced with a substituent such as an alkyl group or an acyl group), —S—, —S(═O)2— and —S(═O)2—O—. When the aliphatic hydrocarbon group is cyclic, the aliphatic hydrocarbon group may contain any of these substituent groups in the ring structure.
Examples of the substituent group for substituting part or all of the hydrogen atoms include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (═O) and a cyano group.
The aforementioned alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
Examples of the halogen atom for the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
Example of the aforementioned halogenated alkyl group as the substituent includes a group in which part or all of the hydrogen atoms within an alkyl group of 1 to carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group) have been substituted with the aforementioned halogen atoms.
As the aliphatic hydrocarbon group for X, a linear or branched saturated hydrocarbon group, a linear or branched unsaturated hydrocarbon group, or a cyclic aliphatic hydrocarbon group (aliphatic cyclic group) is preferable.
The linear saturated hydrocarbon group (alkyl group) preferably has 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group and a docosyl group.
The branched saturated hydrocarbon group (alkyl group) preferably has 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Specific examples include a 1-methylethyl group, a 1-methylpropyl group, a 2-methylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group and a 4-methylpentyl group.
The unsaturated hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 5, still more preferably 2 to 4, and most preferably 3.
Examples of linear unsaturated hydrocarbon groups include a vinyl group CH2═C(CH3)—, a propenyl group (an allyl group) and a butynyl group.
Examples of branched unsaturated hydrocarbon groups include a 1-methylpropenyl group and a 2-methylpropenyl group.
The cyclic aliphatic hydrocabron group (aliphatic cyclic group) may be either a monocyclic group or a polycyclic group. The aliphatic cyclic group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, still more preferably 5 to 20, still more preferably 6 to 15, and most preferably 6 to 12.
As the aliphatic cyclic group, a group in which one or more hydrogen atoms have been removed from a monocycloalkane or a polycycloalkane such as a bicycloalkane, tricycloalkane or tetracycloalkane can be used. Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.
When the aliphatic cyclic group does not contain a hetero atom-containing substituent group in the ring structure thereof, the aliphatic cyclic group is preferably a polycyclic group, more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane, and a group in which one or more hydrogen atoms have been removed from adamantane is particularly desirable.
When the aliphatic cyclic group contains a hetero atom-containing substituent group in the ring structure thereof, the hetero atom-containing substituent group is preferably —O—, —C(═O)—O—, -5-, —S(═O)2— or —S(═O)2—O—. Specific examples of such aliphatic cyclic groups include groups represented by formulas (L1) to (L6) and (S1) to (S4) shown below.




In the formula, Q′′ represents an alkylene group of 1 to 5 carbon atoms, —O—, —S—, —O—R94— or —S—R95— (wherein each of R94 and R95 independently represents an alkylene group of 1 to 5 carbon atoms); and m represents 0 or 1.

In the formulas, the alkylene group for Q′′ and R94 to R95 is preferably a linear or branched alkylene group, and an alkylene group of 1 to 3 carbon atoms (a methylene group, an ethylene group or a propylene group) is particularly desirable.
In these aliphatic cyclic groups, part of the hydrogen atoms bonded to the carbon atoms constituting the ring structure may be substituted with a substituent. Examples of substituents include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group and an oxygen atom (═O).
As the alkyl group for the substituent, an alkyl group of 1 to 5 carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group is particularly desirable.
As the alkoxy group the halogen atom and the halogenated alkyl group for the substituent, the same groups as the aforementioned substituent groups for substituting a part or all of the hydrogen atoms can be used.
The aromatic hydrocarbon group for X is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon ring preferably has 3 to 30 carbon atoms, more preferably 5 to 30, still more preferably 5 to 20, still more preferably 6 to 15, and most preferably 6 to 12. Here, the number of carbon atoms within a substituent(s) is not included in the number of carbon atoms of the aromatic hydrocarbon group.
Specific examples of aromatic hydrocarbon groups include an aryl group which is an aromatic hydrocarbon ring having one hydrogen atom removed therefrom, such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group or a phenanthryl group; and an alkylaryl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group. The alkyl chain within the arylalkyl group preferably has 1 to 4 carbon atom, more preferably 1 or 2, and most preferably 1.
The aromatic hydrocarbon group may have a substituent. For example, part of the carbon atoms constituting the aromatic ring within the aromatic hydrocarbon group may be substituted with a hetero atom, or a hydrogen atom bonded to the aromatic ring within the aromatic hydrocarbon group may be substituted with a substituent.
In the former example, a heteroaryl group in which part of the carbon atoms constituting the ring within the aforementioned aryl group has been substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, and a heteroarylalkyl group in which part of the carbon atoms constituting the aromatic hydrocarbon ring within the aforementioned arylalkyl group has been substituted with the aforementioned heteroatom can be used.
In the latter example, as the substituent for the aromatic hydrocarbon group, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (═O) or the like can be used.
The alkyl group as the substituent for the aromatic hydrocarbon group is preferably an alkyl group of 1 to 5 carbon atoms, and a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group is particularly desirable.
The alkoxy group as the substituent for the aromatic hydrocarbon group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group or tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
Examples of the halogen atom as the substituent for the aromatic hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
Example of the halogenated alkyl group as the substituent for the aromatic hydrocarbon group includes a group in which part or all of the hydrogen atoms within the aforementioned alkyl group have been substituted with the aforementioned halogen atoms.
Among the examples described above, as X, a cyclic group which may have a substituent is preferable. The cyclic group may be either an aromatic hydrocarbon group which may have a substituent, or an aliphatic cyclic group which may have a substituent, and an aliphatic cyclic group which may have a substituent is preferable.
As the aromatic hydrocarbon group, a naphthyl group which may have a substituent, or a phenyl group which may have a substituent is preferable.
As the aliphatic cyclic group which may have a substituent, an aliphatic polycyclic group which may have a substituent is preferable. As the aliphatic polycyclic group, the aforementioned group in which one or more hydrogen atoms have been removed from a polycycloalkane, and groups represented by formulas (L2) to (L5), (S3) and (S4) are preferable.
Further, in the present invention, it is particularly desirable that X have a polar moiety, because it results in improved lithographic properties and resist pattern shape.
Specific examples of X having a polar moiety include those in which a part of the carbon atoms constituting the aliphatic hydrocarbon group for X is substituted with a substituent group containing a hetero atom such as —O—, —C(═O)—O—, —C(═O)—, —C(═O)—NH—, —NH— (wherein H may be substituted with a substituent such as an alkyl group or an acyl group), —S—, —S(═O)2— and —S(═O)2—O—.
In the present invention, R4′′ preferably has X-Q2- as a substituent. In this case, R4′′ is preferably a group represented by formula X-Q2-Y4-[wherein Q2 and X are the same as defined above; and Y4 represents an alkylene group of 1 to 4 carbon atoms which may have a substituent, or a fluorinated alkylene group of 1 to 4 carbon atoms which may have a substituent].
In the group represented by the formula X-Q2-Y4-, as the alkylene group for Y4, the same alkylene group as those described above for Q2 in which the number of carbon atoms is 1 to 4 can be used.
As the fluorinated alkylene group for Y4, the aforementioned alkylene group in which part or all of the hydrogen atoms has been substituted with fluorine atoms can be used.
Specific examples of Y4 include —CF2—, —CF2CF2—, —CF2CF2CF2—, —CF(CF3)CF2—, —CF(CF2CF3)—, —C(CF3)2—, —CF2CF2CF2CF2—, —CF(CF3)CF2CF2—, —CF2CF(CF3)CF2—, —CF(CF3)CF(CF3)—, —C(CF3)2CF2—, —CF(CF2CF3)CF2—, —CF(CF2CF2CF3)—, —C(CF3)(CF2CF3)—; —CHF—, —CH2CF2—, —CH2CH2CF2—, —CH2CF2CF2—, —CH(CF3)CH2—, —CH(CF2CF3)—, —C(CH3)(CF3)—, —CH2CH2CH2CF2—, —CH2CH2CF2CF2—, —CH(CF3)CH2CH2—, —CH2CH(CF3)CH2—, —CH(CF3)CH(CF3)—, —C(CF3)2CH2—; —CH2—, —CH2CH2—, —CH2CH2CH2—, —CH(CH3)CH2—, —CH(CH2CH3)—, —C(CH3)2—, —CH2CH2CH2CH2—, —CH(CH3)CH2CH2—, —CH2CH(CH3)CH2—, —CH(CH3)CH(CH3)—, —C(CH3)2CH2—, —CH(CH2CH3)CH2—, —CH(CH2CH2CH3)—, and —C(CH3)(CH2CH3)—.
Y4 is preferably a fluorinated alkylene group, and particularly preferably a fluorinated alkylene group in which the carbon atom bonded to the adjacent sulfur atom is fluorinated. Examples of such fluorinated alkylene groups include —CF2—, —CF2CF2—, —CF2CF2CF2—, —CF(CF3)CF2—, —CF2CF2CF2CF2—, —CF(CF3)CF2CF2—, —CF2CF(CF3)CF2—, —CF(CF3)CF(CF3)—, —C(CF3)2CF2—, —CF(CF2CF3)CF2—; —CH2CF2—, —CH2CH2CF2—, —CH2CF2CF2—; —CH2CH2CH2CF2—, —CH2CH2CF2CF2—, and —CH2CF2CF2CF2—.
Of these, —CF2—, —CF2CF2—, —CF2CF2CF2— or CH2CF2CF2— is preferable, —CF2—, —CF2CF2— or —CF2CF2CF2— is more preferable, and —CF2— is particularly desirable.
The alkylene group or fluorinated alkylene group may have a substituent. The alkylene group or fluorinated alkylene group “has a substituent” means that part or all of the hydrogen atoms or fluorine atoms in the alkylene group or fluorinated alkylene group has been substituted with groups other than hydrogen atoms and fluorine atoms.
Examples of substituents which the alkylene group or fluorinated alkylene group may have include an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, and a hydroxyl group.
Specific examples of suitable onium salt acid generators represented by formula (b-1) or (b-2) include diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate; bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate or nonafluorobutanesulfonate; triphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; tri(4-methylphenyl)sulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; dimethyl(4-hydroxynaphthyl)sulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; monophenyldimethylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; diphenylmonomethylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; (4-methylphenyl)diphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; tri(4-tert-butyl)phenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; diphenyl(1-(4-methoxy)naphthyl)sulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; di(1-naphthyl)phenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; 1-phenyltetrahydrothiophenium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; 1-(4-methylphenyl)tetrahydrothiophenium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophenium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; 1-(4-methoxynaphthalene-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; 1-(4-ethoxynaphthalene-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; 1-(4-n-butoxynaphthalene-1-yl)tetrahydrothiophenium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; 1-phenyltetrahydrothiopyranium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; 1-(4-hydroxyphenyl)tetrahydrothiopyranium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiopyranium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate; and 1-(4-methylphenyl)tetrahydrothiopyranium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate.
It is also possible to use onium salts in which the anion moiety of these onium salts is replaced by an alkyl sulfonate such as methanesulfonate, n-propanesulfonate, n-butanesulfonate, n-octanesulfonate, 1-adamantanesulfonate, or 2-norbornanesulfonate; or a sulfonate such as d-camphor-10-sulfonate, benzenesulfonate, perfluorobenzenesulfonate, or p-toluenesulfonate.
Furthermore, onium salts in which the anion moiety of these onium salts is replaced by an anion moiety represented by any one of formulas (b1) to (b8) shown below can also be used.




In the formulas, z0 represents an integer of 1 to 3; each of q1 and q2 independently represents an integer of 1 to 5; q3 represents an integer of 1 to 12; t3 represents an integer of 1 to 3; each of r1 and r2 independently represents an integer of 0 to 3; j represents an integer of 1 to 20; R7 represents a substituent; each of m1 to m5 independently represents 0 or 1; each of v0 to v5 independently represents an integer of 0 to 3; each of w1 to w5 independently represents an integer of 0 to 3; and Q′′ is the same as defined above.

As the substituent for R7, the same groups as those which the aforementioned aliphatic hydrocarbon group or aromatic hydrocarbon group for X may have as a substituent can be used.
If there are two or more of the R7 group, as indicated by the values r1, r2, and w1 to w5, then the two or more of the R7 groups may be the same or different from each other.
Among the aforementioned examples, in terms of significantly improving the effects of the present invention, the onium salt-based acid generator represented by formula (b-1) or (b-2) preferably has an anion moiety in which a fluorine atom is bonded to a carbon atom adjacent to the sulfur atom of the —SO3− group, more preferably an anion moiety in which R4′′ represents a halogenated alkyl group which may have a substituent, and most preferably an anion moiety represented by any one of formulas (b1) to (b8).
Further, onium salt-based acid generators in which the anion moiety in general formula (b-1) or (b-2) is replaced by an anion moiety represented by general formula (b-3) or (b-4) shown below (the cation moiety is the same as (b-1) or (b-2)) may also be used.




In the formulas, X′′ represents an alkylene group of 2 to 6 carbon atoms in which at least one hydrogen atom has been substituted with a fluorine atom; and each of Y′′ and Z′′ independently represents an alkyl group of 1 to 10 carbon atoms in which at least one hydrogen atom has been substituted with a fluorine atom.

X′′ represents a linear or branched alkylene group in which at least one hydrogen atom has been substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms.
Each of Y′′ and Z′′ independently represents a linear or branched alkyl group in which at least one hydrogen atom has been substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and most preferably 1 to 3 carbon atoms.
The smaller the number of carbon atoms of the alkylene group for X′′ or those of the alkyl group for Y′′ and Z′′ within the above-mentioned range of the number of carbon atoms, the more the solubility in a resist solvent is improved.
Further, in the alkylene group for X′′ or the alkyl group for Y′′ and Z′′, it is preferable that the number of hydrogen atoms substituted with fluorine atoms is as large as possible because the acid strength increases and the transparency to high energy radiation of 200 nm or less or electron beam is improved.
The fluorination ratio of the alkylene group or alkyl group is preferably from 70 to 100%, more preferably from 90 to 100%, and it is particularly desirable that the alkylene group or alkyl group be a perfluoroalkylene group or perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
Further, an onium salt-based acid generator in which the anion moiety (R4′′SO3−) in general formula (b-1) or (b-2) has been replaced with Ra—COO− (in the formula, Ra represents an alkyl group or a fluorinated alkyl group) can also be used (the cation moiety is the same as that in general formula (b-1) or (b-2)).
In the formula above, as Ra, the same groups as those described above for R4′′ can be used.
Specific examples of the group represented by the formula “Ra—COO−” include a trifluoroacetic acid ion, an acetic acid ion, and a 1-adamantanecarboxylic acid ion.
Further, onium salts having a cation moiety represented by any one of general formulas (b-5) to (b-8) above, and having a fluorinated alkylsulfonate ion (e.g., the anion moiety (R4′′SO3−) in general formula (b-1) or (b-2) above) or an anion moiety represented by general formula (b-3) or (b-4) above as the anion moiety, can be used.
In the present description, an oximesulfonate acid generator is a compound having at least one group represented by general formula (B-1) shown below, and has a feature of generating acid by irradiation. Such oximesulfonate acid generators are widely used for a chemically amplified resist composition, and can be appropriately selected.




In the formula, each of R31 and R32 independently represents an organic group.
The organic group for R31 and R32 refers to a group containing a carbon atom, and may include atoms other than carbon atoms (e.g., a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (such as a fluorine atom and a chlorine atom) and the like).
As the organic group for R31, a linear, branched, or cyclic alkyl group or aryl group is preferable. The alkyl group or the aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include a fluorine atom and a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. The alkyl group or the aryl group “has a substituent” means that part or all of the hydrogen atoms of the alkyl group or the aryl group is substituted with a substituent.
The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, and most preferably 1 to 4 carbon atoms. As the alkyl group, a partially or completely halogenated alkyl group (hereinafter, sometimes referred to as a “halogenated alkyl group”) is particularly desirable. The “partially halogenated alkyl group” refers to an alkyl group in which part of the hydrogen atoms are substituted with halogen atoms and the “completely halogenated alkyl group” refers to an alkyl group in which all of the hydrogen atoms are substituted with halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms, and fluorine atoms are particularly desirable. In other words, the halogenated alkyl group is preferably a fluorinated alkyl group.
The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. As the aryl group, partially or completely halogenated aryl group is particularly desirable. The “partially halogenated aryl group” refers to an aryl group in which some of the hydrogen atoms are substituted with halogen atoms and the “completely halogenated aryl group” refers to an aryl group in which all of hydrogen atoms are substituted with halogen atoms.
As R31, an alkyl group of 1 to 4 carbon atoms which has no substituent or a fluorinated alkyl group of 1 to 4 carbon atoms is particularly desirable.
As the organic group for R32, a linear, branched, or cyclic alkyl group, aryl group, or cyano group is preferable. Examples of the alkyl group and the aryl group for R32 include the same alkyl groups and aryl groups as those described above for R31.
As R32, a cyano group, an alkyl group of 1 to 8 carbon atoms having no substituent or a fluorinated alkyl group of 1 to 8 carbon atoms is particularly desirable.
Preferred examples of the oxime sulfonate acid generator include compounds represented by general formula (B-2) or (B-3) shown below.




In the formula, R33 represents a cyano group, an alkyl group having no substituent or a halogenated alkyl group; R34 represents an aryl group; and R35 represents an alkyl group having no substituent or a halogenated alkyl group.





In the formula, R36 represents a cyano group, an alkyl group having no substituent or a halogenated alkyl group; R37 represents a divalent or trivalent aromatic hydrocarbon group; R38 represents an alkyl group having no substituent or a halogenated alkyl group; and p′′ represents 2 or 3.

In general formula (B-2), the alkyl group having no substituent or the halogenated alkyl group for R33 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.
As R33, a halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.
The fluorinated alkyl group for R33 preferably has 50% or more of the hydrogen atoms thereof fluorinated, more preferably 70% or more, and most preferably 90% or more.
Examples of the aryl group for R34 include groups in which one hydrogen atom has been removed from an aromatic hydrocarbon ring, such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group, and heteroaryl groups in which some of the carbon atoms constituting the ring(s) of these groups are substituted with hetero atoms such as an oxygen atom, a sulfur atom, and a nitrogen atom. Of these, a fluorenyl group is preferable.
The aryl group for R34 may have a substituent such as an alkyl group of 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group. The alkyl group and halogenated alkyl group as the substituent preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Further, the halogenated alkyl group is preferably a fluorinated alkyl group.
The alkyl group having no substituent or the halogenated alkyl group for R35 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.
As R35, a halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.
In terms of enhancing the strength of the acid generated, the fluorinated alkyl group for R35 preferably has 50% or more of the hydrogen atoms fluorinated, more preferably 70% or more, still more preferably 90% or more. A completely fluorinated alkyl group in which 100% of the hydrogen atoms are substituted with fluorine atoms is particularly desirable.
In general formula (B-3), as the alkyl group having no substituent and the halogenated alkyl group for R36, the same alkyl group having no substituent and the halogenated alkyl group described above for R33 can be used.
Examples of the divalent or trivalent aromatic hydrocarbon group for R37 include groups in which one or two hydrogen atoms have been removed from the aryl group for R34.
As the alkyl group having no substituent or the halogenated alkyl group for R38, the same one as the alkyl group having no substituent or the halogenated alkyl group for R35 can be used.
p′′ is preferably 2.
Specific examples of suitable oxime sulfonate acid generators include

    α-(p-toluenesulfonyloxyimino)-benzyl cyanide,
    α-(p-chlorobenzenesulfonyloxyimino)-benzyl cyanide,
    α-(4-nitrobenzenesulfonyloxyimino)-benzyl cyanide,
    α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimino)-benzyl cyanide,
    α-(benzenesulfonyloxyimino)-4-chlorobenzyl cyanide,
    α-(benzenesulfonyloxyimino)-2,4-dichlorobenzyl cyanide,
    α-(benzenesulfonyloxyimino)-2,6-dichlorobenzyl cyanide,
    α-(benzenesulfonyloxyimino)-4-methoxybenzyl cyanide,
    α-(2-chlorobenzenesulfonyloxyimino)-4-methoxybenzyl cyanide,
    α-(benzenesulfonyloxyimino)-thien-2-yl acetonitrile,
    α-(4-dodecylbenzenesulfonyloxyimino)benzyl cyanide,
    α-[(p-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile,
    α-[(dodecylbenzenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile,
    α-(tosyloxyimino)-4-thienyl cyanide, α-(methylsulfonyloxyimino)-1-cyclopentenyl acetonitrile, α-(methylsulfonyloxyimino)-1-cyclohexenyl acetonitrile,
    α-(methylsulfonyloxyimino)-1-cycloheptenyl acetonitrile,
    α-(methylsulfonyloxyimino)-1-cyclooctenyl acetonitrile,
    α-(trifluoromethylsulfonyloxyimino)-1-cyclopentenyl acetonitrile,
    ═-(trifluoromethylsulfonyloxyimino)-cyclohexyl acetonitrile,
    α-(ethylsulfonyloxyimino)-ethyl acetonitrile, α-(propylsulfonyloxyimino)-propyl acetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclopentyl acetonitrile,
    α-(cyclohexylsulfonyloxyimino)-cyclohexyl acetonitrile,
    α-(cyclohexylsulfonyloxyimino)-1-cyclopentenyl acetonitrile,
    α-(ethylsulfonyloxyimino)-1-cyclopentenyl acetonitrile,
    α-(isopropylsulfonyloxyimino)-1-cyclopentenyl acetonitrile,
    α-(n-butylsulfonyloxyimino)-1-cyclopentenyl acetonitrile,
    α-(ethylsulfonyloxyimino)-1-cyclohexenyl acetonitrile,
    α-(isopropylsulfonyloxyimino)-1-cyclohexenyl acetonitrile,
    α-(n-butylsulfonyloxyimino)-1-cyclohexenyl acetonitrile,
    α-(methylsulfonyloxyimino)-phenyl acetonitrile,
    α-(methylsulfonyloxyimino)-p-methoxyphenyl acetonitrile,
    α-(trifluoromethylsulfonyloxyimino)-phenyl acetonitrile,
    α-(trifluoromethylsulfonyloxyimino)-p-methoxyphenyl acetonitrile,
    α-(ethylsulfonyloxyimino)-p-methoxyphenyl acetonitrile,
    α-(propylsulfonyloxyimino)-p-methylphenyl acetonitrile, and
    α-(methylsulfonyloxyimino)-p-bromophenyl acetonitrile.


Further, oxime sulfonate acid generators disclosed in Japanese Unexamined Patent Application, First Publication No. Hei 9-208554 (Chemical Formulas 18 and 19 shown in paragraphs [0012] to [0014]) and oxime sulfonate acid generators disclosed in WO 2004/074242A2 (Examples 1 to 40 described at pages 65 to 85) may be preferably used.
Furthermore, as preferable examples, the following can be used.




Of the aforementioned diazomethane acid generators, specific examples of suitable bisalkyl or bisaryl sulfonyl diazomethanes include bis(isopropylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(2,4-dimethylphenylsulfonyl)diazomethane.
Further, diazomethane acid generators disclosed in Japanese Unexamined Patent Application, First Publication No. Hei 11-035551, Japanese Unexamined Patent Application, First Publication No. Hei 11-035552 and Japanese Unexamined Patent Application, First Publication No. Hei 11-035573 may be preferably used.
Furthermore, as examples of poly(bis-sulfonyl)diazomethanes, those disclosed in Japanese Unexamined Patent Application, First Publication No. Hei 11-322707, including 1,3-bis(phenylsulfonyldiazomethylsulfonyl)propane,

    1,4-bis(phenylsulfonyldiazomethylsulfonyl)butane,
    1,6-bis(phenylsulfonyldiazomethylsulfonyl)hexane,
    1,10-bis(phenylsulfonyldiazomethylsulfonyl)decane,
    1,2-bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane,
    1,3-bis(cyclohexylsulfonyldiazomethylsulfonyl)propane,
    1,6-bis(cyclohexylsulfonyldiazomethylsulfonyl)hexane, and
    1,10-bis(cyclohexylsulfonyldiazomethylsulfonyl)decane, may be given.


As the component (B), one type of acid generator may be used, or two or more types may be used in combination.
In the positive resist composition of the present invention, the amount of the component (B) relative to 100 parts by weight of the component (A) is preferably 0.5 to 50 parts by weight, and more preferably 1 to 40 parts by weight. When the amount of the component (B) is within the above-mentioned range, formation of a resist pattern can be satisfactorily performed. Further, by virtue of the above-mentioned range, a uniform solution can be obtained and the storage stability becomes satisfactory.
<Optional Components>
[Component (S)]
The positive resist composition of the present invention can be produced by dissolving the materials for the resist composition in an organic solvent (hereafter, referred to as “component (S)”).
The component (S) may be any organic solvent which can dissolve the respective components to give a uniform solution, and one or more kinds of any organic solvent can be appropriately selected from those which have been conventionally known as solvents for a chemically amplified resist.
In the positive resist composition of the present invention, it is preferable to include an alcohol organic solvent as the component (S). In a double patterning process, a positive resist composition containing an alcohol organic solvent hardly dissolves the first resist pattern formed by a first patterning, and thus, can be preferably used as a resist composition for a second patterning.
The term “alcohol organic solvent” refers to a compound in which at least one hydrogen atom within an aliphatic hydrocarbon has been substituted with a hydroxyl group, and is a liquid at normal temperature (room temperature) and normal pressure (atmospheric pressure). The structure of the main chain constituting the aforementioned aliphatic hydrocarbon may be a chain-like structure or a cyclic structure, or may include a cyclic structure within the chain-like structure, or may include an ether bond within the chain-like structure.
As the alcohol organic solvent, a monohydric alcohol, a dihydric alcohol or a dihydric alcohol derivative is preferable.
Although it depends on the number of carbon atoms, as the monohydric alcohol, a primary or secondary alcohol is preferable, and a primary monohydric alcohol is particularly desirable.
The term “monohydric alcohol” refers to a compound in which a hydrocarbon compound composed of only carbon and hydrogen has one hydrogen atom substituted with a hydroxy group, and does not include polyhydric alcohol derivatives having two or more hydroxy groups. The hydrocarbon compound may have a chain-like structure or a ring structure.
The term “dihydric alcohol” refers to a compound in which the aforementioned hydrocarbon compound has two hydrogen atoms substituted with hydroxy groups, and does not include polyhydric alcohol derivatives having three or more hydroxy groups.
Examples of the dihydric alcohol derivative include compounds in which a dihydric alcohol has one hydroxy group substituted with a substituent (e.g., alkoxy group, alkoxyalkyloxy group or the like).
The boiling point of the alcohol organic solvent (under normal pressure) is preferably 50 to 160° C., and more preferably 65 to 150° C. In terms of coatability, stability of the composition during storage and the heat temperature in the bake treatment, the boiling point is most preferably 75 to 135° C.
Specific examples of the alcohol organic solvent having a chain-like structure include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1-butoxy-2-propanol (PGB), n-hexanol, 2-heptanol, 3-heptanol, 1-heptanol, 5-methyl-1-hexanol, 6-methyl-2-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 2-ethyl-1-hexanol, 2-(2-butoxyethoxy)ethanol, n-pentylalcohol, s-pentylalcohol, t-pentylalcohol, isopentylalcohol, isobutanol (also referred to as isobutylalcohol or 2-methyl-1-propanol), isopropylalcohol, 2-ethylbutanol, neopentylalcohol, n-butanol, s-butanol, t-butanol, 1-propanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, ethanol and methanol.
Further, specific examples of the alcohol organic solvent having a ring structure include cyclopentane methanol, 1-cyclopentylethanol, cyclohexanol, cyclohexane methanol, cyclohexane ethanol, 1,2,3,6-tetrahydrobenzyl alcohol, exo-norborneol, 2-methylcyclohexanol, cycloheptanol, 3,5-dimethylcyclohexanol, and benzyl alcohol.
Among alcohol organic solvents, a monohydric alcohol or a dihydric alcohol derivative having a chain-like structure is preferable, 1-butoxy-2-propanol (PGB), isobutanol (2-methyl-1-propanol), 4-methyl-2-pentanol, n-butanol or ethanol is more preferable, and 1-butoxy-2-propanol (PGB) is particularly desirable.
As the alcohol organic solvent, one type of solvent may be used, or two or more types of solvents may be used in combination.
In the component (S), the amount of the alcohol organic solvent based on the total weight of the component (S) is preferably 50% by weight or more, more preferably 75% by weight or more, and may even be 100% by weight. When the amount of the alcohol organic solvent is at least as large as the lower limit of the above-mentioned range, in a double patterning process, the first resist pattern formed by a first patterning is more unlikely to be dissolved in the case where the alcohol organic solvent is added to a positive resist composition for a second patterning.
As the component (S), an organic solvent other than alcohol organic solvents may be added.
Examples of the organic solvent other than alcohol organic solvents include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; compounds having an ester bond, such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate; polyhydric alcohol derivatives including compounds having an ether bond, such as a monoalkylether (e.g., monomethylether, monoethylether, monopropylether or monobutylether) or monophenylether of any of these polyhydric alcohols or compounds having an ester bond (among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferable); cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; and aromatic organic solvents such as anisole, ethylbenzylether, cresylmethylether, diphenylether, dibenzylether, phenetole, butylphenylether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene and mesitylene.
These solvents other than alcohol organic solventscan be used individually, or in combination as a mixed solvent.
Among these, cyclohexanone (CH), γ-butyrolactone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) and ethyl lactate (EL) are preferable, and CH, PGMEA and PGME are particularly desirable.
Further, among the mixed solvents, a mixed solvent obtained by mixing PGMEA with a polar solvent is preferable. The mixing ratio (weight ratio) of the mixed solvent can be appropriately determined, taking into consideration the compatibility of the PGMEA with the polar solvent, but is preferably in the range of 1:9 to 9:1, more preferably from 2:8 to 8:2.
Specifically, when EL is mixed as the polar solvent, the PGMEA:EL weight ratio is preferably from 1:9 to 9:1, and more preferably from 2:8 to 8:2.
Alternatively, when PGME is mixed as the polar solvent, the PGMEA:PGME weight ratio is preferably from 1:9 to 9:1, more preferably from 2:8 to 8:2, and still more preferably 3:7 to 7:3.
Alternatively, when cyclohexanone (CH) is mixed as the polar solvent, the PGMEA:CH weight ratio is preferably from 1:9 to 9:1, and more preferably from 2:8 to 9:1.
Furthermore, a mixed solvent of PGMEA, PGME and CH maintaining the aforementioned PGMEA:PGME weight ratio and the PGMEA:CH weight ratio can be preferably used.
In addition, a mixed solvent of at least one of PGMEA and EL with γ-butyrolactone is also preferable. The mixing ratio (former:latter) of such a mixed solvent is preferably from 70:30 to 95:5.
Moreover, as the component (S), a mixed solvent of PGMEA and an alcohol organic solvent may be preferably used. The alcohol organic solvent:PGMEA weight ratio is preferably in the range of 99:1 to 50:50, and more preferably 95:5 to 70:30.
The amount of the component (S) is not particularly limited, and is adjusted appropriately to a concentration that enables application of a coating solution to a substrate in accordance with the thickness of the coating film. The component (S) is used in an amount that yields a solid content for the resist composition that is preferably within a range from 0.5 to 20% by weight, and more preferably from 1 to 15% by weight.
Dissolving of the components for a positive resist composition in the component (S) can be conducted by simply mixing and stirring each of the above components together using conventional methods, and where required, the composition may also be mixed and dispersed using a dispersion device such as a dissolver, a homogenizer, or a triple roll mill.
Furthermore, following mixing, the composition may also be filtered using a mesh, or a membrane filter or the like.
[Component (D)]
In the positive resist composition of the present invention, a nitrogen-containing organic compound (D) (hereafter referred to as the component (D)) may be added as an optional component.
As the component (D), there is no particular limitation as long as it functions as an acid diffusion control agent, i.e., a quencher which traps the acid generated from the component (B) upon exposure. A multitude of these components (D) have already been proposed, and any of these known compounds may be used. Among these, an aliphatic amine, particularly a secondary aliphatic amine or tertiary aliphatic amine, and an aromatic amine is preferable.
An aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 12 carbon atoms.
Examples of these aliphatic amines include amines in which at least one hydrogen atom of ammonia (NH3) has been substituted with an alkyl group or hydroxyalkyl group of no more than 12 carbon atoms (i.e., alkylamines or alkylalcoholamines), and cyclic amines.
Specific examples of alkylamines and alkylalcoholamines 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; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines of 5 to 10 carbon atoms are preferable, and tri-n-pentylamine and tri-n-octylamine are particularly desirable.
Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine), or a polycyclic compound (aliphatic polycyclic amine).
Specific examples of the aliphatic monocyclic amine include piperidine, and piperazine.
The aliphatic polycyclic amine preferably has 6 to 10 carbon atoms, and specific examples thereof include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.
Further, aliphatic amines other than those described above can be used. Examples of other aliphatic amines include 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 and tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl] amine.
Examples of aromatic amines include aniline compounds such as aniline, N,N-n-butyl-aniline, 2,6-diisopropylaniline, N-isopropylaniline, 3-isopropoxyaniline and N-ethylaniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole and derivatives thereof, as well as diphenylamine, triphenylamine and tribenzylamine.
As the component (D), one type of compound may be used alone, or two or more types may be used in combination.
The component (D) is typically used in an amount within a range from 0.01 to 5.0 parts by weight, relative to 100 parts by weight of the component (A). When the amount of the component (D) is within the above-mentioned range, the shape of the resist pattern and the post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer are improved.
[Component (E)]
Furthermore, in the positive resist composition of the present invention, for preventing any deterioration in sensitivity, and improving the resist pattern shape and the post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer, at least one compound (E) (hereafter referred to as the component (E)) selected from the group consisting of an organic carboxylic acid, or a phosphorus oxo acid or derivative thereof can be added.
Examples of suitable organic carboxylic acids include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid.
Examples of phosphorus oxo acids include phosphoric acid, phosphonic acid and phosphinic acid. Among these, phosphonic acid is particularly desirable.
Examples of oxo acid derivatives include esters in which a hydrogen atom within the above-mentioned oxo acids is substituted with a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group of 1 to 5 carbon atoms and an aryl group of 6 to 15 carbon atoms.
Examples of phosphoric acid derivatives include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.
Examples of phosphonic acid derivatives include phosphonic acid esters such as dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate and dibenzyl phosphonate.
Examples of phosphinic acid derivatives include phosphinic acid esters such as phenylphosphinic acid.
As the component (E), one type may be used alone, or two or more types may be used in combination.
As the component (E), an organic carboxylic acid is preferred, and salicylic acid is particularly desirable.
The component (E) is typically used in an amount within a range from 0.01 to 5.0 parts by weight, relative to 100 parts by weight of the component (A).
If desired, other miscible additives can also be added to the positive resist composition of the present invention. Examples of such miscible additives include additive resins for improving the performance of the resist film, surfactants for improving the applicability, dissolution inhibitors, plasticizers, stabilizers, colorants, halation prevention agents, and dyes.
According to the positive resist composition of the present invention, a resist pattern with reduced roughness and having an excellent shape can be formed. The reasons why these effects can be achieved has not been elucidated yet, but are presumed as follows.
The positive resist composition of the present invention contains the component (A1) having the structural unit (a1) and the structural unit (a0) and the component (B). By the action of the acid generated from the component (B) upon exposure, the solubility of the exposed portions of the component (A1) in an alkali developing solution is increased, and the exposed portions are dissolved and removed to thereby form a resist pattern.
The structural unit (a0) has a cyclic group containing a highly polar —SO2— at the terminal of the side chain. Further, the side chain portion of the structural unit (a0) is relatively long, as compared to the side chain portion of other structural units. Therefore, it is presumed that, by virtue of including the structural unit (a0), the component (A1) is likely to interact with the component (B). As a result, the component (B) can be uniformly distributed within the resin film.
Further, in the positive resist composition of the present invention, a salt exchange occurs between the component (C1) represented by general formula (c1) and the acid generated from the component (B1). As a result, diffusion of the acid generated from the component (B1) is effectively suppressed by the component (C1) (i.e., a quenching effect can be expected by the salt exchange). The component (C1) generates an acid upon exposure which exhibits a weaker acid strength than that of an acid generated from a conventional acid generator (e.g., an onium salt having d-camphor-10-sulfonate as the anion moiety). As a result, salt exchange is more likely to occur. Therefore, in the present invention, quenching effect is enhanced at unexposed portions.
For the reasons as described above, according to the positive resist composition of the present invention, diffusion of the acid generated at exposed portions to the unexposed portions can be reliably suppressed, and the acid dissociation reaction is made uniform over the entire exposed portions. As a result, it is presumed that roughness can be reduced, and a resist pattern having an excellent shape can be formed.
<<Method of Forming a Resist Pattern>>
The method of forming a resist pattern according to the second aspect of the present invention includes: using a positive resist composition according to the first aspect of the present invention to form a resist film on a substrate; conducting exposure of the resist film; and alkali-developing the resist film to form a resist pattern.
The method for forming a resist pattern according to the present invention can be performed, for example, as follows.
Firstly, the aforementioned positive resist composition of the present invention is applied to a substrate using a spinner or the like, and a prebake (post applied bake (PAB)) is conducted under temperature conditions of 80 to 150° C. for 40 to 120 seconds, preferably 60 to 90 seconds to form a resist film. Then, for example, using an electron lithography system or the like, the resist film is selectively exposed to an electron beam (EB) through a desired mask pattern, followed by post exposure bake (PEB) under temperature conditions of 80 to 150° C. for 40 to 120 seconds, preferably 60 to 90 seconds. Subsequently, alkali developing is conducted using an alkali developing solution such as a 0.1 to 10% by weight aqueous solution of tetramethylammonium hydroxide (TMAH), preferably followed by rinsing with pure water, and drying. If desired, bake treatment (post bake) can be conducted following the alkali developing. In this manner, a resist pattern that is faithful to the mask pattern can be obtained.
The substrate is not specifically limited and a conventionally known substrate can be used. For example, substrates for electronic components, and such substrates having wiring patterns formed thereon can be used. Specific examples of the material of the substrate include metals such as silicon wafer, copper, chromium, iron and aluminum; and glass. Suitable materials for the wiring pattern include copper, aluminum, nickel, and gold.
Further, as the substrate, any one of the above-mentioned substrates provided with an inorganic and/or organic film on the surface thereof may be used. As the inorganic film, an inorganic antireflection film (inorganic BARC) can be used. As the organic film, an organic antireflection film (organic BARC) can be used.
The wavelength to be used for exposure is not particularly limited and the exposure can be conducted using radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, extreme ultraviolet rays (EUV), vacuum ultraviolet rays (VUV), electron beam (EB), X-rays, and soft X-rays.
The positive resist composition of the present invention is effective to KrF excimer laser, ArF excimer laser, EB and EUV, and particularly effective to EB or EUV.
The exposure of the resist film can be either a general exposure (dry exposure) conducted in air or an inert gas such as nitrogen, or immersion exposure (immersion lithography).
In immersion lithography, exposure (immersion exposure) is conducted in a state where the region between the lens and the resist layer formed on a wafer (which was conventionally filled with air or an inert gas such as nitrogen) is filled with a solvent (a immersion medium) that has a larger refractive index than the refractive index of air.
More specifically, in immersion lithography, the region between the resist film formed in the above-described manner and lens at the lowermost portion of the exposure apparatus is filled with a solvent (a immersion medium) that has a larger refractive index than the refractive index of air, and in this state, the resist film is subjected to exposure (immersion exposure) through a desired mask pattern.
The immersion medium preferably exhibits a refractive index larger than the refractive index of air but smaller than the refractive index of the resist film to be subjected to immersion exposure. The refractive index of the immersion medium is not particularly limited as long at it satisfies the above-mentioned requirements.
Examples of this immersion medium which exhibits a refractive index that is larger than the refractive index of air but smaller than the refractive index of the resist film include water, fluorine-based inert liquids, silicon-based solvents and hydrocarbon-based solvents.
Specific examples of the fluorine-based inert liquids include liquids containing a fluorine-based compound such as C3HCl2F5, C4F9OCH3, C4F9OC2H5 or C5H3F7 as the main component, which have a boiling point within a range from 70 to 180° C. and preferably from 80 to 160° C. A fluorine-based inert liquid having a boiling point within the above-mentioned range is advantageous in that the removal of the immersion medium after the exposure can be conducted by a simple method.
As a fluorine-based inert liquid, a perfluoroalkyl compound in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms is particularly desirable. Examples of these perfluoroalkyl compounds include perfluoroalkylether compounds and perfluoroalkylamine compounds.
Specifically, one example of a suitable perfluoroalkylether compound is perfluoro(2-butyl-tetrahydrofuran) (boiling point 102° C.), and an example of a suitable perfluoroalkylamine compound is perfluorotributylamine (boiling point 174° C.).
The method of forming a resist pattern according to the present invention is also applicable to a double exposure method or a double patterning method.
As a double patterning method, for example, there can be mentioned a method of forming a resist pattern including applying a first resist composition on a substrate to form a first resist film on the substrate; subjecting the first resist film to selective exposure and alkali developing to form a first resist pattern; applying a second resist composition on the substrate on which the first resist pattern is formed to form a second resist film; and subjecting the second resist film to selective exposure and alkali developing to form a resist pattern. A positive resist composition of the present invention which contains an alcohol organic solvent is particularly desirable as the second resist composition.
EXAMPLES
As follows is a description of examples of the present invention, although the scope of the present invention is by no way limited by these examples.
Production of Positive Resist Composition
Examples 1 to 10, Comparative Examples 1 to 7
The components shown in Table 1 were mixed together and dissolved to obtain positive resist compositions.













TABLE 1







Component (A)
Component (B)
Component (C1)
Additive
Component (S)
























Comp. Ex. 1
(A)-1
(B)-1
—
(B)-7
—
—
(S)-1
—



[100]
[15.0] 

[3.5]


[2800]


Ex. 1
(A)-1
(B)-1
—
—
(C1)-1
—
(S)-1
—



[100]
[15.0] 


[4.3]

[2800]


Comp. Ex. 2
(A)-1
(B)-2
(B)-3
(B)-7
—
—
(S)-1
—



[100]
[8.0]
[1.0]
[2.5]


[2800]


Ex. 2
(A)-1
(B)-2
(B)-3
—
(C1)-1
—
(S)-1
—



[100]
[8.0]
[1.0]

 [1.85]

[2800]


Ex. 3
(A)-1
(B)-2
(B)-3
—
(C1)-1
—
(S)-1
—



[100]
[8.0]
[1.0]

[3.0]

[2800]


Ex. 4
(A)-1
(B)-2
(B)-3
—
(C1)-1
—
(S)-1
—



[100]
[8.0]
[1.0]

[6.0]

[2800]


Comp. Ex. 3
(A)-1
(B)-2
(B)-3
(B)-6
—
—
(S)-1
—



[100]
[8.0]
[1.0]
[1.9]


[2800]


Comp. Ex. 4
(A)-1
(B)-2
(B)-3
(B)-8
—
—
(S)-1
—



[100]
[8.0]
[1.0]
[2.1]


[2800]


Ex. 5
(A)-2
(B)-2
(B)-3
—
(C1)-1
—
(S)-1
—



[100]
[8.0]
[1.0]

[3.0]

[2800]


Ex. 6
(A)-2
(B)-2
(B)-3
—
(C1)-1
—
(S)-1
—



[100]
[8.0]
[1.0]

[4.5]

[2800]


Ex. 7
(A)-2
(B)-2
(B)-3
—
(C1)-1
—
(S)-1
—



[100]
[8.0]
[1.0]

[6.0]

[2800]


Comp. Ex. 5
(A)-2
(B)-2
(B)-3
(B)-7
—
—
(S)-1
—



[100]
[8.0]
[1.0]
[2.5]


[2800]


Ex. 8
(A)-1
(B)-2
(B)-3
—
(C1)-2
—
(S)-1
—



[100]
[8.0]
[1.0]

[2.6]

[2800]


Ex. 9
(A)-1
(B)-2
(B)-3
—
(C1)-1
—
(S)-2
—



[100]
[8.0]
[1.0]

 [1.85]

[2800]


Ex. 10
(A)-1
(B)-2
(B)-3
—
(C1)-1
—
(S)-2
—



[100]
[8.0]
[1.0]

[3.0]

[2800]


Comp. Ex. 6
(A)-1
(B)-2
(B)-3
(B)-7
—
—
(S)-2
—



[100]
[8.0]
[1.0]
[2.5]


[2800]


Comp. Ex. 7
(A)-3
(B)-4
(B)-5
(B)-9
—
(D)-1
(S)-3
(S)-4



[100]
[5.0]
[4.0]
[1.2]

[0.15]
[2800]
[25]








(E)-1








[0.5] 









In Table 1, the reference characters indicate the following. Further, the values in brackets [ ] indicate the amount (in terms of parts by weight) of the component added.
(A)-1: a copolymer (A1-1-1) represented by chemical formula shown below. Mw: 5,200, Mw/Mn: 1.58. In the chemical formula, the subscript numerals shown on the bottom right of the parentheses ( ) indicate the percentage (mol %) of the respective structural units, and l/m/n/p/q=25/5/45/15/10.




(A)-1: a copolymer (A1-2-1) represented by chemical formula shown below. Mw: 4,700, Mw/Mn: 1.71. In the chemical formula, the subscript numerals shown on the bottom right of the parentheses ( ) indicate the percentage (mol %) of the respective structural units, and l/m/n/p/q/r=25/5/35/10/15/10.




(A)-3: a copolymer (A2-1) represented by chemical formula shown below. Mw: 10,000, Mw/Mn: 1.59. In the chemical formula, the subscript numerals shown on the bottom right of the parentheses ( ) indicate the percentage (mol %) of the respective structural units, and l/m/n=45/35/20.




(B)-1: a compound represented by chemical formula (B1) shown below.
(B)-2: a compound represented by chemical formula (B2) shown below
(B)-3: a compound represented by chemical formula (B3) shown below.
(B)-4: a compound represented by chemical formula (B4) shown below.
(B)-5: a compound represented by chemical formula (B5) shown below.
(B)-6: a compound represented by chemical formula (B6) shown below.







(B)-7: a compound represented by chemical formula (B7) shown below.
(B)-8: a compound represented by chemical formula (B8) shown below.
(B)-9: a compound represented by chemical formula (B9) shown below.




(C1)-1: a compound represented by chemical formula (c1-1-1) shown below
(C1)-2: a compound represented by chemical formula (c1-1-2) shown below




(D)-1: tri-n-pentylamine
(E)-1: salicylic acid
(S)-1: a mixed solvent of 1-butoxy-2-propanol/PGMEA (weight ratio: 85/15)
(S)-2: a mixed solvent of PGMEA/PGME/CH (weight ratio:45/30/25)
(S)-3: a mixed solvent of PGMEA/PGME (weight ratio:60/40)
(S)-4: γ-butyrolactone
<Evaluation>
Using the obtained positive resist compositions, resist patterns were formed in the following manner, and the following evaluation was conducted.
[Formation of Resist Pattern]
An organic antireflection film composition (product name: ARC29A, manufactured by Brewer Science Ltd.) was applied to an 8-inch silicon wafer using a spinner, and the composition was then baked and dried on a hotplate at 205° C. for 60 seconds, thereby forming an organic antireflection film having a thickness of 82 nm.
Each of the positive resist compositions of the aforementioned examples was then applied to the organic anti-reflection film using a spinner, and was then prebaked (PAB) and dried on a hotplate at 120° C. for 60 seconds, thus forming a resist film having a film thickness indicated in Table 2.
Subsequently, the resist film was selectively irradiated with an ArF excimer laser (193 nm) through a photomask (6% halftone) targeting a line and space resist pattern (LS pattern) with a space width of 120 nm and a pitch of 240 nm, using an ArF exposure apparatus NSR-S302 (manufactured by Nikon Corporation; NA (numerical aperture)=0.60, 2⁄3 annular illumination).
Thereafter, a post exposure bake (PEB) treatment was conducted at a temperature indicated in Table 2 for 60 seconds, followed by alkali development for 30 seconds at 23° C. in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) (trade name: NMD-3; manufactured by Tokyo Ohka Kogyo Co., Ltd.).
As a result, an L/S pattern in which lines having a line width of 120 nm were arranged at equal intervals (pitch: 240 nm) was formed on the resist film. The optimum exposure dose Eop (mJ/cm2) with which the L/S pattern was formed is indicated in Table 2.
[Evaluation of Line Width Roughness (LWR)]
With respect to each of the LS patterns formed with the above Eop and having a line width of 120 nm and a pitch of 240 nm, the line width at 400 points in the lengthwise direction of the line were measured using a measuring scanning electron microscope (SEM) (product name: S-9220, manufactured by Hitachi, Ltd.; acceleration voltage: 800V). From the results, the value of 3 times the standard deviation s (i.e., 3s) was determined, and the average of the 3s values at 5 points was calculated as a yardstick of LWR. The results are shown in Table 2.
The smaller this 3s value is, the lower the level of roughness of the line width, indicating that an L/S pattern with a uniform width was obtained.












TABLE 2







Film






thickness
PEB
Eop
LWR



(nm)
(° C.)
(mJ/cm2)
3s






















Comp. Ex. 1
100
90
14.0
9.3



Ex. 1
80
90
18.0
8.1



Comp. Ex. 2
80
90
28.0
11.0



Ex. 2
80
90
29.0
8.8



Ex. 3
80
90
32.0
8.3



Ex. 4
80
90
40.0
6.9



Comp. Ex. 3
80
90
13.0
12.1



Comp. Ex. 4
100
90
31.0
10.5



Ex. 5
80
90
25.0
7.3



Ex. 6
80
90
31.0
7.0



Ex. 7
80
90
35.0
6.0



Comp. Ex. 5
80
90
21.0
9.3



Ex. 8
80
90
32.0
6.4



Ex. 9
80
90
32.0
7.9



Ex. 10
100
90
35.0
6.5



Comp. Ex. 6
80
90
31.0
14.1



Comp. Ex. 7
100
110
29.0
9.6










From the results shown in Table 2, it was confirmed that the 3s values in Examples 1 to 10 were smaller than those of Comparative Examples 1 to 7, meaning that the roughness of the line width was small, and L/S patterns with a substantially uniform width were formed.
Therefore, it was found that, according to the present invention, roughness can be reduced, and a resist pattern having an excellent shape can be formed.
While preferred embodiments of the invention have been described and illustrated above, it should be understood that these are exemplary of the invention and are not to be considered as limiting. Additions, omissions, substitutions, and other modifications can be made without departing from the spirit or scope of the present invention. Accordingly, the invention is not to be considered as being limited by the foregoing description, and is only limited by the scope of the appended claims.

## Claims

1. A positive resist composition comprising:
a resin component (A1) comprising a structural unit (a1) derived from an acrylate ester which may have an atom other than hydrogen or a group bonded to the carbon atom on the α position and containing an acid dissociable, dissolution inhibiting group, a structural unit (a0) derived from an acrylate ester which may have an atom other than hydrogen or a group bonded to the carbon atom on the α position and containing an —SO2— containing cyclic group, and a structural unit (a5) represented by general formula (a5-1) shown below, a compound (C1) represented by general formula (c1) shown below; and
an acid-generator component (B) which generates acid upon exposure, excluding the compound (C1):





wherein R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; Y5 represents an aliphatic hydrocarbon group which may have a substituent: Z represents a monovalent organic group; a represents an integer of 1 to 3, and b represents an integer of 0 to 2, provided that a+b=1 to 3; and each of c, d and e independently represents an integer of 0 to 3,




wherein R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; Y1 represents a divalent aliphatic hydrocarbon group; R1 represents a hydrogen atom, a fluorine atom, an alkyl group or a fluorinated alkyl group; p represents an integer of 1 to 10; and A+ represents an organic cation.

2. The positive resist composition according to claim 1, which further comprises an alcohol organic solvent.

3. The positive resist composition according to claim 1, wherein the structural unit (a0) is a structural unit represented by general formula (a0-0-1) shown below:



wherein R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms; R4 represents a divalent linking group; and R3 represents an —SO2— containing cyclic group.

4. The positive resist composition according to claim 1, wherein the amount of the compound (C1), relative to 100 parts by weight of the resin component (A1) is in the range of 0.5 to 10 parts by weight.

5. A method of forming a resist pattern, comprising using a positive resist composition of claim 1 to form a resist film on a substrate, subjecting the resist film to exposure, and subjecting the resist film to alkali developing to form a resist pattern.

6. The positive resist composition according to claim 1, wherein, A+ in the general formula (c1) is an organic cation represented by general formula (b′-1) shown below:



wherein each of R1′′ to R3′′ independently represents an aryl group or an alkyl group; two of R1′′ to R3′′ may be mutually bonded to form a ring with the sulfur atom; and at least one of R1′′ to R3′′ represents a substituted aryl group.

7. The positive resist composition according to claim 6, wherein the substituent for the substituted aryl group in the general formula (b′-1) is an alkoxyalkyloxy group, an alkoxycarbonylalkyloxy group, a group represented by the formula —(R4′)—C(═O)—R5′ or an alkylcarbonyloxy group of 10 carbon atoms, wherein R4′ represents an alkylene group of 1 to 5 carbon atoms, and R5′ represents an aryl group.