WO2024190825A1 - レジスト組成物、レジストパターン形成方法、含フッ素高分子化合物、及び化合物 - Google Patents
レジスト組成物、レジストパターン形成方法、含フッ素高分子化合物、及び化合物 Download PDFInfo
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/16—Halogens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/22—Esters containing halogen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
Definitions
- the present invention relates to a resist composition, a method of forming a resist pattern, a fluorine-containing polymeric compound, and a compound.
- a common method of miniaturization is to shorten the wavelength (increase the energy) of the exposure light source.
- Resist materials are required to have lithography properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.
- lithography properties such as sensitivity to these exposure light sources and resolution capable of reproducing patterns with fine dimensions.
- a chemically amplified resist composition that contains a base component whose solubility in a developer changes due to the action of acid, and an acid generator component that generates acid upon exposure, has been used so far.
- Patent Document 1 discloses a resist composition containing a resin component having a structural unit containing an acid-dissociable group of a specific structure, a structural unit containing a fluorine-containing alcohol, and a structural unit containing a phenolic hydroxyl group.
- the present invention has been made in consideration of the above circumstances, and aims to provide a resist composition that can form a resist pattern with high sensitivity, reduced LWR, and excellent defect characteristics after development, a method for forming a resist pattern using the resist composition, a fluorine-containing polymer compound used in the resist composition, and a compound that can be used to manufacture the fluorine-containing polymer compound.
- a first aspect of the present invention is a resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, the resist composition comprising: a resin component (A1) whose solubility in a developer changes due to the action of an acid; and a fluorine-containing polymeric compound (F0) that has a structural unit (f0) derived from a compound represented by the following general formula (f0-1):
- W 1 is a polymerizable group.
- Ar is an aromatic ring.
- Xf is an iodine atom or a substituent containing an iodine atom.
- m1 is an integer of 1 or more as long as the valence allows.
- Lf 01 is a single bond or a linking group having a valence of (n1+1).
- Rf 01 is a fluorinated alkyl group having 1 to 12 carbon atoms.
- Rf 02 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom or a hydrogen atom.
- n1 is an integer of 1 to 3.
- Rf 03 is a substituent other than an iodine atom.
- m2 is an integer of 0 or more as long as the valence allows.
- the second aspect of the present invention is a method for forming a resist pattern, comprising the steps of forming a resist film on a support using the resist composition according to the first aspect, exposing the resist film to light, and developing the exposed resist film to form a resist pattern.
- the third aspect of the present invention is a fluorine-containing polymeric compound having a structural unit (f0) derived from a compound represented by the following general formula (f0-1):
- W 1 is a polymerizable group.
- Ar is an aromatic ring.
- Xf is an iodine atom or a substituent containing an iodine atom.
- m1 is an integer of 1 or more as long as the valence allows.
- Lf 01 is a single bond or a linking group having a valence of (n1+1).
- Rf 01 is a fluorinated alkyl group having 1 to 12 carbon atoms.
- Rf 02 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom or a hydrogen atom.
- n1 is an integer of 1 to 3.
- Rf 03 is a substituent other than an iodine atom.
- m2 is an integer of 0 or more as long as the valence allows.
- the fourth aspect of the present invention is a compound represented by the following general formula (f0-1):
- W 1 is a polymerizable group.
- Ar is an aromatic ring.
- Xf is an iodine atom or a substituent containing an iodine atom.
- m1 is an integer of 1 or more as long as the valence allows.
- Lf 01 is a single bond or a linking group having a valence of (n1+1).
- Rf 01 is a fluorinated alkyl group having 1 to 12 carbon atoms.
- Rf 02 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom or a hydrogen atom.
- n1 is an integer of 1 to 3.
- Rf 03 is a substituent other than an iodine atom.
- m2 is an integer of 0 or more as long as the valence allows.
- the present invention provides a resist composition that can form a resist pattern with high sensitivity, reduced LWR, and excellent defect characteristics after development, a method for forming a resist pattern using the resist composition, a fluorine-containing polymer compound used in the resist composition, and a compound that can be used to manufacture the fluorine-containing polymer compound.
- alkyl group includes linear, branched and cyclic monovalent saturated hydrocarbon groups. The same applies to the alkyl group in an alkoxy group.
- alkylene group includes linear, branched and cyclic divalent saturated hydrocarbon groups.
- halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- structural unit refers to a monomer unit that constitutes a polymeric compound (resin, polymer, copolymer).
- the phrase "may have a substituent” includes both the case where a hydrogen atom (--H) is replaced with a monovalent group and the case where a methylene group (--CH 2 -) is replaced with a divalent group.
- exposure is intended to include the general concept of irradiation with radiation.
- acid-decomposable group refers to a group having acid decomposability in which at least a part of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid.
- acid-decomposable groups whose polarity increases under the action of an acid include groups that are decomposed by the action of an acid to generate a polar group.
- the polar group include a carboxy group, a hydroxyl group, an amino group, and a sulfo group (-SO 3 H).
- the acid-decomposable group include groups in which the polar group is protected with an acid-dissociable group (for example, a group in which the hydrogen atom of an OH-containing polar group is protected with an acid-dissociable group).
- acid dissociable group refers to both (i) a group having acid dissociability in which the bond between the acid dissociable group and an atom adjacent to the acid dissociable group can be cleaved by the action of an acid, and (ii) a group in which a part of the bond is cleaved by the action of an acid and then a decarboxylation reaction occurs, thereby cleaving the bond between the acid dissociable group and an atom adjacent to the acid dissociable group.
- the acid dissociable group constituting the acid decomposable group must be a group with lower polarity than the polar group generated by dissociation of the acid dissociable group, and thus, when the acid dissociable group is dissociated by the action of an acid, a polar group with higher polarity than the acid dissociable group is generated, and the polarity increases.As a result, the polarity of the entire (A1) component increases.By increasing the polarity, the solubility in the developer changes relatively, and when the developer is an alkaline developer, the solubility increases, and when the developer is an organic developer, the solubility decreases.
- the “base material component” is an organic compound that has film-forming ability.
- Organic compounds used as base material components are broadly divided into non-polymers and polymers.
- Non-polymers usually have a molecular weight of 500 or more and less than 4000 (hereinafter referred to as “low molecular weight compounds”).
- “resin,” “polymeric compound,” or “polymer” refers to a polymer with a molecular weight of 1000 or more. The molecular weight of the polymer is determined by the weight average molecular weight calculated in terms of polystyrene using GPC (gel permeation chromatography).
- derived structural unit refers to a structural unit formed by cleavage of a multiple bond between carbon atoms, for example, an ethylenic double bond.
- the hydrogen atom bonded to the carbon atom at the ⁇ -position may be substituted with a substituent.
- the substituent (R ⁇ x ) substituting the hydrogen atom bonded to the carbon atom at the ⁇ -position is an atom or group other than a hydrogen atom.
- an itaconic acid diester in which the substituent (R ⁇ x ) is substituted with a substituent containing an ester bond
- an ⁇ -hydroxyacrylic ester in which the substituent (R ⁇ x ) is substituted with a hydroxyalkyl group or a group in which the hydroxyl group is modified.
- the carbon atom at the ⁇ -position of an acrylic acid ester refers to the carbon atom to which the carbonyl group of acrylic acid is bonded, unless otherwise specified.
- an acrylic ester in which the hydrogen atom bonded to the carbon atom at the ⁇ -position is substituted with a substituent will sometimes be referred to as an ⁇ -substituted acrylic ester.
- derivative refers to a concept that includes compounds in which the hydrogen atom at the ⁇ -position of the target compound is replaced with other substituents such as an alkyl group or a halogenated alkyl group, as well as derivatives thereof.
- examples of such derivatives include compounds in which the hydrogen atom of the hydroxyl group of a target compound, which may have the hydrogen atom at the ⁇ -position replaced with a substituent, is replaced with an organic group; compounds in which the hydrogen atom at the ⁇ -position of a target compound, which may have the hydrogen atom at the ⁇ -position replaced with a substituent, is bonded to a substituent other than a hydroxyl group, and the like.
- the ⁇ -position refers to the first carbon atom adjacent to the functional group, unless otherwise specified.
- Examples of the substituent that substitutes the hydrogen atom at the ⁇ -position of the hydroxystyrene include the same as those for R ⁇ x .
- the resist composition of this embodiment generates an acid upon exposure, and the solubility of the resist composition in a developer changes due to the action of the acid.
- a resist composition contains a base component (A) (hereinafter also referred to as “component (A)”) whose solubility in a developer changes under the action of an acid, and a fluorine-containing polymeric compound (F0) (hereinafter also referred to as “component (F0)”) having a structural unit (f0) derived from a compound represented by (f0-1) described below.
- the resist composition of this embodiment may further contain other components in addition to the above-mentioned components (A) and (F0).
- other components include the following components (B), (D), (E), (F1), and (S).
- the resist composition of this embodiment may be (1) one that further contains an acid generator component (B) that generates an acid upon exposure (hereinafter referred to as “component (B)”); (2) one in which the component (A) is a component that generates an acid upon exposure; or (3) one in which the component (A) is a component that generates an acid upon exposure, and which further contains component (B). That is, in the above cases of (2) and (3), the component (A) is a "base component that generates an acid upon exposure and changes its solubility in a developer by the action of the acid".
- component (B) that generates an acid upon exposure
- the component (A) is a base component that generates an acid upon exposure and changes its solubility in a developer by the action of the acid
- the component (A1) described below is preferably a resin that generates an acid upon exposure and changes its solubility in a developer by the action of the acid.
- a resin a polymer compound having a structural unit that generates an acid upon exposure can be used.
- the structural unit that generates an acid upon exposure the structural unit (a5) described below can be used.
- the resist composition of this embodiment is preferably the above-mentioned case (1).
- the resist composition of this embodiment preferably contains component (A) and component (B).
- a resist film is formed using the resist composition of this embodiment and selective exposure is performed on the resist film, for example, an acid is generated from component (B) in the exposed parts of the resist film, and the solubility of component (A) in the developer changes due to the action of the acid, whereas the solubility of component (A) in the developer does not change in the unexposed parts of the resist film, resulting in a difference in solubility in the developer between the exposed and unexposed parts.
- the resist film when the resist film is developed, if the resist composition is a positive type, the exposed parts of the resist film are dissolved and removed to form a positive type resist pattern, and if the resist composition is a negative type, the unexposed parts of the resist film are dissolved and removed to form a negative type resist pattern.
- the resist composition of this embodiment may be a positive resist composition or a negative resist composition.
- the resist composition of this embodiment may be for an alkaline development process in which an alkaline developer is used in the development treatment during resist pattern formation, or may be for a solvent development process in which a developer containing an organic solvent (organic developer) is used in the development treatment.
- ⁇ Component (A)> In the resist composition of this embodiment, by using the component (A1), the polarity of the base component changes between before and after exposure, and therefore a good development contrast can be obtained not only in an alkali development process, but also in a solvent development process.
- the component (A) other polymeric compounds and/or low molecular weight compounds may be used in combination with the component (A1).
- the component (A) may be used alone or in combination of two or more types.
- the component (A1) is a resin component whose solubility in a developer changes due to the action of an acid.
- the component (A1) preferably has a structural unit (a1) that contains an acid-decomposable group whose polarity increases when acted on by an acid.
- the component (A1) may contain other structural units, in addition to the structural unit (a1), as necessary.
- the structural unit (a1) is a structural unit that contains an acid-decomposable group whose polarity increases when acted upon by an acid.
- Examples of the acid-dissociable group include those that have been proposed as acid-dissociable groups in base resins for chemically amplified resist compositions.
- Specific examples of the acid dissociable group that have been proposed for the base resin of the chemically amplified resist composition include the "acetal type acid dissociable group,”"tertiary alkyl ester type acid dissociable group,””tertiary alkyloxycarbonyl acid dissociable group,” and “secondary alkyloxycarbonyl acid dissociable group,” which are explained below.
- Acetal-type acid-dissociable group Among the polar groups, examples of the acid dissociable group protecting a carboxy group or a hydroxyl group include an acid dissociable group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as an “acetal-type acid dissociable group”).
- Ra' 1 and Ra' 2 are a hydrogen atom or an alkyl group.
- Ra' 3 is a hydrocarbon group, and Ra' 3 may be bonded to either Ra' 1 or Ra' 2 to form a ring.
- At least one of Ra'1 and Ra'2 is preferably a hydrogen atom, and more preferably both are hydrogen atoms.
- Ra'1 or Ra'2 is an alkyl group
- examples of the alkyl group include the same alkyl groups as those exemplified as the substituent that may be bonded to the carbon atom at the ⁇ -position in the description of the above ⁇ -substituted acrylic acid ester, and an alkyl group having 1 to 5 carbon atoms is preferred.
- preferred examples are linear or branched alkyl groups.
- More 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, and a neopentyl group, and the like.
- a methyl group or an ethyl group is more preferred, and a methyl group is particularly preferred.
- the hydrocarbon group for Ra'3 includes a linear or branched alkyl group, or a cyclic hydrocarbon group.
- the linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms.
- Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Of these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
- the branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably has 3 to 5 carbon atoms. Specific examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, and 2,2-dimethylbutyl groups, with isopropyl being preferred.
- the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
- the monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the aromatic hydrocarbon group of Ra'3 is an aromatic hydrocarbon group
- the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
- the aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons, and may be monocyclic or polycyclic.
- the aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
- aromatic ring examples include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- aromatic heterocycle examples include a pyridine ring and a thiophene ring.
- aromatic hydrocarbon group in Ra'3 include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (e.g., arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.).
- the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably has 1 to 2 carbon atoms, and particularly preferably has 1 carbon atom.
- the cyclic hydrocarbon group in Ra'3 may have a substituent.
- substituents include -R P1 , -R P2 -O-R P1 , -R P2 -CO-R P1 , -R P2 -CO-OR P1 , -R P2 -O-CO-R P1 , -R P2 -OH, -R P2 -CN or -R P2 -COOH (hereinafter these substituents are collectively referred to as "Ra x5 ").
- R P1 is a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms.
- R P2 is a single bond, a divalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms.
- the hydrogen atoms of the linear saturated hydrocarbon group, the aliphatic cyclic saturated hydrocarbon group, and the aromatic hydrocarbon group of R P1 and R P2 may be substituted with fluorine atoms.
- the aliphatic cyclic hydrocarbon group may have one or more of the above-mentioned substituents alone, or may have one or more of each of the above-mentioned substituents.
- Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms 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, and a decyl group.
- Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; and polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.02,6]decanyl group, a tricyclo[3.3.1.13,7]decanyl group, a tetracyclo[6.2.1.13,6.02,7]dodecanyl group, and an adamantyl group.
- monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group,
- Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include groups in which one hydrogen atom has been removed from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.
- the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring.
- Specific examples of the cyclic group include a tetrahydropyranyl group and a tetrahydrofuranyl group.
- Tertiary alkyl ester type acid-dissociable group examples of the acid-dissociable group that protects the carboxy group include acid-dissociable groups represented by the following general formula (a1-r-2).
- acid-dissociable groups represented by the following formula (a1-r-2) those constituted by an alkyl group may be referred to as "tertiary alkyl ester-type acid-dissociable groups" hereinafter for the sake of convenience.
- Ra' 4 to Ra' 6 are each a hydrocarbon group, and Ra' 5 and Ra' 6 may be bonded to each other to form a ring.
- Examples of the hydrocarbon group for Ra'4 include a linear or branched alkyl group, a linear or cyclic alkenyl group, or a cyclic hydrocarbon group.
- Examples of the linear or branched alkyl group and cyclic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group, and aromatic hydrocarbon group) in Ra'4 are the same as those for Ra'3 .
- the chain or cyclic alkenyl group for Ra'4 is preferably an alkenyl group having 2 to 10 carbon atoms.
- Examples of the hydrocarbon group for Ra'5 and Ra'6 include the same as those for Ra'3 .
- Ra'5 and Ra'6 are bonded to each other to form a ring
- suitable examples of such a ring include a group represented by the following general formula (a1-r2-1), a group represented by the following general formula (a1-r2-2), and a group represented by the following general formula (a1-r2-3).
- suitable examples include groups represented by the following general formula (a1-r2-4).
- Ra' 10 represents a linear or branched alkyl group having 1 to 12 carbon atoms, some of which may be substituted with a halogen atom or a heteroatom-containing group.
- Ra' 11 represents a group which forms an aliphatic cyclic group together with the carbon atom to which Ra' 10 is bonded.
- Ya represents a carbon atom.
- Xa represents a group which forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group may be substituted.
- Ra 101 to Ra 103 are each independently a hydrogen atom, a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Some or all of the hydrogen atoms in this linear saturated hydrocarbon group and aliphatic cyclic saturated hydrocarbon group may be substituted. Two or more of Ra 101 to Ra 103 may be bonded to each other to form a cyclic structure.
- Yaa is a carbon atom.
- Xaa is a group forming an aliphatic cyclic group together with Yaa.
- Ra 104 is an aromatic hydrocarbon group which may have a substituent.
- Ra' 12 and Ra' 13 are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group may be substituted.
- Ra' 14 is a hydrocarbon group which may have a substituent. * indicates a bond (the same applies hereinafter).]
- Ra' 10 is a linear or branched alkyl group having 1 to 12 carbon atoms which may be partially substituted with a halogen atom or a heteroatom-containing group.
- the linear alkyl group for Ra' 10 has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
- Examples of the branched alkyl group in Ra'10 include the same as those in Ra'3 .
- the alkyl group in Ra' 10 may be partially substituted with a halogen atom or a heteroatom-containing group.
- some of the hydrogen atoms constituting the alkyl group may be substituted with a halogen atom or a heteroatom-containing group.
- some of the carbon atoms (e.g., methylene groups) constituting the alkyl group may be substituted with a heteroatom-containing group.
- the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom.
- Ra' 11 (the aliphatic cyclic group formed together with the carbon atom to which Ra' 10 is bonded) is preferably the same as those exemplified as the monocyclic or polycyclic aliphatic hydrocarbon group (alicyclic hydrocarbon group) for Ra' 3 in formula (a1-r-1).
- a monocyclic alicyclic hydrocarbon group is preferred, and specifically, a cyclopentyl group or a cyclohexyl group is more preferred.
- examples of the cyclic hydrocarbon group formed by Xa together with Ya include groups in which one or more hydrogen atoms have been further removed from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) in Ra'3 in formula (a1-r-1).
- the cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. Examples of the substituent include the same substituents as those which the cyclic hydrocarbon group in Ra'3 may have.
- examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms for Ra 101 to Ra 103 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, and a decyl group.
- Examples of the monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in Ra 101 to Ra 103 include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group; and polycyclic aliphatic saturated hydrocarbon groups such as a bicyclo[2.2.2]octanyl group, a tricyclo[5.2.1.02,6]decanyl group, a tricyclo[3.3.1.13,7]decanyl group, a tetracyclo[6.2.1.13,6.02,7]dodecanyl group, and an adamantyl group.
- monocyclic aliphatic saturated hydrocarbon groups such as a cycl
- Ra 101 to Ra 103 are preferably a hydrogen atom or a monovalent linear saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom.
- Examples of the substituent that the chain saturated hydrocarbon group or the alicyclic saturated hydrocarbon group represented by the above Ra 101 to Ra 103 may have include the same groups as those for the above Ra x5 .
- Examples of groups containing a carbon-carbon double bond formed by two or more of Ra 101 to Ra 103 bonding to each other to form a cyclic structure include a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, a methylcyclohexenyl group, a cyclopentylidene-ethenyl group, a cyclohexylidene-ethenyl group, etc.
- a cyclopentenyl group, a cyclohexenyl group, and a cyclopentylidene-ethenyl group are preferred.
- the aliphatic cyclic group formed by Xaa together with Yaa is preferably the same as those exemplified as the monocyclic or polycyclic aliphatic hydrocarbon group for Ra'3 in formula (a1-r-1).
- examples of the aromatic hydrocarbon group for Ra 104 include groups in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 5 to 30 carbon atoms.
- Ra 104 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene, or phenanthrene, even more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from benzene or naphthalene, and most preferably a group in which one or more hydrogen atoms have been removed from benzene.
- Examples of the substituent that Ra 104 in formula (a1-r2-3) may have include a methyl group, an ethyl group, a propyl group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group), an alkyloxycarbonyl group, and the like.
- Ra' 12 and Ra' 13 are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms.
- Examples of the monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms in Ra' 12 and Ra' 13 include the same monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms in the above Ra 101 to Ra 103.
- Some or all of the hydrogen atoms in this chain saturated hydrocarbon group may be substituted.
- Ra' 12 and Ra' 13 are preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
- examples of the substituent include the same groups as those for the above Ra -x5 .
- Ra' 14 is a hydrocarbon group which may have a substituent.
- Examples of the hydrocarbon group in Ra' 14 include a linear or branched alkyl group, and a cyclic hydrocarbon group.
- the linear alkyl group for Ra' 14 preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2.
- Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Of these, a methyl group, an ethyl group, or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.
- the branched alkyl group for Ra' 14 preferably has 3 to 10 carbon atoms, and more preferably has 3 to 5 carbon atoms. Specific examples include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and is preferably an isopropyl group.
- the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
- the monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the aliphatic hydrocarbon group that is a polycyclic group a group in which one hydrogen atom has been removed from a polycycloalkane is preferable, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
- Ra' 14 examples include the same as the aromatic hydrocarbon group for Ra 104.
- Ra' 14 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene or phenanthrene, still more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from naphthalene or anthracene, and most preferably a group in which one or more hydrogen atoms have been removed from naphthalene.
- substituent which Ra' 14 may have include the same substituents as those which Ra 104 may have.
- Ra' 14 in formula (a1-r2-4) is a naphthyl group
- the position at which it bonds to the tertiary carbon atom in formula (a1-r2-4) may be either the 1st or 2nd position of the naphthyl group.
- Ra' 14 in formula (a1-r2-4) is an anthryl group
- the position at which it bonds to the tertiary carbon atom in formula (a1-r2-4) may be any one of the 1-position, 2-position or 9-position of the anthryl group.
- Tertiary alkyloxycarbonyl acid dissociating group Among the polar groups, examples of the acid dissociable group that protects the hydroxyl group include acid dissociable groups represented by the following general formula (a1-r-3) (hereinafter, for convenience, may be referred to as “tertiary alkyloxycarbonyl acid dissociable group”).
- Ra' 7 to Ra' 9 each represent an alkyl group.
- Ra' 7 to Ra' 9 are each preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
- the total number of carbon atoms in each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 or 4.
- Secondary alkyl ester type acid-dissociable group Among the above polar groups, examples of the acid-dissociable group that protects the carboxy group include acid-dissociable groups represented by the following general formula (a1-r-4).
- Ra'10 is a hydrocarbon group.
- Ra'11a and Ra'11b are each independently a hydrogen atom, a halogen atom or an alkyl group.
- Ra'12 is a hydrogen atom or a hydrocarbon group.
- Ra'10 and Ra'11a or Ra'11b may be bonded to each other to form a ring.
- Ra'11a or Ra'11b and Ra'12 may be bonded to each other to form a ring.
- examples of the hydrocarbon group in Ra'10 and Ra'12 include the same as those in Ra'3 above.
- examples of the alkyl group in Ra'11a and Ra'11b include the same as the alkyl group in Ra'1 .
- the hydrocarbon groups in Ra'10 and Ra'12 and the alkyl groups in Ra'11a and Ra'11b may have a substituent. Examples of the substituent include the above-mentioned Rax5 .
- Ra'10 and Ra'11a or Ra'11b may be bonded to each other to form a ring.
- the ring may be a polycyclic or monocyclic ring, an alicyclic or aromatic ring.
- the alicyclic and aromatic rings may contain heteroatoms.
- the ring formed by Ra'10 and Ra'11a or Ra'11b bonding to each other is preferably a monocycloalkene, a ring in which a part of the carbon atoms of a monocycloalkene is substituted with a heteroatom (oxygen atom, sulfur atom, etc.), or a monocycloalkadiene, more preferably a cycloalkene having 3 to 6 carbon atoms, and more preferably cyclopentene or cyclohexene.
- the ring formed by bonding Ra'10 and Ra'11a or Ra'11b to each other may be a condensed ring.
- Specific examples of the condensed ring include indan.
- the ring formed by bonding Ra'10 and Ra'11a or Ra'11b together may have a substituent.
- substituents include the above-mentioned Rax5 .
- Ra'11a or Ra'11b and Ra'12 may be bonded to each other to form a ring, and examples of such a ring include the same as the ring formed by Ra'10 and Ra'11a or Ra'11b being bonded to each other.
- the structural unit (a1) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the ⁇ -position may be substituted with a substituent.
- Preferred specific examples of the structural unit (a1) include structural units represented by the following general formulas (a1-1), (a1-2) and (a1-3).
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- Va 1 is a divalent hydrocarbon group which may have an ether bond.
- n a1 is an integer of 0 to 2.
- Ra 1 is an acid dissociable group represented by the above general formula (a1-r-1), (a1-r-2) or (a1-r-4).
- Wa 1 is n a2 +1 valent hydrocarbon group
- n a2 is an integer of 1 to 3
- Ra 2 is an acid dissociable group represented by the above general formula (a1-r-1) or (a1-r-3).
- Ya 001 is a single bond or a divalent linking group.
- Ya 01 is a single bond or a divalent linking group.
- Rax01 is an acid dissociable group represented by the above general formula (a1-r-1), (a1-r-2) or (a1-r-4).
- q is an integer of 0 to 3.
- n is an integer of 0 or more, provided that n ⁇ q ⁇ 2+4.
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- the alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and 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 having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms.
- a fluorine atom is particularly preferable.
- R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is most preferred.
- the divalent hydrocarbon group for Va1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
- the aliphatic hydrocarbon group as the divalent hydrocarbon group in Va1 may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group may be a straight-chain or branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.
- the linear aliphatic hydrocarbon group preferably contains 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.
- a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
- the branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably has 3 to 6 carbon atoms, even more preferably has 3 or 4 carbon atoms, and most preferably has 3 carbon atoms.
- a branched alkylene group is preferable, and specific examples thereof include 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- , -CH( CH2CH3 ) CH2- , and -C ( CH2CH3 ) 2 - CH2- ; alkyltrim
- Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc.
- Examples of the linear or branched aliphatic hydrocarbon group include the same as the linear aliphatic hydrocarbon group or the branched aliphatic hydrocarbon group.
- the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
- the alicyclic hydrocarbon group may be polycyclic or monocyclic.
- the monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
- the aromatic hydrocarbon group as the divalent hydrocarbon group in Va1 is a hydrocarbon group having an aromatic ring.
- the aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in the substituents.
- Specific examples of the aromatic ring contained in the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom, etc.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- aromatic hydrocarbon group examples include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring (arylene group); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring (aryl group) has been substituted with an alkylene group (for example, a group in which one hydrogen atom has been further removed from the aryl group in 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 number of carbon atoms in the alkylene group is preferably 1 to 4, more preferably 1
- Ra 1 is an acid-dissociable group represented by the above formula (a1-r-1), (a1-r-2) or (a1-r-4).
- the n a2 +1 valent hydrocarbon group in Wa 1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
- the aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity, and may be saturated or unsaturated, and is usually preferably saturated.
- Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing a ring in the structure, and groups that combine linear or branched aliphatic hydrocarbon groups with aliphatic hydrocarbon groups containing a ring in the structure.
- the n a2 +1 valency is preferably divalent to tetravalent, and more preferably divalent or trivalent.
- Ra2 is an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-3).
- the divalent linking group for Ya 001 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
- the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
- the divalent linking group for Ya 01 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
- Rax 01 is preferably an acid dissociable group represented by the above general formula (a1-r-2) or (a1-r-4), and among these, an acid dissociable group represented by general formula (a1-r-2) is more preferable, and a group represented by general formula (a1-r2-1) is even more preferable.
- q is an integer of 0 to 3.
- the structure is a benzene structure
- when q is 1 the structure is a naphthalene structure
- when q is 2 the structure is an anthracene structure
- when q is 3, the structure is a tetracene structure.
- n is an integer of 0 or more, preferably 0 to 5, more preferably 0 to 3, and even more preferably 0 to 2.
- the naphthalene structure is a naphthalene structure
- all six hydrogen atoms of the naphthalene may be substituted with hydroxy groups.
- the substitution positions of Ya 001 , -Ya 01 -C( ⁇ O)-O-Ra 01 group, and hydroxy group are not particularly limited.
- R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
- the structural unit (a1) contained in the component (A1) may be of one type, or two or more types.
- a structural unit represented by the above formula (a1-1) or a structural unit represented by the above formula (a1-3) is more preferable, since these structural units are capable of more easily improving the characteristics (sensitivity, shape, etc.) in electron beam or EUV lithography.
- the acid-dissociable groups (Ra 1 , Rax 01 ) are acid-dissociable groups represented by the above general formulas (a1-r2-1), (a1-r2-3), (a1-r2-4) or (a1-r-4), respectively, and among these, it is particularly preferable to select those which are cyclic groups.
- the proportion of the structural unit (a1) in the component (A1) is preferably 5 to 80 mol %, more preferably 10 to 75 mol %, even more preferably 30 to 70 mol %, and particularly preferably 40 to 70 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
- lithography properties such as sensitivity, resolution, and roughness can be improved.
- the proportion is at most the upper limit of the aforementioned preferred range, a balance with other structural units can be achieved, and various lithography properties become favorable.
- the component (A1) may contain other structural units, in addition to the structural unit (a1) described above, as necessary.
- Examples of the other structural units include a structural unit represented by general formula (a10-1) below; a structural unit (a5) that generates acid upon exposure; a structural unit (a2) that includes a lactone-containing cyclic group; and a structural unit derived from a compound represented by general formula (a8-1) below.
- Structural unit (a10) The structural unit (a10) is a structural unit represented by general formula (a10-1) shown below.
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- Ya x1 is a single bond or a divalent linking group.
- Wa x1 is an aromatic hydrocarbon group which may have a substituent.
- n ax1 is an integer of 1 or more.
- R is the same as R in the general formula (a1-1).
- R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is particularly preferred.
- Ya x1 represents a single bond or a divalent linking group.
- the divalent linking group for Ya x1 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
- the divalent hydrocarbon group which may have a substituent may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
- the aliphatic hydrocarbon group refers to a hydrocarbon group having no aromaticity.
- the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
- Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups containing a ring in the structure.
- the straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably has 1 to 6 carbon atoms, even more preferably has 1 to 4 carbon atoms, and most preferably has 1 to 3 carbon atoms.
- a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
- the branched chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably has 3 to 6 carbon atoms, even more preferably has 3 or 4 carbon atoms, and most preferably has 3 carbon atoms.
- a branched alkylene group is preferable, and specific examples thereof include 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- , -CH( CH2CH3 ) CH2- , and -C ( CH2CH3 ) 2 - CH2- ; alkyltrimethylene groups such as -CH( CH3 ) CH2CH2CH2- , -CH2CH ( CH3 ) CH2CH2- , etc.; and alkylalkylene groups such as alkyltetramethylene groups
- the linear or branched aliphatic hydrocarbon group may or may not have a substituent.
- substituents include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and a carbonyl group.
- Aliphatic hydrocarbon groups containing a ring in the structure examples include cyclic aliphatic hydrocarbon groups (groups in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring) which may contain a substituent containing a heteroatom in the ring structure, groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc.
- Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above.
- the cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
- the cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group.
- the monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
- the cyclic aliphatic hydrocarbon group may or may not have a substituent, which may include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, etc.
- the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
- the alkoxy group as the 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 further preferably a methoxy group or an ethoxy group.
- the halogen atom as the substituent is preferably a fluorine atom. Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.
- some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom.
- the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
- the aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons, and may be monocyclic or polycyclic.
- the aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.
- aromatic ring examples include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- aromatic heterocycle examples include a pyridine ring and a thiophene ring.
- aromatic hydrocarbon group examples include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) has been substituted with an alkylene group (e.g., a group in which one hydrogen atom has been further removed from the aryl group in 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 number of carbon
- the aromatic hydrocarbon group may have a hydrogen atom substituted with a substituent.
- a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent.
- the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
- the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
- the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the cyclic aliphatic hydrocarbon group.
- alkyl group examples include
- the H may be substituted with a substituent such as an alkyl group, an acyl group, etc.
- the substituent alkyl group, acyl group, etc.
- the substituent preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.
- Y 21 is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or ethylene group.
- Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group.
- the alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
- m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as the group represented by the formula -[Y 21 -C( ⁇ O)-O] m" -Y 22 -, a group represented by the formula -Y 21 -C( ⁇ O)-O-Y 22 - is particularly preferred. Of these, a group represented by the formula -(CH 2 ) a' -C( ⁇ O)-O-(CH 2 ) b' - is preferred.
- a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, even 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, even more preferably 1 or 2, and most preferably 1.
- Wa x1 represents an aromatic hydrocarbon group which may have a substituent.
- the aromatic hydrocarbon group in Wa x1 may be a group in which (n ax1 +1) hydrogen atoms have been removed from an aromatic ring which may have a substituent.
- the aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons.
- the aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.
- aromatic ring examples include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom.
- heteroatoms in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom.
- aromatic heterocycle include a pyridine ring and a thiophene ring.
- examples of the aromatic hydrocarbon group in Wa x1 include groups in which (n ax1 +1) hydrogen atoms have been removed from an aromatic compound containing an aromatic ring which may have two or more substituents (e.g., biphenyl, fluorene, etc.).
- Wa x1 is preferably a group in which (n ax1 +1) hydrogen atoms have been removed from benzene, naphthalene, anthracene or biphenyl, more preferably a group in which (n ax1 +1) hydrogen atoms have been removed from benzene or naphthalene, and even more preferably a group in which (n ax1 +1) hydrogen atoms have been removed from benzene.
- the aromatic hydrocarbon group in Wa x1 may or may not have a substituent.
- substituents include an alkyl group, an alkoxy group, a halogen atom, and a halogenated alkyl group.
- alkyl group, alkoxy group, halogen atom, and halogenated alkyl group as the substituent include the same as those exemplified as the substituent of the cyclic aliphatic hydrocarbon group in Ya x1 .
- the substituent is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, further preferably an ethyl group or a methyl group, and particularly preferably a methyl group. It is preferable that the aromatic hydrocarbon group in Wa x1 does not have a substituent.
- n ax1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, still more preferably 1, 2 or 3, and particularly preferably 1 or 2.
- R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
- the structural unit (a10) contained in the component (A1) may be of one type, or may be of two or more types.
- the component (A1) may or may not have the structural unit (a10), although it is preferable for the component (A1) to have the structural unit (a10).
- the proportion of the structural unit (a10) in the component (A1) is preferably 20 to 80 mol %, more preferably 25 to 70 mol %, even more preferably 30 to 60 mol %, and particularly preferably 40 to 60 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
- the component (A1) may have a structural unit (a2) that contains a lactone-containing cyclic group (provided that this does not correspond to the structural unit (a1)).
- the lactone-containing cyclic group of the structural unit (a2) is effective in improving the adhesion of the resist film to the substrate when the component (A1) is used to form a resist film.
- the structural unit (a2) has the effects of, for example, appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development, thereby improving the lithography properties, etc.
- the lactone ring is counted as the first ring, and when there is only a lactone ring, it is called a monocyclic group, and when there is further contained another ring structure, it is called a polycyclic group regardless of the structure.
- the lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
- the lactone-containing cyclic group in the structural unit (a2) is not particularly limited and any suitable group can be used. Specific examples include the groups represented by the following general formulae (a2-r-1) to (a2-r-7).
- R" is a hydrogen atom, an alkyl group or a lactone-containing cyclic group;
- A" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom or a sulfur atom, n' is an integer of 0 to 2, and m' is 0 or 1.
- * represents a bond (the same applies hereinafter).
- the alkyl group in Ra'21 is preferably an alkyl group having 1 to 6 carbon atoms.
- the alkyl group is preferably linear or branched. Specific examples 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. Of these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.
- the alkoxy group in Ra' 21 is preferably an alkoxy group having 1 to 6 carbon atoms.
- the alkoxy group is preferably linear or branched. Specific examples include groups in which the alkyl groups listed above as the alkyl groups in Ra' 21 are linked to an oxygen atom (-O-).
- the halogen atom in Ra'21 is preferably a fluorine atom.
- the halogenated alkyl group in Ra' 21 may be a group in which some or all of the hydrogen atoms in the alkyl group in Ra' 21 have been substituted with the halogen atoms.
- a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.
- R" is both a hydrogen atom, an alkyl group, or a lactone-containing cyclic group.
- the alkyl group for R′′ may be linear, branched, or cyclic, and preferably has 1 to 15 carbon atoms.
- R′′ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and is particularly preferably a methyl group or an ethyl group.
- R" is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms.
- Specific examples include groups in which one or more hydrogen atoms have been removed from a monocycloalkane which may or may not be substituted with a fluorine atom or a fluorinated alkyl group; and groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a bicycloalkane, tricycloalkane, or tetracycloalkane.
- More 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.
- Examples of the lactone-containing cyclic group for R′′ include the same groups as those represented by the general formulae (a2-r-1) to (a2-r-7).
- the hydroxyalkyl group for Ra' 21 preferably has 1 to 6 carbon atoms, and specific examples include the alkyl group for Ra' 21 in which at least one hydrogen atom has been substituted with a hydroxyl group.
- Ra'21 each independently represents a hydrogen atom or a cyano group.
- the alkylene group having 1 to 5 carbon atoms in A" is preferably a straight-chain or branched-chain alkylene group, such as a methylene group, an ethylene group, an n-propylene group or an isopropylene group.
- the alkylene group contains an oxygen atom or a sulfur atom
- specific examples thereof include groups in which -O- or -S- is present at the terminal or between the carbon atoms of the alkylene group, such as -O-CH 2 -, -CH 2 -O-CH 2 -, -S-CH 2 - and -CH 2 -S-CH 2 -.
- A" is preferably an alkylene group having 1 to 5 carbon atoms or -O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.
- the structural unit (a2) is preferably a structural unit derived from an acrylate ester in which the hydrogen atom bonded to the carbon atom at the ⁇ -position may be substituted with a substituent.
- the structural unit (a2) is preferably a structural unit represented by general formula (a2-1) shown below.
- R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- Ya 21 is a single bond or a divalent linking group.
- La 21 is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, and R' represents a hydrogen atom or a methyl group.
- Ra 21 is a lactone-containing cyclic group.
- R is the same as above.
- R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and from the viewpoint of industrial availability, a hydrogen atom or a methyl group is particularly preferred.
- the divalent linking group in Ya 21 is not particularly limited, and suitable examples thereof include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, etc.
- suitable examples thereof include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, etc.
- Examples of the divalent linking group in Ya 21 include the same as the divalent linking group in Ya x1 in the general formula (a10-1) above.
- Ya 21 is preferably a single bond, an ester bond [--C(.dbd.O)--O--], an ether bond (--O--), a linear or branched alkylene group, or a combination thereof.
- Ya 21 is a single bond, and La 21 is --COO-- or --OCO--.
- Ra 21 represents a lactone-containing cyclic group.
- Suitable examples of the lactone-containing cyclic group for Ra 21 include the groups represented by the above-mentioned general formulae (a2-r-1) to (a2-r-7), respectively.
- the structural unit (a2) contained in the component (A1) may be of one type, or may be of two or more types.
- the component (A1) may or may not have the structural unit (a2).
- the proportion of the structural unit (a2) is preferably 1 to 20 mol %, more preferably 1 to 15 mol %, and even more preferably 1 to 10 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
- the proportion of the structural unit (a2) is at least as large as the preferable lower limit, the effects achieved by including the structural unit (a2) can be fully obtained due to the effects described above.
- the proportion of the structural unit (a2) is no more than the upper limit, a balance with other structural units can be achieved, and various lithography properties become favorable.
- Structural unit (a5) is a structural unit that generates an acid upon exposure, and a known structural unit can be used. By including the structural unit (a5), the acid generated upon exposure tends to be distributed uniformly within the resist film. Suitable examples of the structural unit (a5) include structural units represented by general formula (a5-1) shown below.
- R m is an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogen atom, or a hydrogen atom.
- La 1 is a divalent linking group or a single bond.
- Ra 050 is a divalent hydrocarbon group which may have a substituent.
- n a5 is an integer of 0 to 2.
- La 0 is a divalent linking group.
- Ya 0 is a divalent linking group which may have a hetero atom, or a single bond.
- Ra 051 and Ra 052 are each independently a hydrogen atom, a fluorine atom, or a fluorinated alkyl group.
- n0 is an integer of 1 to 4.
- m is an integer of 1 or more, and M' m+ is an m-valent onium cation.
- R m represents an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogen atom or a hydrogen atom.
- the alkyl group having 1 to 5 carbon atoms for R m is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, 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 having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.
- a fluorine atom is particularly preferred.
- R m is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms, and is most preferably a hydrogen atom or a methyl group in terms of industrial availability.
- La1 is a divalent linking group or a single bond.
- the divalent linking group for La 1 is not particularly limited, and preferred examples thereof include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom, which are the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom exemplified as the divalent linking group for Ya x1 above, respectively.
- Ra 050 represents a divalent hydrocarbon group which may have a substituent.
- the divalent hydrocarbon group for Ra 050 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
- the aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity.
- the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
- Examples of the aliphatic hydrocarbon group include linear or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups containing a ring in the structure.
- the straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.
- a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
- the branched aliphatic hydrocarbon group preferably contains 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
- a branched alkylene group is preferable, and specific examples thereof include 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- , -CH( CH2CH3 ) CH2- , and -C ( CH2CH3 ) 2 - CH2- ; alkyltrimethylene groups such as -CH( CH3 )-
- the linear or branched aliphatic hydrocarbon group may or may not have a substituent.
- substituents include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and a carbonyl group.
- Aliphatic hydrocarbon groups containing a ring in the structure examples include cyclic aliphatic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) which may contain a substituent containing a heteroatom in the ring structure, groups in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, groups in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc.
- Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above.
- the cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
- the cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group.
- the monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
- the cyclic aliphatic hydrocarbon group may or may not have a substituent, which may include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, etc.
- the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
- the alkoxy group as the 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.
- the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.
- halogenated alkyl group examples include groups in which some or all of the hydrogen atoms of the alkyl group are substituted with the halogen atoms.
- some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom.
- the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
- the aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 ⁇ electrons, and may be monocyclic or polycyclic.
- the number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituent.
- aromatic ring examples include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- aromatic heterocycle include a pyridine ring and a thiophene ring.
- aromatic hydrocarbon group examples include a group (arylene group or heteroarylene group) in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle; a group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group (aryl group or heteroaryl group) in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (e.g., a group in which one hydrogen atom has been further removed from the aryl group in 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 number of carbon
- the aromatic hydrocarbon group may have a hydrogen atom substituted with a substituent.
- a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent.
- the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group.
- the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
- the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the cyclic aliphatic hydrocarbon group.
- n a5 is an integer from 0 to 2.
- Ra 050 is preferably an aliphatic hydrocarbon group containing a ring in its structure, more preferably a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom in the ring structure, and further preferably an alicyclic hydrocarbon group which is a polycyclic group or a monocyclic group and may have a substituent.
- Ra 050 is preferably an aromatic hydrocarbon group.
- the two Ra 050 may each be an alicyclic hydrocarbon group which may have a substituent, or each may be an aromatic hydrocarbon group, or may be a combination of an alicyclic hydrocarbon group and an aromatic hydrocarbon group which may have a substituent.
- La 0 is a divalent linking group.
- a sulfonyl group (-SO 2 -) may be further linked to this combination.
- Examples of such divalent linking groups include linking groups represented by the following general formulae (L-al-1) to (L-al-8), respectively.
- L-al-1 to (L-al-8) it is V' 101 in the following general formulae (L-al-1) to (L-al-8) that bonds to Ra 050 in the above formula (a5-1).
- V' 101 is a single bond or an alkylene group having 1 to 5 carbon atoms
- V' 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.
- the divalent saturated hydrocarbon group for V' 102 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.
- the alkylene group in V'101 and V'102 may be a linear alkylene group or a branched alkylene group, with a linear alkylene group being preferred.
- Specific examples of the alkylene group in V' 101 and V' 102 include a methylene group [-CH 2 -]; alkylmethylene groups such as -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, and -C(CH 2 CH 3 ) 2 -; an ethylene group [-CH 2 CH 2 -]; alkylethylene groups such as -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, and -CH(CH 2 CH 3 )CH 2 -; a trim
- some of the methylene groups in the alkylene group in V'101 or V'102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms.
- the aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group) of Ra'3 in formula (a1-r-1), and more preferably a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group.
- La 0 is preferably a divalent linking group containing an ester bond or a divalent linking group containing an ether bond, more preferably a linking group represented by each of the above formulas (L-al-1) to (L-al-5) and (L-al-8), and further preferably a linking group represented by (L-al-3) or (L-al-8).
- Ya 0 is a divalent linking group which may have a heteroatom, or a single bond.
- the divalent linking group for Ya 0 is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
- the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom for Ya 0 are the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom exemplified as the divalent linking group for Ya x1 above.
- Ya 0 is preferably a linear or branched alkylene group or a single bond, and more preferably a single bond.
- Ra 051 and Ra 052 each independently represent a hydrogen atom, a fluorine atom or a fluorinated alkyl group.
- the fluorinated alkyl group in Ra 051 and Ra 052 is preferably a linear or branched fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a trifluoromethyl group.
- n0 is an integer from 1 to 4, preferably 1, 2 or 3.
- M'm + represents an onium cation having a valence of m.
- M'm+ is preferably a sulfonium cation or an iodonium cation.
- m is an integer of 1 or more.
- Preferred cationic moieties include organic cations represented by the following general formulas (ca-1) to (ca-3).
- R 201 to R 207 each independently represent an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent.
- R 201 to R 203 and R 206 to R 207 may be bonded to each other to form a ring together with the sulfur atom in the formula.
- R 208 to R 209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an -SO 2 - containing cyclic group which may have a substituent.
- the aryl group for R 201 to R 207 can be an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group or a naphthyl group is preferable.
- the alkyl group for R 201 to R 207 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
- the alkenyl group for R 201 to R 207 preferably has 2 to 10 carbon atoms.
- R 201 to R 207 and R 210 may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following general formulas (ca-r-1) to (ca-r-7), respectively.
- R'201 each independently represents a hydrogen atom, a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent.
- the cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
- the aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity.
- the aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.
- the aromatic hydrocarbon group in R' 201 is a hydrocarbon group having an aromatic ring.
- the aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, even more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. However, this number of carbon atoms does not include the number of carbon atoms in the substituent.
- Specific examples of the aromatic ring contained in the aromatic hydrocarbon group in R'201 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which some of the carbon atoms constituting these aromatic rings are substituted with heteroatoms.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- Specific examples of the aromatic hydrocarbon group for R'201 include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.).
- the alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon
- the cyclic aliphatic hydrocarbon group for R'201 includes an aliphatic hydrocarbon group containing a ring in the structure.
- Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group.
- the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
- the alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.
- the monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms.
- the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.
- the cyclic aliphatic hydrocarbon group for R'201 is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, particularly preferably an adamantyl group or a norbornyl group, and most preferably an adamantyl group.
- the linear or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
- a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], etc.
- a branched alkylene group is preferable, and specific examples thereof include 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- , -CH( CH2CH3 ) CH2- , and -C ( CH2CH3 ) 2 - CH2- ; alkyltrimethylene groups such as -CH( CH3 ) CH2CH2CH2- , -CH2CH ( CH3 ) CH2CH2- , etc.; and alkylalkylene groups such as alkyltetramethylene groups
- the cyclic hydrocarbon group in R'201 may contain a heteroatom, such as a heterocycle.
- a heteroatom such as a heterocycle.
- Specific examples include the lactone-containing cyclic groups represented by the above general formulae (a2-r-1) to (a2-r-7), the -SO2 -containing cyclic groups represented by the following general formulae (b5-r-1) to (b5-r-4), and other heterocyclic groups represented by the following chemical formulae (r-hr-1) to (r-hr-16).
- * represents a bond bonded to Y101 in formula (b-1).
- R is a hydrogen atom, an alkyl group, a lactone-containing cyclic group or an -SO 2 - containing cyclic group;
- B" is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, and n' is an integer of 0 to 2. * represents a bond.
- B" represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom.
- B" is preferably an alkylene group having 1 to 5 carbon atoms or --O--, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably a methylene group.
- Examples of the substituent in the cyclic group of R'201 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
- the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
- the alkoxy group as 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.
- a fluorine atom is preferred.
- halogenated alkyl group as a substituent examples include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms.
- the carbonyl group as a substituent is a group that substitutes a methylene group (-CH 2 -) constituting a cyclic hydrocarbon group.
- a chain alkyl group which may have a substituent may be either linear or branched.
- the linear alkyl group preferably has 1 to 20 carbon atoms, more preferably has 1 to 15 carbon atoms, and most preferably has 1 to 10 carbon atoms.
- the branched alkyl group preferably has 3 to 20 carbon atoms, more preferably has 3 to 15 carbon atoms, and most preferably has 3 to 10 carbon atoms.
- 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.
- a chain alkenyl group which may have a substituent may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, even more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms.
- Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups.
- Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.
- Examples of the substituent in the chain alkyl or alkenyl group of R'201 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic groups in R'201 described above.
- the optionally substituted cyclic group, optionally substituted chain alkyl group, or optionally substituted chain alkenyl group for R'201 is as described above, and examples of the optionally substituted cyclic group or optionally substituted chain alkyl group include the same as the acid dissociable group represented by formula (a1-r-2) above.
- R'201 is preferably a cyclic group which may have a substituent, and more preferably a cyclic hydrocarbon group which may have a substituent. More specifically, for example, a phenyl group, a naphthyl group, a group in which one or more hydrogen atoms have been removed from a polycycloalkane, a lactone-containing cyclic group represented by each of the general formulae (a2-r-1) to (a2-r-7), or an -SO2- containing cyclic group represented by each of the general formulae (b5-r-1) to (b5-r-4) is preferred.
- R 201 to R 203 and R 206 to R 207 when bonded to each other to form a ring together with the sulfur atom in the formula, they may be bonded via a heteroatom such as a sulfur atom, an oxygen atom or a nitrogen atom, or a functional group such as a carbonyl group, -SO-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )- (wherein R N is an alkyl group having 1 to 5 carbon atoms).
- a heteroatom such as a sulfur atom, an oxygen atom or a nitrogen atom
- a functional group such as a carbonyl group, -SO-, -SO 2 -, -SO 3 -, -COO-, -CONH- or -N(R N )- (wherein R N is an alkyl group having 1 to 5 carbon atoms).
- one ring containing the sulfur atom in the ring skeleton in the formula is preferably a 3- to 10-membered ring including the sulfur atom, and particularly preferably a 5- to 7-membered ring.
- the ring formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thioxanthone ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.
- R 208 to R 209 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they represent an alkyl group, they may be bonded to each other to form a ring.
- R 210 is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an --SO 2 -- containing cyclic group which may have a substituent.
- the aryl group for R 210 includes an unsubstituted aryl group having 6 to 20 carbon atoms, and is preferably a phenyl group or a naphthyl group.
- the alkyl group for R 210 is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
- the alkenyl group for R 210 preferably has 2 to 10 carbon atoms.
- a "-SO 2 -containing polycyclic group” is preferable, and a group represented by the above general formula (b5-r-1) is more preferable.
- Suitable cations represented by the formula (ca-1) include the cations represented by the following chemical formulas.
- g1, g2, and g3 each represent a repeating number, where g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 0 to 20.
- R′′ 201 is a hydrogen atom or a substituent, and the substituent is the same as those exemplified as the substituents that may be possessed by R 201 to R 207 and R 210 to R 212. ]
- Suitable cations represented by the formula (ca-2) include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, etc.
- Suitable cations represented by the formula (ca-3) include the cations represented by the following formulas (ca-3-1) to (ca-3-6).
- the cation moiety ((M' m+ ) 1/m ) in the formula (a5-1) is preferably a sulfonium cation, more preferably a cation represented by each of the formulas (ca-1) to (ca-3), still more preferably a cation represented by the formula (ca-1), and particularly preferably a cation represented by each of the formulas (ca-1-1) to (ca-1-83).
- R ⁇ represents a hydrogen atom, a methyl group or a trifluoromethyl group
- m and M′ m+ are the same as m and M′ m+ in the above general formula (a5-1).
- the structural unit (a5) contained in the component (A1) may be of one type, or two or more types.
- the proportion of the structural unit (a5) in the component (A1) is preferably 5 to 25 mol %, more preferably 10 to 20 mol %, and even more preferably 12 to 20 mol %, based on the total (100 mol %) of all structural units constituting the component (A1).
- the proportion of the structural unit (a5) is at least the lower limit of the above-mentioned preferred range, it becomes easier to achieve even higher sensitivity and improved resolution, while when the proportion is at most the upper limit of the above-mentioned preferred range, it becomes easier to achieve a balance with other structural units.
- Structural unit (a8) The structural unit (a8) is a structural unit derived from a compound represented by general formula (a8-1) shown below.
- W2 is a polymerizable group-containing group.
- Yax2 is a single bond or a (n ax2 +1)-valent linking group.
- Yax2 and W2 may form a condensed ring.
- R1 is a fluorinated alkyl group having 1 to 12 carbon atoms.
- R2 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom or a hydrogen atom.
- R2 and Yax2 may be bonded to each other to form a ring structure.
- n ax2 is an integer of 1 to 3.
- the "polymerizable group" in the polymerizable group-containing group of W2 is a group that enables a compound having a polymerizable group to be polymerized by radical polymerization or the like, and is, for example, a group that contains a multiple bond between carbon atoms, such as an ethylenic double bond.
- the polymerizable group-containing group may be a group composed only of a polymerizable group, or may be a group composed of a polymerizable group and a group other than the polymerizable group.
- the group other than the polymerizable group include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.
- R X11 , R X12 and R X13 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, and Ya x0 represents a single bond or a divalent linking group.
- Examples of the fused ring formed by Ya x2 and W2 include a fused ring formed by the polymerizable group at the W2 site and Ya x2 , and a fused ring formed by Ya x2 and a group other than the polymerizable group at the W2 site.
- the fused ring formed by Ya x2 and W 2 may have a substituent.
- R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
- the structural unit (a8) is preferably at least one selected from the group consisting of structural units represented by the chemical formulas (a8-1-01) to (a8-1-04), (a8-1-06), (a8-1-08), (a8-1-09), and (a8-1-10), and more preferably at least one selected from the group consisting of structural units represented by the chemical formulas (a8-1-01) to (a8-1-04), and (a8-1-09).
- the structural unit (a8) contained in the component (A1) may be of one type, or may be of two or more types.
- the component (A1) may or may not have the structural unit (a8).
- the amount of the structural unit (a8) in the component (A1) relative to the total amount (100 mol %) of all structural units constituting the component (A1), is preferably 0 to 50 mol %, and more preferably 0 to 30 mol %.
- the resist composition may contain one type of component (A1) alone or two or more types in combination.
- Examples of the (A1) component include polymeric compounds that contain a repeating structure of the structural unit (a1) and the structural unit (a10).
- the component (A1) can be produced by dissolving monomers from which each structural unit is derived in a polymerization solvent, and then adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601), and polymerizing the resulting mixture.
- a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601)
- AIBN azobisisobutyronitrile
- V-601 dimethyl azobisisobutyrate
- the component (A1) can be produced by dissolving a monomer that derives the structural unit (a1) and a monomer that derives an arbitrary structural unit (for example, a monomer that derives the structural unit (a10, etc.) in a polymerization solvent, adding the above-mentioned radical polymerization initiator to the solution to polymerize, and
- a chain transfer agent such as HS-CH 2 -CH 2 -CH 2 -C(CF 3 ) 2 -OH may be used in combination to introduce a -C(CF 3 ) 2 -OH group to the end.
- a copolymer having a hydroxyalkyl group in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms in this way is effective in reducing development defects and LER (line edge roughness: non-uniform unevenness of the line sidewalls).
- the weight average molecular weight (Mw) of the component (A1) (based on polystyrene equivalent by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and even more preferably 5,000 to 30,000.
- Mw of the component (A1) is no more than the preferred upper limit of this range, the compound has sufficient solubility in a resist solvent for use as a resist, and when it is no less than the preferred lower limit of this range, the compound has good dry etching resistance and good cross-sectional shape of the resist pattern.
- the dispersity (Mw/Mn) of the component (A1) is not particularly limited, but is preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0, and particularly preferably from 1.0 to 2.0, where Mn represents the number average molecular weight.
- the resist composition of this embodiment may also use, as the component (A), a base component (A2) (hereafter referred to as the component (A2)) that does not fall under the category of the component (A1) above and whose solubility in a developer changes under the action of an acid.
- a base component (A2) hereafter referred to as the component (A2)
- the component (A2) may be any compound selected from the many compounds conventionally known as base components for chemically amplified resist compositions.
- the component (A2) may be a polymeric compound or a low molecular weight compound, and may be a combination of two or more of these.
- the proportion of component (A1) in component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, and even more preferably 75% by mass or more, and may be 100% by mass, based on the total mass of component (A). If the proportion is 25% by mass or more, a resist pattern that is excellent in various lithography properties such as high sensitivity, resolution, and improved roughness is easily formed.
- the content of component (A) in the resist composition of this embodiment may be adjusted according to the thickness of the resist film to be formed, etc.
- the resist composition of this embodiment preferably further contains an acid generator component (B) that generates an acid upon exposure.
- an acid generator component (B) that generates an acid upon exposure.
- Such acid generators include onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators such as bisalkyl- or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators.
- onium salt-based acid generators such as iodonium salts and sulfonium salts
- oxime sulfonate-based acid generators such as bisalkyl- or bisarylsulfonyl diazomethanes and poly(bissulfonyl) diazomethanes
- nitrobenzylsulfonate-based acid generators iminosulfonate-based acid generators
- onium salt acid generators examples include a compound represented by the following general formula (b-1) (hereinafter also referred to as “component (b-1)”), a compound represented by general formula (b-2) (hereinafter also referred to as “component (b-2)”), or a compound represented by general formula (b-3) (hereinafter also referred to as “component (b-3)”).
- Onium salt acid generators include, for example, a compound represented by the following general formula (b-1) (hereinafter also referred to as “component (b-1)”), a compound represented by general formula (b-2) (hereinafter also referred to as “component (b-2)”), or a compound represented by general formula (b-3) (hereinafter also referred to as “component (b-3)”).
- component (b-1) a compound represented by the following general formula (b-1)
- component (b-2) hereinafter also referred to as “component (b-2)
- component (b-3) hereinafter also referred to as “component (b-3)
- R 101 and R 104 to R 108 are each independently a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.
- R 104 and R 105 may be bonded to each other to form a ring structure.
- R 102 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom.
- Y 101 is a divalent linking group containing an oxygen atom or a single bond.
- V 101 to V 103 are each independently a single bond, an alkylene group, or a fluorinated alkylene group. However, Y 101 and V 101 are not simultaneously single bonds.
- L 101 to L 102 are each independently a single bond or an oxygen atom.
- L 103 to L 105 are each independently a single bond, -CO-, or -SO 2 -.
- m is an integer of 1 or more, and M'm+ is an onium cation having a valence of m.
- R 101 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.
- the cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.
- An aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity.
- the aliphatic hydrocarbon group is preferably saturated.
- the aromatic hydrocarbon group for R 101 is a hydrocarbon group having an aromatic ring.
- the number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituent.
- Specific examples of the aromatic ring contained in the aromatic hydrocarbon group of R 101 include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which a part of the carbon atoms constituting these aromatic rings are substituted with heteroatoms, etc.
- heteroatom in the aromatic heterocycle examples include an oxygen atom, a sulfur atom, and a nitrogen atom.
- Specific examples of the aromatic hydrocarbon group for R 101 include a group in which one hydrogen atom has been removed from the aromatic ring (aryl group: for example, a phenyl group, a naphthyl group, etc.), a group in which one hydrogen atom of the aromatic ring has been substituted with an alkylene group (for example, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, etc.), etc.
- the number of carbon atoms in the alkylene group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
- the cyclic aliphatic hydrocarbon group for R 101 includes an aliphatic hydrocarbon group containing a ring in the structure.
- Examples of the aliphatic hydrocarbon group containing a ring in its structure include alicyclic hydrocarbon groups (groups in which one hydrogen atom has been removed from an aliphatic hydrocarbon ring), groups in which an alicyclic hydrocarbon group is bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which an alicyclic hydrocarbon group is present in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group.
- the alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
- the alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group.
- the monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms.
- the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.
- the cyclic aliphatic hydrocarbon group for R 101 is preferably a group in which one or more hydrogen atoms have been removed from a monocycloalkane or polycycloalkane, more preferably a group in which one hydrogen atom has been removed from a polycycloalkane, further preferably an adamantyl group or a norbornyl group, and particularly preferably an adamantyl group.
- the linear aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3.
- linear alkylene groups are preferred, and specific examples thereof include a methylene group [-CH 2 -], an ethylene group [-(CH 2 ) 2 -], a trimethylene group [-(CH 2 ) 3 -], a tetramethylene group [-(CH 2 ) 4 -], a pentamethylene group [-(CH 2 ) 5 -], and the like.
- the branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
- a branched alkylene group is preferable, and specific examples thereof include 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- , -CH( CH2CH3 ) CH2- , and -C ( CH2CH3 ) 2 - CH2- ; alkyltrimethylene groups such as -CH( CH3 ) CH2CH2CH2- , -CH2CH ( CH3 ) CH2CH2- , etc.; and alkylalkylene groups such as alkyltetramethylene groups
- the cyclic hydrocarbon group in R 101 may contain a heteroatom, such as a heterocycle.
- a heteroatom such as a heterocycle.
- Specific examples include the lactone-containing cyclic groups represented by the general formulae (a2-r-1) to (a2-r-7) above, the —SO 2 —-containing cyclic groups represented by the general formulae (b5-r-1) to (b5-r-4) above, and the heterocyclic groups represented by the chemical formulae (r-hr-1) to (r-hr-16) above.
- Examples of the substituent in the cyclic group of R 101 include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
- the alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms.
- the alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
- halogen atom as a substituent, a fluorine atom, a bromine atom or an iodine atom is preferred.
- halogenated alkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms.
- the carbonyl group as a substituent is a group that substitutes a methylene group (-CH 2 -) constituting a cyclic hydrocarbon group.
- the cyclic hydrocarbon group in R 101 may be a fused ring group containing a fused ring in which an aliphatic hydrocarbon ring and an aromatic ring are fused.
- the fused ring include a polycycloalkane having a polycyclic skeleton of a bridged ring system to which one or more aromatic rings are fused.
- Specific examples of the bridged ring polycycloalkane include bicycloalkanes such as bicyclo[2.2.1]heptane (norbornane) and bicyclo[2.2.2]octane.
- the fused ring group is preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicycloalkane, and more preferably a group containing a fused ring in which two or three aromatic rings are fused to a bicyclo[2.2.2]octane.
- Specific examples of the fused ring group in R 101 include those represented by the following formulae (r-br-1) to (r-br-2). In the formula, * represents a bond bonded to Y 101 in formula (b-1).
- Examples of the substituent that the fused cyclic group for R 101 may have include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group.
- Examples of the alkyl group, alkoxy group, halogen atom and halogenated alkyl group as the substituent of the condensed cyclic group include the same as those exemplified as the substituent of the cyclic group in R 101 above.
- aromatic hydrocarbon group as the substituent of the fused ring group
- aryl group for example, a phenyl group, a naphthyl group, etc.
- an alkylene group for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.
- heterocyclic groups represented by the above formulas (r-hr-1) to (r-hr-6), respectively.
- Examples of the alicyclic hydrocarbon group as a substituent of the fused cyclic group include groups in which one hydrogen atom has been removed from a monocycloalkane, such as cyclopentane or cyclohexane; groups in which one hydrogen atom has been removed from a polycycloalkane, such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane; lactone-containing cyclic groups represented by each of the general formulae (a2-r-1) to (a2-r-7); —SO 2 -containing cyclic groups represented by each of the general formulae (b5-r-1) to (b5-r-4); and heterocyclic groups represented by each of the formulae (r-hr-7) to (r-hr-16).
- a monocycloalkane such as cyclopentane or cyclohexane
- a chain alkyl group which may have a substituent may be either linear or branched.
- the linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms.
- the branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms.
- 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.
- a chain alkenyl group which may have a substituent may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and particularly preferably 3.
- Examples of linear alkenyl groups include vinyl groups, propenyl groups (allyl groups), and butynyl groups.
- Examples of branched alkenyl groups include 1-methylvinyl groups, 2-methylvinyl groups, 1-methylpropenyl groups, and 2-methylpropenyl groups. Of the above chain alkenyl groups, linear alkenyl groups are preferred, vinyl groups and propenyl groups are more preferred, and vinyl groups are particularly preferred.
- Examples of the substituent in the chain alkyl or alkenyl group of R 101 include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the cyclic groups in R 101 above.
- Y 101 is a single bond or a divalent linking group containing an oxygen atom.
- Y 101 may contain an atom other than an oxygen atom.
- the atom other than an oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, and a nitrogen atom.
- the divalent linking group containing an oxygen atom include linking groups represented by the following general formulae (y-al-1) to (y-al-7), respectively.
- general formulae (y-al-1) to (y-al-7) what is bonded to R 101 in the above formula (b-1) is V' 101 in the following general formulae (y-al-1) to (y-al-7).
- V' 101 is a single bond or an alkylene group having 1 to 5 carbon atoms
- V' 102 is a divalent saturated hydrocarbon group having 1 to 30 carbon atoms.
- the divalent saturated hydrocarbon group for V' 102 is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.
- the alkylene group in V'101 and V'102 may be a linear alkylene group or a branched alkylene group, with a linear alkylene group being preferred.
- Specific examples of the alkylene group in V' 101 and V' 102 include a methylene group [-CH 2 -]; alkylmethylene groups such as -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C(CH 3 ) 2 -, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, and -C(CH 2 CH 3 ) 2 -; an ethylene group [-CH 2 CH 2 -]; alkylethylene groups such as -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )-, -C(CH 3 ) 2 CH 2 -, and -CH(CH 2 CH 3 )CH 2 -; a trim
- some of the methylene groups in the alkylene group in V'101 or V'102 may be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms.
- the aliphatic cyclic group is preferably a divalent group obtained by further removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group) of Ra'3 in formula (a1-r-1), and more preferably a cyclohexylene group, a 1,5-adamantylene group or a 2,6-adamantylene group.
- V 101 is a single bond, an alkylene group or a fluorinated alkylene group. Of these, V 101 is preferably a single bond or a linear fluorinated alkylene group having 1 to 4 carbon atoms.
- R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms.
- R 102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.
- anion moiety represented by formula (b-1) include, for example, when Y 101 is a single bond, fluorinated alkylsulfonate anions such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion; and, when Y 101 is a divalent linking group containing an oxygen atom, anions represented by any of the following formulas (an-1) to (an-3) are included.
- R" 101 is an aliphatic cyclic group which may have a substituent, a monovalent heterocyclic group represented by each of the above chemical formulas (r-hr-1) to (r-hr-6), a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), a chain-like alkyl group which may have a substituent, or an aromatic cyclic group which may have a substituent.
- R" 102 is an aliphatic cyclic group which may have a substituent, a fused cyclic group represented by the above formula (r-br-1) or (r-br-2), a lactone-containing cyclic group represented by each of the above general formulas (a2-r-1), (a2-r-3) to (a2-r-7), or an -SO 2 - containing cyclic group represented by each of the above general formulas (b5-r-1) to (b5-r-4).
- R" 103 is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like alkenyl group which may have a substituent.
- V" 101 is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms.
- R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms.
- Each v" is independently an integer of 0 to 3
- each q" is independently an integer of 0 to 20, and n" is 0 or 1.
- the aliphatic cyclic groups which may have a substituent of R" 101 , R" 102 and R" 103 are preferably the groups exemplified as the cyclic aliphatic hydrocarbon group in R 101 in formula (b-1) above.
- substituents include the same as the substituents which may substitute the cyclic aliphatic hydrocarbon group in R 101 in formula (b-1) above.
- the aromatic cyclic group which may have a substituent in R" 101 and R" 103 is preferably a group exemplified as the aromatic hydrocarbon group in the cyclic hydrocarbon group in R101 in the above formula (b-1).
- substituents include the same as the substituent which may substitute the aromatic hydrocarbon group in R101 in the above formula (b-1).
- the chain alkyl group which may have a substituent in R′′ 101 is preferably a group exemplified as the chain alkyl group in R 101 in the above formula (b-1).
- the chain alkenyl group which may have a substituent in R′′ 103 is preferably a group exemplified as the chain alkenyl group in R 101 in the above formula (b-1).
- R 104 and R 105 each independently represent a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and examples of these include the same as R 101 in formula (b-1). However, R 104 and R 105 may be bonded to each other to form a ring. R 104 and R 105 are preferably a chain alkyl group which may have a substituent, and more preferably a linear or branched alkyl group, or a linear or branched fluorinated alkyl group.
- the number of carbon atoms in the chain-like alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3.
- the number of carbon atoms in the chain-like alkyl group of R 104 and R 105 is preferably as small as possible within the above range of the number of carbon atoms, for reasons such as good solubility in a resist solvent.
- the more hydrogen atoms substituted with fluorine atoms the stronger the acid strength becomes, and the more the transparency to high-energy light and electron beams of 250 nm or less is improved, which is preferable.
- the ratio of fluorine atoms in the chain-like alkyl group i.e., the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
- V 102 and V 103 each independently represent a single bond, an alkylene group, or a fluorinated alkylene group, and examples of V 101 in formula (b-1) include the same as those described above.
- L 101 and L 102 each independently represent a single bond or an oxygen atom.
- R to R each independently represent a cyclic group which may have a substituent , a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent, and examples of these include the same as R 101 in formula (b-1).
- L 103 to L 105 each independently represent a single bond, —CO— or —SO 2 —.
- the anion portion of component (B) is preferably the anion in component (b-1), and more preferably the anion represented by formula (an-1).
- M'm+ represents an m-valent onium cation. Among these, sulfonium cation and iodonium cation are preferred. m is an integer of 1 or more. M' m+ in the above formulae (b-1), (b-2) and (b-3) is the same as M' m+ in the above formula (a5-1).
- the cation portion of component (B) is preferably a sulfonium cation, more preferably the cations represented by the formulas (ca-1) to (ca-3), still more preferably the cation represented by the formula (ca-1), and particularly preferably the cations represented by the formulas (ca-1-1) to (ca-1-83).
- the component (B) may use either a single type, or a combination of two or more types.
- the amount of the component (B) is preferably less than 50 parts by mass, and more preferably 10 to 40 parts by mass, per 100 parts by mass of the component (A).
- the content of the (B) component in the resist composition is preferably less than 50 parts by mass, more preferably 0 to 40 parts by mass, and even more preferably 0 to 30 parts by mass, per 100 parts by mass of the (A) component.
- the resist composition of this embodiment may contain, in addition to the component (A), a base component (component (D)) that traps acid generated upon exposure (i.e., controls the diffusion of acid).
- the component (D) acts as a quencher (acid diffusion controller) that traps acid generated in the resist composition upon exposure.
- Examples of the component (D) include a photodegradable base (D1) (hereinafter referred to as "component (D1)”) that decomposes upon exposure to light and loses its acid diffusion controllability, and a nitrogen-containing organic compound (D2) (hereinafter referred to as "component (D2)”) that does not fall under the category of component (D1).
- the photodegradable base (component (D1)) is preferred because it is likely to enhance all of the properties of increasing sensitivity, reducing roughness, and suppressing the occurrence of coating defects.
- component (D1) there are no particular limitations on the component (D1) so long as it decomposes upon exposure to light and loses its acid diffusion controllability, and the component (D1) is preferably one or more compounds selected from the group consisting of a compound represented by the following general formula (d1-1) (hereinafter referred to as "component (d1-1)”), a compound represented by the following general formula (d1-2) (hereinafter referred to as “component (d1-2)”), and a compound represented by the following general formula (d1-3) (hereinafter referred to as “component (d1-3)”):
- component (d1-1) to (d1-3) do not act as quenchers in the exposed areas of the resist film because they decompose and lose their acid diffusion control ability (basicity), but act as quenchers in the unexposed areas of the resist film.
- Rd 1 to Rd 4 are a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent.
- Rd 2 in formula (d1-2) a fluorine atom is not bonded to the carbon atom adjacent to the S atom.
- Yd 1 is a single bond or a divalent linking group.
- m is an integer of 1 or more, and each M m+ is independently an m-valent organic cation.
- Rd 1 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or It is a long chain alkenyl group, and examples thereof include the same as those for R'201 .
- Rd1 is preferably an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain-like group which may have a substituent.
- substituents that these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluorinated alkyl group, and the groups represented by the above general formulas (a2-r-1) to (a2-r-8) is a lactone-containing cyclic group, an ether bond, an ester bond, or a combination thereof.
- the alkylene group is interposed therebetween.
- the substituent is preferably a linking group represented by each of the above formulae (y-al-1) to (y-al-5).
- the aromatic hydrocarbon group, the aliphatic cyclic group, or the chain alkyl group in Rd1 may be, as a substituent, any one of the general formulae (y-al-1) to (y-al-7) shown above.
- Rd 1 in formula (d3-1) has a linking group
- the aromatic hydrocarbon group, the aliphatic cyclic group, or V' 101 in the above general formulae (y-al-1) to (y-al-7) is bonded to a carbon atom constituting a chain alkyl group.
- Suitable examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and a polycyclic structure containing a bicyclooctane skeleton (a polycyclic structure consisting of a bicyclooctane skeleton and another ring structure).
- the aliphatic cyclic group is more preferably a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane.
- the chain alkyl group preferably has 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
- linear alkyl groups such as 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-
- branched alkyl groups include an ethylbutyl group, a 2-ethylbutyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, and a 4-methylpentyl group.
- the chain-like alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent
- the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4.
- the fluorinated alkyl group may contain atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, and nitrogen atoms.
- M m+ represents an m-valent organic cation.
- Suitable examples of the organic cation of M m+ include the same cations as those represented by the general formulas (ca-1) to (ca-3), respectively, more preferably the cation represented by the general formula (ca-1), and even more preferably the cations represented by the general formulas (ca-1-1) to (ca-1-84).
- the component (d1-1) may be used alone or in combination of two or more.
- Rd2 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or It is a long chain alkenyl group, and examples thereof include the same as those for R'201 .
- the carbon atom adjacent to the S atom in Rd2 does not have a fluorine atom bonded thereto (is not substituted with fluorine). This allows the anion of the (d1-2) component to become an appropriately weak acid anion. , the quenching ability of the component (D) is improved.
- Rd2 is preferably a chain alkyl group which may have a substituent, or an aliphatic cyclic group which may have a substituent, and More preferably, it is a group of the formula:
- the chain alkyl group preferably has 1 to 10 carbon atoms, and more preferably has 3 to 10 carbon atoms.
- the aliphatic cyclic group is preferably a group (which may have a substituent) in which one or more hydrogen atoms have been removed from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like; or a group in which one or more hydrogen atoms have been removed from camphor.
- the hydrocarbon group of Rd2 may have a substituent, and examples of the substituent include the same as the substituents that may be possessed by the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in Rd1 of the above formula (d1-1).
- M m+ represents an m-valent organic cation and is the same as M m+ in formula (d1-1).
- the component (d1-2) may be used alone or in combination of two or more.
- Rd3 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or an anion portion which may have a substituent. It is a chain alkenyl group, and examples thereof include the same as those of R'201 , and it is preferably a fluorine atom-containing cyclic group, a chain alkyl group, or a chain alkenyl group. An alkyl group is preferable, and the same fluorinated alkyl group as Rd1 is more preferable.
- Rd4 represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent
- examples of R'201 include the same as those described above.
- an alkyl group, an alkoxy group, an alkenyl group, or a cyclic group, which may have a substituent is preferable.
- the alkyl group in Rd 4 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, etc.
- a portion of the hydrogen atoms of the alkyl group in Rd 4 may be substituted with a hydroxyl group, a cyano group, etc.
- the alkoxy group in Rd 4 is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Of these, a methoxy group and an ethoxy group are preferred.
- the alkenyl group in Rd4 may be the same as the alkenyl group in R'201 , and preferably a vinyl group, a propenyl group (allyl group), a 1-methylpropenyl group, or a 2-methylpropenyl group. These groups may further have an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms as a substituent.
- the cyclic group in Rd 4 may be the same as the cyclic group in R' 201 , and is preferably an alicyclic group in which one or more hydrogen atoms have been removed from a cycloalkane such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane, or an aromatic group such as a phenyl group or naphthyl group.
- a cycloalkane such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane
- an aromatic group such as a phenyl group or naphthyl group.
- Rd 4 is an alicyclic group
- the resist composition dissolves well in an organic solvent, resulting in good lithography properties.
- Yd1 represents a single bond or a divalent linking group.
- the divalent linking group in Yd 1 is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent (an aliphatic hydrocarbon group, an aromatic hydrocarbon group), a divalent linking group containing a hetero atom, etc. These include the same as the divalent hydrocarbon group which may have a substituent and the divalent linking group containing a hetero atom mentioned in the description of the divalent linking group in Ya 21 in the above formula (a2-1).
- Yd1 is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof.
- the alkylene group is more preferably a linear or branched alkylene group, and further preferably a methylene group or an ethylene group.
- M m+ represents an m-valent organic cation and is the same as M m+ in formula (d1-1).
- the component (d1-3) may be used alone or in combination of two or more.
- the component (D1) may be any one of the above components (d1-1) to (d1-3), or a combination of two or more of them.
- the amount of the component (D1) in the resist composition relative to 100 parts by mass of the component (A) is preferably 0.5 to 15 parts by mass, more preferably 1 to 12 parts by mass, and even more preferably 2 to 10 parts by mass.
- the component (D1) preferably contains the component (d1-1) above. Of the entire component (D1), the content of the component (d1-1) is preferably 50 mass% or more, preferably 70 mass% or more, and more preferably 90 mass% or more.
- the component (D1) may consist solely of the compound component (d1-1).
- Production method of component (D1) The method for producing the components (d1-1) and (d1-2) is not particularly limited, and they can be produced by known methods.
- the method for producing the component (d1-3) is not particularly limited, and it can be produced, for example, in the same manner as the method described in US 2012-0149916.
- the component (D) may contain a nitrogen-containing organic compound component (hereinafter referred to as “component (D2)”) that does not fall under the category of the above-mentioned component (D1).
- component (D2) is not particularly limited as long as it acts as an acid diffusion controller and does not fall under the category of component (D1), and any known component may be used.
- aliphatic amines are preferred, and among these, secondary aliphatic amines and tertiary aliphatic amines are more preferred.
- Aliphatic amines are amines that have one or more aliphatic groups, preferably having 1 to 12 carbon atoms.
- aliphatic amines include amines in which at least one of the hydrogen atoms of ammonia NH3 is substituted with an alkyl group or hydroxyalkyl group having 12 or less carbon atoms (alkylamines or alkyl alcohol amines), or cyclic amines.
- alkylamines and alkyl alcohol amines 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-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkyl alcohol amines such as diethanolamine, triethanolamine, diis
- cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom.
- the heterocyclic compounds may be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Specific examples of the aliphatic monocyclic amine include piperidine and piperazine.
- the aliphatic polycyclic amine is preferably one having 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.
- 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, tris[2- ⁇ 2-(2-hydroxyethoxy)ethoxy ⁇ ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred.
- aromatic amine may be used as the component (D2).
- aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, 2,6-di-tert-butylpyridine, and 2,6-di-tert-butylpyridine.
- the component (D2) may be used alone or in combination of two or more types.
- the amount of the component (D2) in the resist composition is typically within the range from 0.01 to 5 parts by mass relative to 100 parts by mass of the component (A). By ensuring that the amount is within this range, the resist pattern shape and the storage stability over time are improved.
- the resist composition of this embodiment may contain, as an optional component, at least one compound (E) selected from the group consisting of organic carboxylic acids, and phosphorus oxoacids and derivatives thereof (hereafter referred to as "component (E)").
- component (E) phosphorus oxoacids and derivatives thereof
- the organic carboxylic acid include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, and among these, salicylic acid is preferred.
- phosphorus oxoacids include phosphoric acid, phosphonic acid, and phosphinic acid, with phosphonic acid being particularly preferred.
- the component (E) may use either a single type, or a combination of two or more types.
- the amount of the component (E) per 100 parts by mass of the component (A) is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass. By ensuring that the amount is within this range, lithography properties are further improved.
- the resist composition of this embodiment contains a fluorine additive component (hereafter referred to as "component (F)”) as a hydrophobic resin.
- Component (F) is used to impart water repellency to the resist film, and when used as a resin separate from component (A), it can improve lithography properties.
- the component (F) contains a fluorine-containing polymeric compound (F0) having a structural unit (f0) derived from a compound represented by the following general formula (f0-1):
- the structural unit (f0) is a structural unit derived from a compound represented by general formula (f0-1) shown below.
- W 1 is a polymerizable group.
- Ar is an aromatic ring.
- Xf is an iodine atom or a substituent containing an iodine atom.
- m1 is an integer of 1 or more as long as the valence allows.
- Lf 01 is a single bond or a linking group having a valence of (n1+1).
- Rf 01 is a fluorinated alkyl group having 1 to 12 carbon atoms.
- Rf 02 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom or a hydrogen atom.
- n1 is an integer of 1 to 3.
- Rf 03 is a substituent other than an iodine atom.
- m2 is an integer of 0 or more as long as the valence allows.
- the “polymerizable group” refers to a group that enables a compound having a polymerizable group to be polymerized by radical polymerization or the like, and refers to a group that contains a multiple bond between carbon atoms, such as an ethylenic double bond.
- the multiple bond in the polymerizable group is cleaved to form the main chain.
- Examples of the polymerizable group in W1 include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a fluorovinyl group, a difluorovinyl group, a trifluorovinyl group, a difluorotrifluoromethylvinyl group, a trifluoroallyl group, a perfluoroallyl group, a trifluoromethylacryloyl group, a nonylfluorobutylacryloyl group, a vinyl ether group, a fluorine-containing vinyl ether group, an allyl ether group, a fluorine-containing allyl ether group, a styryl group, a vinyl naphthyl group, a fluorine-containing styryl group, a fluorine-containing vinyl naphthyl group, a norbornyl group, a fluorine-containing norbornyl group, and a sily
- Suitable examples of the polymerizable group for W 01 include a group represented by C(R x11 ) (R x12 ) ⁇ C(R x13 )-C( ⁇ O)-O-, a group represented by C(R x14 ) (R x15 ) ⁇ C(R x16 )-Ar x11 -C( ⁇ O)-O-, a group represented by C(R x17 ) (R x18 ) ⁇ C(R x19 )-, and a group represented by C(R x20 ) (R x21 ) ⁇ C(R x22 )-C( ⁇ O)-O-C(Rf x11 ) (Rf x12 )-.
- R x11 to R x22 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- Rf x11 and Rf x12 are each independently a fluorinated alkyl group having 1 to 5 carbon atoms.
- the aromatic ring in Ar preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituents.
- Specific examples of the aromatic ring in Ar include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, and aromatic heterocycles in which a part of the carbon atoms constituting these aromatic rings is replaced with a heteroatom.
- the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Among these, a benzene ring is preferred as Ar from the viewpoint of ease of synthesis.
- the iodine-atom-containing substituent in Xf is not particularly limited as long as it is an organic group having an iodine atom, but an organic group containing an aromatic ring having an iodine atom as a substituent is preferred, and a group represented by the following formula (Xf-r-1) is more preferred.
- Ar2 is an aromatic ring.
- m22 is an integer of 1 or more as long as the valence allows.
- Rf 032 is a substituent other than an iodine atom.
- m32 is an integer of 0 or more as long as the valence allows.
- Lf 022 is a divalent linking group. * is a bond bonded to Ar in formula (f0-1).]
- the aromatic ring in Ar2 is the same as the aromatic ring in Ar in the formula (f0-1). Among them, from the viewpoint of ease of synthesis, a benzene ring is preferable as Ar.
- m22 is preferably an integer of 1 to 3, and more preferably 2 or 3.
- examples of the substituent other than the iodine atom in Rf 032 include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a bromine atom, a chlorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms, an amino group, a hydroxy group, a cyano group, and a nitro group.
- m32 is preferably an integer from 0 to 3, more preferably an integer from 0 to 2, even more preferably 0 or 1, and particularly preferably 0. When m32 is an integer of 2 or more, each of the multiple Rf 032 may be the same or different.
- R L 01 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
- m1 is preferably an integer of 1 to 3.
- m1 when Xf is an iodine atom, m1 is preferably an integer of 1 to 3, and more preferably 2 or 3.
- m1 when Xf is a substituent containing an iodine atom, m1 is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
- examples of the substituent other than the iodine atom in Rf 03 include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a bromine atom, a chlorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms, an amino group, a hydroxyl group, a cyano group, and a nitro group.
- m2 is preferably an integer from 0 to 3, more preferably an integer from 0 to 2, even more preferably 0 or 1, and particularly preferably 0.
- the (n1+1)-valent linking group in Lf 01 is not particularly limited, but is preferably an organic group containing a carbonyloxy group, and more preferably a group represented by any of the following general formulae (Lf 01 -01) to (Lf 01 -03).
- *1 is a bond bonded to Ar in the formula (f0-1).
- Lf 11 is a hydrocarbon group which may have a substituent.
- *2 is a bond bonded to -C(Rf 01 )(Rf 02 )(OH) in the formula (f0-1).
- n1 is an integer of 1 to 3.
- the hydrocarbon group in Lf 11 to Lf 13 which may have a substituent may be a linear hydrocarbon group, a branched hydrocarbon group, a cyclic hydrocarbon group, or a combination thereof.
- the group represented by the formula (Lf 01 -01) is preferably a group represented by any one of the following general formulae (Lf 01 -01-1) to (Lf 01 -01-3).
- *1 is a bond bonded to Ar in the formula (f0-1).
- RLf 1 is a linear or branched alkyl group or a cycloalkyl group.
- Z is an aliphatic ring.
- *2 is a bond bonded to -C(Rf 01 )(Rf 02 )(OH) in the formula (f0-1).
- n1 is an integer of 1 to 3.
- the linear or branched alkyl group for RLf 1 is preferably a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 2 to 5 carbon atoms, and more preferably a methyl group or an isobutyl group.
- the aliphatic ring for Z is preferably a norbornene ring or a cyclohexane ring.
- the group represented by the formula (Lf 01 -02) is preferably a group represented by any one of the following general formulae (Lf 01 -02-1) to (Lf 01 -02-3).
- the linear or branched alkyl group for RLf 1 is preferably a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 2 to 5 carbon atoms, and more preferably a methyl group or an isobutyl group.
- the aliphatic ring for Z is preferably a norbornene ring or a cyclohexane ring.
- Lf 13 is preferably a linear alkyl group, more preferably an alkylene group having 1 to 5 carbon atoms, and further preferably a methylene group.
- Rf 01 is a fluorinated alkyl group having 1 to 12 carbon atoms, in which some or all of the hydrogen atoms of an alkyl group having 1 to 12 carbon atoms have been substituted with fluorine atoms.
- the alkyl group may be linear or branched. Specific examples of linear fluorinated alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups in which some or all of the hydrogen atoms have been substituted with fluorine atoms.
- branched fluorinated alkyl groups having 1 to 12 carbon atoms include 1-methylethyl, 1,1-dimethylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups in which some or all of the hydrogen atoms have been substituted with fluorine atoms.
- fluorinated alkyl group having 1 to 12 carbon atoms for Rf 01 among the above, a fluorinated alkyl group having 1 to 5 carbon atoms is more preferable, and specifically, a trifluoromethyl group is particularly preferable.
- examples of the organic group having 1 to 12 carbon atoms which may have a fluorine atom for Rf 02 include monovalent hydrocarbon groups having 1 to 12 carbon atoms which may have a fluorine atom.
- examples of the hydrocarbon group include a linear or branched alkyl group, and a cyclic hydrocarbon group.
- linear alkyl group 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 decyl group, an undecyl group, and a dodecyl group.
- branched alkyl group examples include a 1-methylethyl group, a 1,1-dimethylethyl 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.
- Rf 02 is a cyclic hydrocarbon group
- the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group.
- the monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane.
- the monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
- the aliphatic hydrocarbon group that is a polycyclic group a group in which one hydrogen atom has been removed from a polycycloalkane is preferable, and the polycycloalkane is preferably one having 7 to 12 carbon atoms, and specific examples thereof include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.
- Rf 02 is a cyclic hydrocarbon group that is an aromatic hydrocarbon group
- the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.
- Specific examples of the aromatic hydrocarbon group include groups in which one hydrogen atom has been removed from an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, phenanthrene, biphenyl, and fluorene.
- the organic group having 1 to 12 carbon atoms of Rf 02 may have a substituent other than a fluorine atom.
- substituents include a hydroxy group, a carboxy group, a halogen atom (such as a chlorine atom or a bromine atom), an alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group), and an alkyloxycarbonyl group.
- Rf 02 is preferably a fluorinated alkyl group having 1 to 12 carbon atoms, more preferably a fluorinated alkyl group having 1 to 5 carbon atoms, and further preferably a trifluoromethyl group.
- n1 is preferably 1 or 2, and more preferably 1.
- the structural unit (f0) preferably contains at least one selected from the group consisting of a structural unit (f01) derived from a compound represented by the following general formula (f0-1-1) and a structural unit (f02) derived from a compound represented by the following general formula (f0-1-2).
- W 01 is a polymerizable group.
- Ar is an aromatic ring.
- I is an iodine atom.
- m11 is an integer of 1 or more, as long as the valence allows.
- Lf 011 is a single bond or a linking group having a valence of (n1+1).
- Rf 011 is a fluorinated alkyl group having 1 to 12 carbon atoms.
- Rf 021 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom, or a hydrogen atom.
- n11 is an integer of 1 to 3.
- Rf 03 is a substituent other than an iodine atom.
- m21 is an integer of 0 or more, as long as the valence allows.
- W 02 is a polymerizable group.
- Ar1 and Ar2 are each independently an aromatic ring.
- Rf 031 and Rf 032 are each independently a substituent other than an iodine atom.
- m12 and m32 are each independently an integer of 0 or more, as long as the valence allows.
- I is an iodine atom.
- m22 is an integer of 1 or more, as long as the valence allows.
- Lf 012 is a single bond or a (n1+1)-valent linking group.
- Lf 022 is a divalent linking group.
- Rf 021 is a fluorinated alkyl group having 1 to 12 carbon atoms.
- Rf 022 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom, or a hydrogen atom.
- n21 is an integer of 1 to 3.
- the polymerizable group for W 01 is the same as the polymerizable group for W 1 in the above formula (f0-1).
- W 01 is preferably a group represented by the above formula C(R X11 ) (R X12 ) ⁇ C(R X13 )-C( ⁇ O)-O-, a group represented by the above formula C(R X14 ) (R X15 ) ⁇ C(R X16 )-Ar x11 -C( ⁇ O)-O-, a group represented by the above formula C(R X17 ) (R X18 ) ⁇ C(R X19 )-, or a group represented by the above formula C(R X20 ) (R X21 ) ⁇ C(R X22 )-C( ⁇ O)-O-C(Rf x11 ) (Rf x12 )-, and more preferably a group represented by the above formula C(R X11 ) (R X12 )
- Ar is the same as Ar in the formula (f0-1), and is preferably a benzene ring.
- m11 is preferably an integer of 1 to 3, and more preferably 2 or 3.
- Rf 03 is the same as Rf 03 in the formula (f0-1).
- m21 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 0.
- the (n1+1)-valent linking group in Lf 011 is the same as the (n1+1)-valent linking group in Lf 01 in the formula (f0-1), and is preferably an organic group containing a carbonyloxy group, and more preferably a group represented by any of the general formulae (Lf 01 -01) to (Lf 01 -03).
- the fluorinated alkyl group having 1 to 12 carbon atoms in Rf 011 is the same as the fluorinated alkyl group having 1 to 12 carbon atoms in Rf 01 in the formula (f0-1), preferably a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a trifluoromethyl group.
- the organic group having 1 to 12 carbon atoms which may have a fluorine atom in Rf 021 is the same as the organic group having 1 to 12 carbon atoms which may have a fluorine atom in Rf 02 in the formula (f0-1), and is preferably a fluorinated alkyl group having 1 to 12 carbon atoms, more preferably a fluorinated alkyl group having 1 to 5 carbon atoms, and even more preferably a trifluoromethyl group.
- n11 is preferably 1 or 2, and more preferably 1.
- the aromatic rings in Ar1 and Ar2 are the same as the aromatic rings in Ar in the formula (f0-1), and are preferably a benzene ring.
- the substituents other than iodine atoms in Rf 031 and Rf 032 are the same as the substituents other than iodine atoms in Rf 03 in the formula (f0-1).
- m12 and m32 each independently represent preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 0.
- m22 is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
- the (n1+1)-valent linking group in Lf 021 is the same as the (n1+1)-valent linking group in Lf 01 in the formula (f0-1), and is preferably an organic group containing a carbonyloxy group, and more preferably a group represented by any of the general formulae (Lf 01 -01) to (Lf 01 -03).
- the fluorinated alkyl group having 1 to 12 carbon atoms for Rf 012 is the same as the fluorinated alkyl group having 1 to 12 carbon atoms for Rf 01 in the formula (f0-1), and is preferably a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a trifluoromethyl group.
- the organic group having 1 to 12 carbon atoms which may have a fluorine atom in Rf 022 is the same as the organic group having 1 to 12 carbon atoms which may have a fluorine atom in Rf 02 in the formula (f0-1), and is preferably a fluorinated alkyl group having 1 to 12 carbon atoms, more preferably a fluorinated alkyl group having 1 to 5 carbon atoms, and even more preferably a trifluoromethyl group.
- n21 is preferably 1 or 2, and more preferably 1.
- R ⁇ represents a hydrogen atom, a methyl group, or a trifluoromethyl group.
- the structural unit (f0) contained in the component (F0) may be of one type, or two or more types.
- the proportion of the structural unit (f0) in the component (F0) is preferably 40 to 90 mol%, more preferably 45 to 85 mol%, and even more preferably 50 to 75 mol%, based on the total (100 mol%) of all structural units constituting the component (F0).
- the component (A1) may contain other structural units, in addition to the structural unit (a1) described above, as necessary.
- Examples of other structural units include a structural unit (f1) containing an acid-decomposable group whose polarity increases by the action of acid; a structural unit (f2) containing a lactone-containing cyclic group; and the structural unit (f3) represented by the general formula (a10-1) above.
- the structural unit (f1) is a structural unit that contains an acid-decomposable group whose polarity increases when acted on by an acid, and is the same as the structural unit (a1) within the component (A1) described above.
- the structural unit (f1) is preferably a structural unit represented by general formula (a1-1), (a1-2) or (a1-3) above.
- the structural unit (f1) contained in the component (F0) may be of one type or of two or more types.
- the component (F0) may or may not contain the structural unit (f1), but preferably contains the structural unit (f1).
- the proportion of the structural unit (f1) in the component (F0) is preferably 1 to 60 mol %, more preferably 5 to 55 mol %, and even more preferably 10 to 50 mol %, based on the total (100 mol %) of all structural units constituting the component (F0).
- the proportion of the structural unit (f1) is at least as large as the lower limit of the aforementioned preferred range, lithography properties such as sensitivity, resolution, and roughness can be improved.
- the proportion of the structural unit (f1) is at most the upper limit of the aforementioned preferred range, a balance with other structural units can be achieved, and various lithography properties become favorable.
- Structural unit (f2) is a structural unit that contains a lactone-containing cyclic group, and is the same as the structural unit (a2) within the component (A1). Of these, the structural unit (f2) is preferably a structural unit represented by general formula (a2-1) above.
- the structural unit (f2) contained in the component (F0) may be of one type or of two or more types.
- the component (F0) may or may not have the structural unit (f2), but preferably has the structural unit (f2).
- the proportion of the structural unit (f2) in the component (F0) is preferably 1 to 60 mol %, more preferably 5 to 55 mol %, and even more preferably 10 to 50 mol %, based on the total (100 mol %) of all structural units constituting the component (F0).
- the proportion of the structural unit (f2) By setting the proportion of the structural unit (f2) to at least the lower limit of the above-mentioned preferred range, the solubility of the resist composition in a developer is likely to be improved.
- the proportion of the structural unit (f2) to no more than the upper limit of the above-mentioned preferred range, a balance with other structural units can be achieved, and various lithography properties are likely to be improved.
- Structural unit (f3) The structural unit (f3) is a structural unit represented by general formula (a10-1) above, and is the same as the structural unit (a10) within the component (A1).
- the structural unit (f3) contained in the component (F0) may be of one type or of two or more types.
- the component (F0) may or may not have the structural unit (f3), but preferably has the structural unit (f3).
- the proportion of the structural unit (f3) in the component (F0) is preferably 1 to 40 mol %, more preferably 1 to 35 mol %, and even more preferably 5 to 30 mol %, based on the total (100 mol %) of all structural units constituting the component (F0).
- Examples of the (F0) component include polymeric compounds containing a repeating structure of structural units (f0) and (f2), polymeric compounds containing a repeating structure of structural units (f0) and (f1), polymeric compounds containing a repeating structure of structural units (f0) and (f3), and polymeric compounds containing a repeating structure of structural units (f0), (f2), and (f3).
- Such component (F0) can be produced by dissolving monomers from which each structural unit is derived in a polymerization solvent, and adding a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) to the solution, followed by polymerization.
- a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601)
- AIBN azobisisobutyronitrile
- V-601 dimethyl azobisisobutyrate
- the component (A1) can be produced by dissolving a monomer that derives the structural unit (f0) and a monomer that derives an arbitrary structural unit (for example, the structural unit (f3)) in a polymerization solvent, adding the above-mentioned radical polymerization initiator to the solution to polymerize, and then carrying out a deprotection
- the weight average molecular weight (Mw) of the component (F0) (based on polystyrene equivalent by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 4,000 to 35,000, and even more preferably 4,000 to 20,000.
- the dispersity (Mw/Mn) of the component (F0) is not particularly limited, but is preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0, and particularly preferably from 1.0 to 2.0, where Mn represents the number average molecular weight.
- the resist composition of this embodiment may also use, as the component (F), a fluorine additive component that does not fall under the category of the component (F0) and that is decomposable in an alkaline developer.
- the proportion of the component (F0) in the component (F) is preferably 25 mass % or more, more preferably 50 mass % or more, and even more preferably 75 mass % or more, relative to the total mass of the component (F), and may be 100 mass %.
- the component (F) may use either a single type, or a combination of two or more types.
- the amount of the component (F0) relative to 100 parts by mass of the component (A) is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 25 parts by mass, even more preferably 0.5 to 20 parts by mass, and particularly preferably 0.9 to 17 parts by mass.
- the content of the component (F0) is at least the lower limit of the above-mentioned range, it is easy to increase the sensitivity and reduce the LWR.
- the content of the component (F0) is at most the upper limit of the above-mentioned preferred range, it is easy to form a pattern with good defect characteristics after development by improving the solubility of the resist composition in a developer.
- the resist composition of this embodiment can be produced by dissolving the resist materials in an organic solvent component (hereafter referred to as “component (S)”).
- component (S) may be used alone or as a mixed solvent of two or more different types.
- PGMEA, PGME, ⁇ -butyrolactone, EL, cyclohexanone, and diacetone alcohol are preferred.
- a mixed solvent of PGMEA and a polar solvent is also preferred.
- the blending ratio (mass ratio) may be appropriately determined taking into consideration the compatibility between PGMEA and the polar solvent, etc.
- a mixed solvent of at least one selected from PGMEA and EL and ⁇ -butyrolactone is also preferred.
- the mixing ratio of the former to the latter is preferably 70:30 to 95:5 by mass.
- the amount of the component (S) used is used so that the solids concentration of the resist composition falls within the range of 0.1 to 20 mass %, and preferably 0.2 to 15 mass %.
- the resist composition of this embodiment after dissolving the resist material in the (S) component, impurities and the like may be removed using a polyimide porous film, a polyamideimide porous film, or the like.
- the resist composition may be filtered using a filter made of a polyimide porous film, a filter made of a polyamideimide porous film, or a filter made of a polyimide porous film and a polyamideimide porous film.
- the polyimide porous film and the polyamideimide porous film include those described in JP 2016-155121 A.
- the resist composition of this embodiment described above contains a resin component (A1) and a fluorine-containing polymeric compound (F0).
- the component (F0) has a structural unit (f0) derived from a compound represented by general formula (f0-1).
- the structural unit (f0) has an iodine atom or a substituent containing an iodine atom on the aromatic ring Ar. Iodine atoms have high absorption of EUV light with a wavelength of 13.5 nm. Therefore, the structural unit (f0) is likely to generate secondary electrons during exposure.
- the secondary electrons generated from the iodine atoms present on Ar of the structural unit (f0) upon exposure promote the decomposition of the cation moiety of components that generate acid upon exposure, such as the structural unit (a5) in the component (A1) and the component (B), thereby achieving high sensitivity and improving resolution.
- the structural unit (f0) contains a fluorine alcohol structure.
- the hydrophilicity of the resist composition is improved and the solubility in the developer is improved, which contributes to the improvement of LWR and development defect characteristics. It is presumed that the combined effects described above enable the resist composition of this embodiment to achieve high sensitivity, reduced LWR, and enable the formation of a resist pattern with favorable defect characteristics after development.
- a method for forming a resist pattern according to the second aspect of the present invention is a method comprising the steps of forming a resist film on a support using the resist composition according to the first aspect of the present invention, exposing the resist film to light, and developing the exposed resist film to form a resist pattern.
- One embodiment of the resist pattern forming method is, for example, a resist pattern forming method carried out as follows.
- the resist composition of the above-described embodiment is applied onto a support using a spinner or the like, and then baked (post-applied bake (PAB)) at a temperature of, for example, 80 to 150° C. for 40 to 120 seconds, preferably 60 to 90 seconds, to form a resist film.
- the resist film is selectively exposed using an exposure device such as an electron beam lithography device or an ArF lithography device, either through a mask (mask pattern) on which a predetermined pattern has been formed, or by lithography using direct irradiation with an electron beam without using a mask pattern, and then baked (post-exposure bake (PEB)) at a temperature of, for example, 80 to 150° C. for 40 to 120 seconds, preferably 60 to 90 seconds.
- the resist film is developed using an alkaline developer in the case of an alkaline development process, or a developer containing an organic solvent (organic developer) in the case of a solvent development process.
- a rinse process is preferably carried out.
- the rinse process is preferably a water rinse using pure water, and in the case of a solvent development process, a rinse liquid containing an organic solvent is preferably used.
- a treatment may be carried out in which the developer or rinsing liquid adhering to the pattern is removed by using a supercritical fluid. After the development or rinsing treatment, the resist is dried. In some cases, a baking treatment (post-baking) may be performed after the development treatment.
- the support is not particularly limited, and conventionally known materials can be used, such as substrates for electronic components and substrates on which a predetermined wiring pattern is formed. More specifically, examples include silicon wafers, substrates made of metals such as copper, chromium, iron, and aluminum, and glass substrates. Materials that can be used for the wiring pattern include, for example, copper, aluminum, nickel, and gold.
- the wavelength used for exposure is not particularly limited, and radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays can be used.
- radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays can be used.
- the exposure method for the resist film may be a normal exposure method (dry exposure) performed in air or an inert gas such as nitrogen, or may be liquid immersion exposure (liquid immersion lithography).
- Immersion exposure is an exposure method in which the space between the resist film and the lowest lens of the exposure tool is filled with a solvent (immersion medium) that has a refractive index greater than that of air, and exposure (immersion exposure) is then performed in that state.
- the immersion medium is preferably a solvent having a refractive index greater than that of air and less than that of the resist film to be exposed, and examples of such a solvent include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent.
- water is preferably used as the liquid immersion medium.
- the alkaline developer used in the development treatment in the alkaline development process may be, for example, a 0.1 to 10% by weight aqueous solution of tetramethylammonium hydroxide (TMAH).
- TMAH tetramethylammonium hydroxide
- the organic solvent contained in the organic developer used in the development treatment in the solvent development process may be any organic solvent capable of dissolving the component (A) (the component (A) before exposure), and may be appropriately selected from known organic solvents.
- Specific examples of the organic solvent include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.
- ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
- nitrile solvents examples include acetonitrile, propionitrile, valeronitrile, butyronitrile, etc.
- additives can be added to the organic developer as necessary.
- additives include surfactants.
- surfactants There are no particular limitations on the surfactants, but examples of surfactants that can be used include ionic or non-ionic fluorine-based and/or silicon-based surfactants.
- the development process can be carried out by a known development method, such as a method of immersing the support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the support by surface tension and leaving it still for a certain period of time (paddle method), a method of spraying the developer on the surface of the support (spray method), or a method of continuously applying developer by scanning a developer application nozzle at a constant speed onto a support rotating at a constant speed (dynamic dispense method).
- a known development method such as a method of immersing the support in a developer for a certain period of time (dip method), a method of piling up the developer on the surface of the support by surface tension and leaving it still for a certain period of time (paddle method), a method of spraying the developer on the surface of the support (spray method), or a method of continuously applying developer by scanning a developer application nozzle at a constant speed onto a support rotating at a constant speed (dynamic
- the organic solvent contained in the rinse solution used in the rinsing treatment after the development treatment in the solvent development process can be appropriately selected from the organic solvents listed above as the organic solvents used in the organic developer, which do not easily dissolve the resist pattern.
- at least one solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. These organic solvents may be used alone or in combination of two or more thereof, and may be used in combination with other organic solvents or water.
- the rinse process (cleaning process) using a rinse solution can be carried out by a known rinse method.
- the rinse process include a method in which the rinse solution is continuously applied onto a support rotating at a constant speed (spin coating method), a method in which the support is immersed in the rinse solution for a certain period of time (dip method), and a method in which the rinse solution is sprayed onto the surface of the support (spray method).
- the resist pattern forming method of this embodiment described above uses the resist composition described above, which allows for high sensitivity and the formation of a resist pattern with excellent lithography properties such as resolution and roughness.
- the resist composition of the above-mentioned embodiment and the various materials used in the pattern formation method of the above-mentioned embodiment preferably do not contain impurities such as metals, metal salts containing halogens, acids, alkalis, and components containing sulfur atoms or phosphorus atoms.
- impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, and salts thereof.
- the content of impurities contained in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially free (below the detection limit of the measuring device).
- the fluorine-containing polymeric compound of this embodiment has a structural unit (f0) derived from a compound represented by the following general formula (f0-1).
- W 1 is a polymerizable group.
- Ar is an aromatic ring.
- Xf is an iodine atom or a substituent containing an iodine atom.
- m1 is an integer of 1 or more as long as the valence allows.
- Lf 01 is a single bond or a linking group having a valence of (n1+1).
- Rf 01 is a fluorinated alkyl group having 1 to 12 carbon atoms.
- Rf 02 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom or a hydrogen atom.
- n1 is an integer of 1 to 3.
- Rf 03 is a substituent other than an iodine atom.
- m2 is an integer of 0 or more as long as the valence allows.
- the fluorine-containing polymeric compound of this embodiment is the same as the component (F0) of the resist composition related to the first aspect.
- the fluorine-containing polymeric compound of this embodiment is useful as a fluorine additive component for use in a resist composition.
- W 1 is a polymerizable group.
- Ar is an aromatic ring.
- Xf is an iodine atom or a substituent containing an iodine atom.
- m1 is an integer of 1 or more as long as the valence allows.
- Lf 01 is a single bond or a linking group having a valence of (n1+1).
- Rf 01 is a fluorinated alkyl group having 1 to 12 carbon atoms.
- Rf 02 is an organic group having 1 to 12 carbon atoms which may have a fluorine atom or a hydrogen atom.
- n1 is an integer of 1 to 3.
- Rf 03 is a substituent other than an iodine atom.
- m2 is an integer of 0 or more as long as the valence allows.
- the fluorine-containing polymer compound of this embodiment is the same as the compound that derives the structural unit (f0) contained in the component (F0) of the resist composition according to the first aspect.
- the method for producing the compound of the present embodiment is not particularly limited, and the compound can be produced by appropriately combining known methods.
- the compound of this embodiment is useful for producing a fluorine-containing polymer compound having the structural unit (f0) (the fluorine-containing polymer compound (F0) in the first aspect).
- the obtained compound was subjected to NMR measurement, and its structure was identified from the following results.
- the obtained compound was subjected to NMR measurement, and its structure was identified from the following results.
- the obtained compound was subjected to NMR measurement, and its structure was identified from the following results.
- the obtained compound was subjected to NMR measurement, and its structure was identified from the following results.
- the obtained compound was subjected to NMR measurement, and its structure was identified from the following results.
- the obtained compound was subjected to NMR measurement, and its structure was identified from the following results.
- the obtained compound was subjected to NMR measurement, and its structure was identified from the following results.
- the polymer compounds (P-01) to (P-39) were each obtained by radical polymerization of monomers that derive the structural units constituting each polymer compound in a predetermined molar ratio, followed by a deprotection reaction as necessary.
- the weight average molecular weight (Mw) and the molecular weight dispersity (Mw/Mn) of each of the obtained polymer compounds were determined by GPC measurement (converted into standard polystyrene). The results are shown in Tables 1 and 2.
- the copolymer composition ratio (the ratio (molar ratio) of each structural unit in the structural formula) of each obtained polymer compound was determined by carbon-13 nuclear magnetic resonance spectroscopy (600 MHz, 13C-NMR). The results are shown in Tables 1 and 2.
- (A1)-1 A polymer compound represented by the following formula (A1-1).
- the weight average molecular weight (Mw) calculated in terms of standard polystyrene by GPC measurement was 5,800, and the molecular weight dispersity (Mw/Mn) was 1.54.
- (A1)-2 A polymer compound represented by the following formula (A1-2).
- the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 6,000, and the molecular weight dispersity (Mw/Mn) was 1.55.
- (A1)-3 A polymeric compound represented by the following formula (A1-3).
- the weight average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 5,900, and the molecular weight dispersity (Mw/Mn) was 1.54.
- (B1)-1 An acid generator comprising the following compound (B1-1):
- (D1)-1 An acid diffusion controller consisting of the following compound (D1-1).
- (F0)-1 to (F0)-39 the polymer compounds (P-01) to (P-39).
- (F1)-2 Polymer compound represented by the following formula (F1-2).
- Standard polystyrene-equivalent weight average molecular weight (Mw) determined by GPC measurement was 12,200, and molecular weight dispersity (Mw/Mn) was 1.49.
- (F1)-3 Polymer compound represented by the following formula (F1-3).
- Standard polystyrene-equivalent weight average molecular weight (Mw) determined by GPC measurement was 12,100, and molecular weight dispersity (Mw/Mn) was 1.50.
- (F1)-4: Polymer compound represented by the following formula (F1-4). Standard polystyrene-equivalent weight average molecular weight (Mw) determined by GPC measurement was 12,100, and molecular weight dispersity (Mw/Mn) was 1.51. Copolymer composition ratio (proportion (molar ratio) of each structural unit in the structural formula) determined by 13C -NMR was l/m 25/75.
- ⁇ Formation of Resist Pattern> Each resist composition of the examples was applied using a spinner onto an 8-inch silicon substrate that had been treated with hexamethyldisilazane (HMDS), and the substrate was pre-baked (PAB) on a hot plate at a temperature of 110° C. for 60 seconds, followed by drying to form a resist film with a thickness of 50 nm.
- the resist film was subjected to drawing (exposure) using an electron beam lithography apparatus JEOL-JBX-9300FS (manufactured by JEOL Ltd.) at an acceleration voltage of 100 kV, with a target size of a 1:1 line and space pattern (hereinafter referred to as "LS pattern”) with a line width of 25 nm.
- LS pattern target size of a 1:1 line and space pattern
- a post-exposure bake (PEB) treatment was performed at 110°C for 60 seconds.
- PEB post-exposure bake
- an alkali development was performed for 60 seconds at 23°C using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.).
- TMAH tetramethylammonium hydroxide
- the resist compositions of the examples were superior in sensitivity, LWR, and defects compared to the resist compositions of the comparative examples.
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Abstract
Description
本願は、2023年3月14日に日本に出願された、特願2023-039556号に基づき優先権主張し、その内容をここに援用する。
このような要求を満たすレジスト材料として、従来、酸の作用により現像液に対する溶解性が変化する基材成分と、露光により酸を発生する酸発生剤成分と、を含有する化学増幅型レジスト組成物が用いられている。
例えば、特許文献1には、特定構造の酸解離性基を含む構成単位と、フッ素アルコールを含む構成単位と、フェノール性水酸基を含む構成単位とを有する樹脂成分を含有するレジスト組成物が開示されている。
すなわち、本発明の第1の態様は、露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化するレジスト組成物であって、酸の作用により現像液に対する溶解性が変化する樹脂成分(A1)と、下記一般式(f0-1)で表される化合物から誘導される構成単位(f0)を有する含フッ素高分子化合物(F0)と、を含有するレジスト組成物である。
「アルキル基」は、特に断りがない限り、直鎖状、分岐鎖状及び環状の1価の飽和炭化水素基を包含するものとする。アルコキシ基中のアルキル基も同様である。
「アルキレン基」は、特に断りがない限り、直鎖状、分岐鎖状及び環状の2価の飽和炭化水素基を包含するものとする。
「ハロゲン原子」は、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
「構成単位」とは、高分子化合物(樹脂、重合体、共重合体)を構成するモノマー単位(単量体単位)を意味する。
「置換基を有してもよい」と記載する場合、水素原子(-H)を1価の基で置換する場合と、メチレン基(-CH2-)を2価の基で置換する場合との両方を含む。
「露光」は、放射線の照射全般を含む概念とする。
酸の作用により極性が増大する酸分解性基としては、例えば、酸の作用により分解して極性基を生じる基が挙げられる。
極性基としては、例えばカルボキシ基、水酸基、アミノ基、スルホ基(-SO3H)等が挙げられる。
酸分解性基としてより具体的には、前記極性基が酸解離性基で保護された基(例えばOH含有極性基の水素原子を、酸解離性基で保護した基)が挙げられる。
酸分解性基を構成する酸解離性基は、当該酸解離性基の解離により生成する極性基よりも極性の低い基であることが必要で、これにより、酸の作用により該酸解離性基が解離した際に、該酸解離性基よりも極性の高い極性基が生じて極性が増大する。その結果、(A1)成分全体の極性が増大する。極性が増大することにより、相対的に、現像液に対する溶解性が変化し、現像液がアルカリ現像液の場合には溶解性が増大し、現像液が有機系現像液の場合には溶解性が減少する。
「アクリル酸エステル」は、α位の炭素原子に結合した水素原子が置換基で置換されていてもよい。該α位の炭素原子に結合した水素原子を置換する置換基(Rαx)は、水素原子以外の原子又は基である。また、置換基(Rαx)がエステル結合を含む置換基で置換されたイタコン酸ジエステルや、置換基(Rαx)がヒドロキシアルキル基やその水酸基を修飾した基で置換されたαヒドロキシアクリルエステルも含むものとする。なお、アクリル酸エステルのα位の炭素原子とは、特に断りがない限り、アクリル酸のカルボニル基が結合している炭素原子のことである。
以下、α位の炭素原子に結合した水素原子が置換基で置換されたアクリル酸エステルを、α置換アクリル酸エステルということがある。
ヒドロキシスチレンのα位の水素原子を置換する置換基としては、Rαxと同様のものが挙げられる。
本実施形態のレジスト組成物は、露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化するものである。
かかるレジスト組成物は、酸の作用により現像液に対する溶解性が変化する基材成分(A)(以下「(A)成分」ともいう)と、後述する(f0-1)で表される化合物から誘導される構成単位(f0)を有する含フッ素高分子化合物(F0)(以下「(F0)成分ともいう」)を含有する。
すなわち、上記(2)及び(3)の場合、(A)成分は、「露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化する基材成分」となる。(A)成分が露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化する基材成分である場合、後述する(A1)成分が、露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化する樹脂であることが好ましい。このような樹脂としては、露光により酸を発生する構成単位を有する高分子化合物を用いることができる。露光により酸を発生する構成単位としては、後述の構成単位(a5)等を用いることができる。
本実施形態のレジスト組成物においては、(A1)成分を用いることにより、露光前後で基材成分の極性が変化するため、アルカリ現像プロセスだけでなく、溶剤現像プロセスにおいても、良好な現像コントラストを得ることができる。
(A)成分としては、該(A1)成分とともに他の高分子化合物及び/又は低分子化合物を併用してもよい。
(A1)成分は、酸の作用により現像液に対する溶解性が変化する樹脂成分である。
(A1)成分としては、酸の作用により極性が増大する酸分解性基を含む構成単位(a1)を有するものが好ましい。
(A1)成分は、構成単位(a1)に加え、必要に応じてその他構成単位を有するものでもよい。
構成単位(a1)は、酸の作用により極性が増大する酸分解性基を含む構成単位である。
化学増幅型レジスト組成物用のベース樹脂の酸解離性基として提案されているものとして具体的には、以下に説明する「アセタール型酸解離性基」、「第3級アルキルエステル型酸解離性基」、「第3級アルキルオキシカルボニル酸解離性基」、「第2級アルキルオキシカルボニル酸解離性基」が挙げられる。
前記極性基のうちカルボキシ基または水酸基を保護する酸解離性基としては、例えば、下記一般式(a1-r-1)で表される酸解離性基(以下「アセタール型酸解離性基」ということがある。)が挙げられる。
Ra’1又はRa’2がアルキル基である場合、該アルキル基としては、上記α置換アクリル酸エステルについての説明で、α位の炭素原子に結合してもよい置換基として挙げたアルキル基と同様のものが挙げられ、炭素原子数1~5のアルキル基が好ましい。具体的には、直鎖状または分岐鎖状のアルキル基が好ましく挙げられる。より具体的には、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基などが挙げられ、メチル基またはエチル基がより好ましく、メチル基が特に好ましい。
該直鎖状のアルキル基は、炭素原子数が1~5であることが好ましく、炭素原子数が1~4がより好ましく、炭素原子数1または2がさらに好ましい。具体的には、メチル基、エチル基、n-プロピル基、n-ブチル基、n-ペンチル基等が挙げられる。これらの中でも、メチル基、エチル基またはn-ブチル基が好ましく、メチル基またはエチル基がより好ましい。
単環式基である脂肪族炭化水素基としては、モノシクロアルカンから1個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数3~6のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。
多環式基である脂肪族炭化水素基としては、ポリシクロアルカンから1個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数7~12のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等が挙げられる。
この芳香環は、4n+2個のπ電子をもつ環状共役系であれば特に限定されず、単環式でも多環式でもよい。芳香環の炭素原子数は5~30であることが好ましく、炭素原子数5~20がより好ましく、炭素原子数6~15がさらに好ましく、炭素原子数6~12が特に好ましい。
芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環;前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。
Ra’3における芳香族炭化水素基として具体的には、前記芳香族炭化水素環または芳香族複素環から水素原子を1つ除いた基(アリール基またはヘテロアリール基);2以上の芳香環を含む芳香族化合物(例えばビフェニル、フルオレン等)から水素原子を1つ除いた基;前記芳香族炭化水素環または芳香族複素環の水素原子の1つがアルキレン基で置換された基(例えば、ベンジル基、フェネチル基、1-ナフチルメチル基、2-ナフチルメチル基、1-ナフチルエチル基、2-ナフチルエチル基等のアリールアルキル基など)等が挙げられる。前記芳香族炭化水素環または芳香族複素環に結合するアルキレン基の炭素原子数は、1~4であることが好ましく、炭素原子数1~2であることがより好ましく、炭素原子数1であることが特に好ましい。
ここで、RP1は、炭素原子数1~10の1価の鎖状飽和炭化水素基、炭素原子数3~20の1価の脂肪族環状飽和炭化水素基又は炭素原子数6~30の1価の芳香族炭化水素基である。また、RP2は、単結合、炭素原子数1~10の2価の鎖状飽和炭化水素基、炭素原子数3~20の2価の脂肪族環状飽和炭化水素基又は炭素原子数6~30の2価の芳香族炭化水素基である。但し、RP1及びRP2の鎖状飽和炭化水素基、脂肪族環状飽和炭化水素基及び芳香族炭化水素基の有する水素原子の一部又は全部はフッ素原子で置換されていてもよい。上記脂肪族環状炭化水素基は、上記置換基を1種単独で1つ以上有していてもよいし、上記置換基のうち複数種を各1つ以上有していてもよい。
炭素原子数1~10の1価の鎖状飽和炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基等が挙げられる。
炭素原子数3~20の1価の脂肪族環状飽和炭化水素基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、シクロドデシル基等の単環式脂肪族飽和炭化水素基;ビシクロ[2.2.2]オクタニル基、トリシクロ[5.2.1.02,6]デカニル基、トリシクロ[3.3.1.13,7]デカニル基、テトラシクロ[6.2.1.13,6.02,7]ドデカニル基、アダマンチル基等の多環式脂肪族飽和炭化水素基が挙げられる。
炭素原子数6~30の1価の芳香族炭化水素基としては、例えば、ベンゼン、ビフェニル、フルオレン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環から水素原子1個を除いた基が挙げられる。
上記極性基のうち、カルボキシ基を保護する酸解離性基としては、例えば、下記一般式(a1-r-2)で表される酸解離性基が挙げられる。
なお、下記式(a1-r-2)で表される酸解離性基のうち、アルキル基により構成されるものを、以下、便宜上「第3級アルキルエステル型酸解離性基」ということがある。
Ra’4における直鎖状もしくは分岐鎖状のアルキル基、環状の炭化水素基(単環式基である脂肪族炭化水素基、多環式基である脂肪族炭化水素基、芳香族炭化水素基)は、前記Ra’3と同様のものが挙げられる。
Ra’4における鎖状もしくは環状のアルケニル基は、炭素原子数2~10のアルケニル基が好ましい。
Ra’5、Ra’6の炭化水素基としては、前記Ra’3と同様のものが挙げられる。
一方、Ra’4~Ra’6が互いに結合せず、独立した炭化水素基である場合、下記一般式(a1-r2-4)で表される基が好適に挙げられる。
Ra’10における、分岐鎖状のアルキル基としては、前記Ra’3と同様のものが挙げられる。
ここでいうヘテロ原子としては、酸素原子、硫黄原子、窒素原子が挙げられる。ヘテロ原子含有基としては、(-O-)、-C(=O)-O-、-O-C(=O)-、-C(=O)-、-O-C(=O)-O-、-C(=O)-NH-、-NH-、-S-、-S(=O)2-、-S(=O)2-O-等が挙げられる。
XaがYaと共に形成する環状の炭化水素基は、置換基を有してもよい。この置換基としては、上記Ra’3における環状の炭化水素基が有していてもよい置換基と同様のものが挙げられる。
式(a1-r2-2)中、Ra101~Ra103における、炭素原子数1~10の1価の鎖状飽和炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基等が挙げられる。
Ra101~Ra103における、炭素原子数3~20の1価の脂肪族環状飽和炭化水素基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、シクロドデシル基等の単環式脂肪族飽和炭化水素基;ビシクロ[2.2.2]オクタニル基、トリシクロ[5.2.1.02,6]デカニル基、トリシクロ[3.3.1.13,7]デカニル基、テトラシクロ[6.2.1.13,6.02,7]ドデカニル基、アダマンチル基等の多環式脂肪族飽和炭化水素基等が挙げられる。
Ra101~Ra103は、中でも、合成容易性の観点から、水素原子、炭素原子数1~10の1価の鎖状飽和炭化水素基が好ましく、その中でも、水素原子、メチル基、エチル基がより好ましく、水素原子が特に好ましい。
式(a1-r2-3)中、Ra104における芳香族炭化水素基としては、炭素原子数5~30の芳香族炭化水素環から水素原子1個以上を除いた基が挙げられる。中でも、Ra104は、炭素原子数6~15の芳香族炭化水素環から水素原子1個以上を除いた基が好ましく、ベンゼン、ナフタレン、アントラセン又はフェナントレンから水素原子1個以上を除いた基がより好ましく、ベンゼン、ナフタレン又はアントラセンから水素原子1個以上を除いた基がさらに好ましく、ベンゼン又はナフタレンから水素原子1個以上を除いた基が特に好ましく、ベンゼンから水素原子1個以上を除いた基が最も好ましい。
Ra’12及びRa’13は、中でも、炭素原子数1~5のアルキル基が好ましく、炭素原子数1~5のアルキル基がより好ましく、メチル基、エチル基がさらに好ましく、メチル基が特に好ましい。
上記Ra’12及びRa’13で表される鎖状飽和炭化水素基が置換されている場合、その置換基としては、例えば、上述のRax5と同様の基が挙げられる。
単環式基である脂肪族炭化水素基としては、モノシクロアルカンから1個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数3~6のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。
多環式基である脂肪族炭化水素基としては、ポリシクロアルカンから1個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数7~12のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等が挙げられる。
Ra’14が有していてもよい置換基としては、Ra104が有していてもよい置換基と同様のものが挙げられる。
式(a1-r2-4)中のRa’14がアントリル基である場合、前記式(a1-r2-4)における第3級炭素原子と結合する位置は、アントリル基の1位、2位又は9位のいずれであってもよい。
前記極性基のうち水酸基を保護する酸解離性基としては、例えば、下記一般式(a1-r-3)で表される酸解離性基(以下便宜上「第3級アルキルオキシカルボニル酸解離性基」ということがある)が挙げられる。
また、各アルキル基の合計の炭素原子数は、3~7であることが好ましく、炭素原子数3~5であることがより好ましく、炭素原子数3~4であることが最も好ましい。
上記極性基のうち、カルボキシ基を保護する酸解離性基としては、例えば、下記一般式(a1-r-4)で表される酸解離性基が挙げられる。
式中、Ra’11a及びRa’11bにおけるアルキル基としては、前記Ra’1におけるアルキル基と同様のものが挙げられる。
式中、Ra’10及びRa’12における炭化水素基、並びに、Ra’11a及びRa’11bにおけるアルキル基は置換基を有してもよい。この置換基としては、例えば、上述したRax5等が挙げられる。
該脂環及び芳香環は、ヘテロ原子を含むものでもよい。
かかる構成単位(a1)の好ましい具体例としては、下記一般式(a1-1)、(a1-2)又は(a1-3)で表される構成単位が挙げられる。
Rとしては、水素原子、炭素原子数1~5のアルキル基又は炭素原子数1~5のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子又はメチル基が最も好ましい。
該脂肪族炭化水素基として、より具体的には、直鎖状もしくは分岐鎖状の脂肪族炭化水素基、又は、構造中に環を含む脂肪族炭化水素基等が挙げられる。
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基[-CH2-]、エチレン基[-(CH2)2-]、トリメチレン基[-(CH2)3-]、テトラメチレン基[-(CH2)4-]、ペンタメチレン基[-(CH2)5-]等が挙げられる。
前記分岐鎖状の脂肪族炭化水素基は、炭素原子数が2~10であることが好ましく、炭素原子数3~6がより好ましく、炭素原子数3又は4がさらに好ましく、炭素原子数3が最も好ましい。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等のアルキルメチレン基;-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-等のアルキルエチレン基;-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-等のアルキルトリメチレン基;-CH(CH3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2-等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素原子数1~5の直鎖状のアルキル基が好ましい。
前記脂環式炭化水素基は、炭素原子数が3~20であることが好ましく、炭素原子数3~12であることがより好ましい。
前記脂環式炭化水素基は、多環式であってもよく、単環式であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから2個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては炭素原子数3~6のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから2個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては炭素原子数7~12のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等が挙げられる。
かかる芳香族炭化水素基は、炭素原子数が3~30であることが好ましく、5~30であることがより好ましく、5~20がさらに好ましく、6~15が特に好ましく、6~12が最も好ましい。ただし、該炭素原子数には、置換基における炭素原子数を含まないものとする。
芳香族炭化水素基が有する芳香環として具体的には、ベンゼン、ビフェニル、フルオレン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環;前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。
該芳香族炭化水素基として具体的には、前記芳香族炭化水素環から水素原子を2つ除いた基(アリーレン基);前記芳香族炭化水素環から水素原子を1つ除いた基(アリール基)の水素原子の1つがアルキレン基で置換された基(例えば、ベンジル基、フェネチル基、1-ナフチルメチル基、2-ナフチルメチル基、1-ナフチルエチル基、2-ナフチルエチル基等のアリールアルキル基におけるアリール基から水素原子をさらに1つ除いた基)等が挙げられる。前記アルキレン基(アリールアルキル基中のアルキル鎖)の炭素原子数は、1~4であることが好ましく、1~2であることがより好ましく、1であることが特に好ましい。
前記na2+1価は、2~4価が好ましく、2又は3価がより好ましい。
Ya001としては、エステル結合[-C(=O)-O-、-O-C(=O)-]、エーテル結合(-O-)、直鎖状若しくは分岐鎖状のアルキレン基、芳香族炭化水素基又はこれらの組合せ、あるいは単結合であることが好ましい。アルキレン基の炭素原子数は、1~10であることが好ましく、炭素原子数1~6がより好ましく、炭素原子数1~4がさらに好ましく、炭素原子数1~3が特に好ましい。
これらの中でも、Ya001としては、エステル結合[-C(=O)-O-、-O-C(=O)-]と直鎖状のアルキレン基との組み合わせ、又は単結合であることがより好ましく、単結合であることがさらに好ましい。
Ya01は、上記の中でも、エステル結合[-C(=O)-O-、-O-C(=O)-]、エーテル結合(-O-)、直鎖状若しくは分岐鎖状のアルキレン基、芳香族炭化水素基又はこれらの組合せ、あるいは単結合であることが好ましい。これらの中でも、Ya01としては、エステル結合[-C(=O)-O-、-O-C(=O)-]と直鎖状のアルキレン基との組み合わせ、又は単結合であることがより好ましく、単結合であることがさらに好ましい。
前記式(a1-3)中、nは、0以上の整数であり、好ましくは0~5であり、より好ましくは0~3であり、さらに好ましくは0~2である。
前記式(a1-3)中、n≦q×2+4である。例えば、qが1でナフタレン構造である場合、該ナフタレンは、6個全部の水素原子がヒドロキシ基で置換されていてもよい。また、該ナフタレンにおいて、Ya001、-Ya01-C(=O)-O-Ra01基、及びヒドロキシ基の置換位置は特に限定されない。
以下の各式中、Rαは、水素原子、メチル基またはトリフルオロメチル基を示す。
構成単位(a1)としては、電子線やEUVによるリソグラフィーでの特性(感度、形状等)をより高められやすいことから、前記式(a1-1)で表される構成単位、又は前記式(a1-3)で表される構成単位がより好ましい。
中でも、EB用又はEUV用において反応性を高められて好適なことから、酸解離性基(Ra1、Rax01)が、それぞれ、上記の一般式(a1-r2-1)、(a1-r2-3)、(a1-r2-4)又は(a1-r-4)で表される酸解離性基であることが好ましく、その中でも環式基であるものを選択することが特に好ましい。
構成単位(a1)の割合を、前記の好ましい範囲の下限値以上とすることによって、感度、解像性、ラフネス改善等のリソグラフィー特性が向上する。一方、前記の好ましい範囲の上限値以下であると、他の構成単位とのバランスを取ることができ、種々のリソグラフィー特性が良好となる。
(A1)成分は、上述した構成単位(a1)に加え、必要に応じてその他構成単位を有するものでもよい。
その他構成単位としては、例えば、下記一般式(a10-1)で表される構成単位;露光により酸を発生する構成単位(a5);ラクトン含有環式基を含む構成単位(a2);下記一般式(a8-1)で表される化合物から誘導される構成単位などが挙げられる。
構成単位(a10)は、下記一般式(a10-1)で表される構成単位である。
前記の化学式中、Yax1における2価の連結基としては、特に限定されないが、置換基を有してもよい2価の炭化水素基、ヘテロ原子を含む2価の連結基等が好適なものとして挙げられる。
置換基を有してもよい2価の炭化水素基は、脂肪族炭化水素基であってもよく、芳香族炭化水素基であってもよい。
脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。該脂肪族炭化水素基は、飽和であってもよく、不飽和であってもよく、通常は飽和であることが好ましい。
前記脂肪族炭化水素基としては、直鎖状若しくは分岐鎖状の脂肪族炭化水素基、又は構造中に環を含む脂肪族炭化水素基等が挙げられる。
該直鎖状の脂肪族炭化水素基は、炭素原子数1~10でが好ましく、炭素原子数1~6がより好ましく、炭素原子数1~4がさらに好ましく、炭素原子数1~3が最も好ましい。
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基[-CH2-]、エチレン基[-(CH2)2-]、トリメチレン基[-(CH2)3-]、テトラメチレン基[-(CH2)4-]、ペンタメチレン基[-(CH2)5-]等が挙げられる。
該分岐鎖状の脂肪族炭化水素基は、炭素原子数2~10が好ましく、炭素原子数3~6がより好ましく、炭素原子数3又は4がさらに好ましく、炭素原子数3が最も好ましい。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等のアルキルメチレン基;-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-等のアルキルエチレン基;-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-等のアルキルトリメチレン基;-CH(CH3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2-等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素原子数1~5の直鎖状のアルキル基が好ましい。
該構造中に環を含む脂肪族炭化水素基としては、環構造中にヘテロ原子を含む置換基を含んでもよい環状の脂肪族炭化水素基(脂肪族炭化水素環から水素原子を2個除いた基)、前記環状の脂肪族炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の末端に結合した基、前記環状の脂肪族炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の途中に介在する基などが挙げられる。前記直鎖状または分岐鎖状の脂肪族炭化水素基としては前記と同様のものが挙げられる。
環状の脂肪族炭化水素基は、炭素原子数3~20が好ましく、炭素原子数3~12がより好ましい。
環状の脂肪族炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから2個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数3~6のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから2個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数7~12のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等が挙げられる。
前記置換基としてのアルキル基としては、炭素原子数1~5のアルキル基が好ましく、メチル基、エチル基、プロピル基、n-ブチル基、tert-ブチル基であることがより好ましい。
前記置換基としてのアルコキシ基としては、炭素原子数1~5のアルコキシ基が好ましく、メトキシ基、エトキシ基、n-プロポキシ基、iso-プロポキシ基、n-ブトキシ基、tert-ブトキシ基がより好ましく、メトキシ基、エトキシ基がさらに好ましい。
前記置換基としてのハロゲン原子としては、フッ素原子が好ましい。
前記置換基としてのハロゲン化アルキル基としては、前記アルキル基の水素原子の一部または全部が前記ハロゲン原子で置換された基が挙げられる。
環状の脂肪族炭化水素基は、その環構造を構成する炭素原子の一部がヘテロ原子を含む置換基で置換されてもよい。該ヘテロ原子を含む置換基としては、-O-、-C(=O)-O-、-S-、-S(=O)2-、-S(=O)2-O-が好ましい。
該芳香族炭化水素基は、芳香環を少なくとも1つ有する炭化水素基である。
この芳香環は、4n+2個のπ電子をもつ環状共役系であれば特に限定されず、単環式でもよいし、多環式でもよい。芳香環の炭素原子数は5~30であることが好ましく、炭素原子数5~20がより好ましく、炭素原子数6~15がさらに好ましく、炭素原子数6~12が特に好ましい。ただし、該炭素原子数には、置換基における炭素原子数を含まないものとする。
芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環;前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。
芳香族炭化水素基として具体的には、前記芳香族炭化水素環または芳香族複素環から水素原子を2つ除いた基(アリーレン基またはヘテロアリーレン基);2以上の芳香環を含む芳香族化合物(例えばビフェニル、フルオレン等)から水素原子を2つ除いた基;前記芳香族炭化水素環または芳香族複素環から水素原子を1つ除いた基(アリール基またはヘテロアリール基)の水素原子の1つがアルキレン基で置換された基(例えば、ベンジル基、フェネチル基、1-ナフチルメチル基、2-ナフチルメチル基、1-ナフチルエチル基、2-ナフチルエチル基等のアリールアルキル基におけるアリール基から水素原子をさらに1つ除いた基)等が挙げられる。前記アリール基またはヘテロアリール基に結合するアルキレン基の炭素原子数は、1~4であることが好ましく、炭素原子数1~2であることがより好ましく、炭素原子数1であることが特に好ましい。
前記置換基としてのアルキル基としては、炭素原子数1~5のアルキル基が好ましく、メチル基、エチル基、プロピル基、n-ブチル基、tert-ブチル基であることがより好ましい。
前記置換基としてのアルコキシ基、ハロゲン原子およびハロゲン化アルキル基としては、前記環状の脂肪族炭化水素基が有する水素原子を置換する置換基として例示したものが挙げられる。
ヘテロ原子を含む2価の連結基としては、-O-、-C(=O)-O-、-O-C(=O)-、-C(=O)-、-O-C(=O)-O-、-C(=O)-NH-、-NH-、-NH-C(=NH)-(Hはアルキル基、アシル基等の置換基で置換されていてもよい。)、-S-、-S(=O)2-、-S(=O)2-O-、一般式-Y21-O-Y22-、-Y21-O-、-Y21-C(=O)-O-、-C(=O)-O-Y21-、-[Y21-C(=O)-O]m”-Y22-、-Y21-O-C(=O)-Y22-または-Y21-S(=O)2-O-Y22-で表される基[式中、Y21およびY22はそれぞれ独立して置換基を有してもよい2価の炭化水素基であり、Oは酸素原子であり、m”は0~3の整数である。]等が挙げられる。
前記ヘテロ原子を含む2価の連結基が-C(=O)-NH-、-C(=O)-NH-C(=O)-、-NH-、-NH-C(=NH)-の場合、そのHはアルキル基、アシル基等の置換基で置換されていてもよい。該置換基(アルキル基、アシル基等)は、炭素原子数が1~10であることが好ましく、1~8であることがさらに好ましく、1~5であることが特に好ましい。
一般式-Y21-O-Y22-、-Y21-O-、-Y21-C(=O)-O-、-C(=O)-O-Y21-、-[Y21-C(=O)-O]m”-Y22-、-Y21-O-C(=O)-Y22-または-Y21-S(=O)2-O-Y22-中、Y21およびY22は、それぞれ独立して、置換基を有してもよい2価の炭化水素基である。該2価の炭化水素基としては、前記と同様のものが挙げられる。
Y21としては、直鎖状の脂肪族炭化水素基が好ましく、直鎖状のアルキレン基がより好ましく、炭素原子数1~5の直鎖状のアルキレン基がさらに好ましく、メチレン基またはエチレン基が特に好ましい。
Y22としては、直鎖状または分岐鎖状の脂肪族炭化水素基が好ましく、メチレン基、エチレン基またはアルキルメチレン基がより好ましい。該アルキルメチレン基におけるアルキル基は、炭素原子数1~5の直鎖状のアルキル基が好ましく、炭素原子数1~3の直鎖状のアルキル基がより好ましく、メチル基が最も好ましい。
式-[Y21-C(=O)-O]m”-Y22-で表される基において、m”は0~3の整数であり、0~2の整数であることが好ましく、0または1がより好ましく、1が特に好ましい。つまり、式-[Y21-C(=O)-O]m”-Y22-で表される基としては、式-Y21-C(=O)-O-Y22-で表される基が特に好ましい。なかでも、式-(CH2)a’-C(=O)-O-(CH2)b’-で表される基が好ましい。該式中、a’は、1~10の整数であり、1~8の整数が好ましく、1~5の整数がより好ましく、1または2がさらに好ましく、1が最も好ましい。b’は、1~10の整数であり、1~8の整数が好ましく、1~5の整数がより好ましく、1または2がさらに好ましく、1が最も好ましい。
Wax1における芳香族炭化水素基としては、置換基を有してもよい芳香環から(nax1+1)個の水素原子を除いた基が挙げられる。ここでの芳香環は、4n+2個のπ電子をもつ環状共役系であれば特に限定されない。芳香環の炭素原子数は5~30であることが好ましく、炭素原子数5~20がより好ましく、炭素原子数6~15がさらに好ましく、炭素原子数6~12が特に好ましい。該芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環;前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。
また、Wax1における芳香族炭化水素基としては、2以上の置換基を有してもよい芳香環を含む芳香族化合物(例えばビフェニル、フルオレン等)から(nax1+1)個の水素原子を除いた基も挙げられる。
上記の中でも、Wax1としては、ベンゼン、ナフタレン、アントラセンまたはビフェニルから(nax1+1)個の水素原子を除いた基が好ましく、ベンゼン又はナフタレンから(nax1+1)個の水素原子を除いた基がより好ましく、ベンゼンから(nax1+1)個の水素原子を除いた基がさらに好ましい。
以下の各式中、Rαは、水素原子、メチル基又はトリフルオロメチル基を表す。
(A1)成分が構成単位(a10)を有する場合、(A1)成分中の構成単位(a10)の割合は、(A1)成分を構成する全構成単位の合計(100モル%)に対して、20~80モル%が好ましく、25~70モル%がより好ましく、30~60モル%がさらに好ましく、40~60モル%が特に好ましい。
構成単位(a10)の割合を下限値以上とすることにより、感度がより高められやすくなる。一方、上限値以下とすることにより、他の構成単位とのバランスをとりやすくなる。
(A1)成分は、ラクトン含有環式基を含む構成単位(a2)(但し、構成単位(a1)に該当するものを除く)を有してもよい。
構成単位(a2)のラクトン含有環式基は、(A1)成分をレジスト膜の形成に用いた場合に、レジスト膜の基板への密着性を高める上で有効である。また、構成単位(a2)を有することで、例えば酸拡散長を適切に調整する、レジスト膜の基板への密着性を高める、現像時の溶解性を適切に調整する等の効果により、リソグラフィー特性等が良好となる。
構成単位(a2)におけるラクトン含有環式基としては、特に限定されることなく任意のものが使用可能である。具体的には、下記一般式(a2-r-1)~(a2-r-7)でそれぞれ表される基が挙げられる。
Ra’21におけるアルコキシ基としては、炭素原子数1~6のアルコキシ基が好ましい。該アルコキシ基は、直鎖状または分岐鎖状であることが好ましい。具体的には、前記Ra’21におけるアルキル基として挙げたアルキル基と酸素原子(-O-)とが連結した基が挙げられる。
Ra’21におけるハロゲン原子としては、フッ素原子が好ましい。
Ra’21におけるハロゲン化アルキル基としては、前記Ra’21におけるアルキル基の水素原子の一部または全部が前記ハロゲン原子で置換された基が挙げられる。該ハロゲン化アルキル基としては、フッ素化アルキル基が好ましく、特にパーフルオロアルキル基が好ましい。
R”におけるアルキル基としては、直鎖状、分岐鎖状、環状のいずれでもよく、炭素原子数は1~15が好ましい。
R”が直鎖状もしくは分岐鎖状のアルキル基の場合は、炭素原子数1~10であることが好ましく、炭素原子数1~5であることがさらに好ましく、メチル基またはエチル基であることが特に好ましい。
R”が環状のアルキル基の場合は、炭素原子数3~15であることが好ましく、炭素原子数4~12であることがさらに好ましく、炭素原子数5~10が最も好ましい。具体的には、フッ素原子またはフッ素化アルキル基で置換されていてもよいし、されていなくてもよいモノシクロアルカンから1個以上の水素原子を除いた基;ビシクロアルカン、トリシクロアルカン、テトラシクロアルカンなどのポリシクロアルカンから1個以上の水素原子を除いた基などを例示できる。より具体的には、シクロペンタン、シクロヘキサン等のモノシクロアルカンから1個以上の水素原子を除いた基;アダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカンなどのポリシクロアルカンから1個以上の水素原子を除いた基などが挙げられる。
R”におけるラクトン含有環式基としては、前記一般式(a2-r-1)~(a2-r-7)でそれぞれ表される基と同様のものが挙げられる。
Ra’21におけるヒドロキシアルキル基としては、炭素原子数が1~6であるものが好ましく、具体的には、前記Ra’21におけるアルキル基の水素原子の少なくとも1つが水酸基で置換された基が挙げられる。
かかる構成単位(a2)は、下記一般式(a2-1)で表される構成単位であることが好ましい。
Ra21におけるラクトン含有環式基としてはそれぞれ、前述した一般式(a2-r-1)~(a2-r-7)でそれぞれ表される基が好適に挙げられる。
(A1)成分が構成単位(a2)を有する場合、構成単位(a2)の割合は、当該(A1)成分を構成する全構成単位の合計(100モル%)に対して、1~20モル%であることが好ましく、1~15モル%であることがより好ましく、1~10モル%であることがさらに好ましい。
構成単位(a2)の割合を好ましい下限値以上とすると、前述した効果によって、構成単位(a2)を含有させることによる効果が充分に得られ、上限値以下であると、他の構成単位とのバランスを取ることができ、種々のリソグラフィー特性が良好となる。
本実施形態において、構成単位(a5)は、露光により酸を発生する構成単位であり、公知のものを用いることができる。構成単位(a5)を有することにより、露光によって発生する酸が、レジスト膜内で、均一に分布しやすくなる。
構成単位(a5)としては、例えば、下記一般式(a5-1)で表される構成単位が好適に挙げられる。
前記式(a5-1)中、Rmは、炭素数1~5のアルキル基、炭素数1~5のハロゲン化アルキル基、ハロゲン原子又は水素原子である。
Rmの炭素数1~5のアルキル基は、炭素数1~5の直鎖状または分岐鎖状のアルキル基が好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。
炭素数1~5のハロゲン化アルキル基は、前記炭素数1~5のアルキル基の水素原子の一部または全部がハロゲン原子で置換された基である。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。ハロゲン化アルキル基におけるハロゲン原子としては、特にフッ素原子が好ましい。
Rmとしては、水素原子、炭素数1~5のアルキル基又は炭素数1~5のフッ素化アルキル基が好ましく、工業上の入手の容易さから、水素原子又はメチル基が最も好ましい。
La1における2価の連結基としては、特に限定されないが、置換基を有してもよい2価の炭化水素基、及びヘテロ原子を含む2価の連結基が好適なものとして挙げられ、それぞれ、上記Yax1における2価の連結基として例示した、置換基を有してもよい2価の炭化水素基、ヘテロ原子を含む2価の連結基と同様である。
上記の中でも、La1としては、エステル結合[-C(=O)-O-、-O-C(=O)-]、エーテル結合(-O-)、直鎖状若しくは分岐鎖状のアルキレン基、芳香族炭化水素基又はこれらの組合せ、あるいは単結合であることが好ましい。これらの中でも、La1としては、エステル結合[-C(=O)-O-、-O-C(=O)-]、単結合であることがより好ましく、エステル結合[-C(=O)-O-、-O-C(=O)-]であることがさらに好ましい。
Ra050における2価の炭化水素基は、脂肪族炭化水素基であってもよく、芳香族炭化水素基であってもよい。
該脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。該脂肪族炭化水素基は、飽和であってもよく不飽和であってもよく、通常は飽和であることが好ましい。
前記脂肪族炭化水素基としては、直鎖状若しくは分岐鎖状の脂肪族炭化水素基、又は構造中に環を含む脂肪族炭化水素基等が挙げられる。
該直鎖状の脂肪族炭化水素基は、炭素原子数が1~10であることが好ましく、炭素原子数1~6がより好ましく、炭素原子数1~4がさらに好ましく、炭素原子数1~3が最も好ましい。
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基[-CH2-]、エチレン基[-(CH2)2-]、トリメチレン基[-(CH2)3-]、テトラメチレン基[-(CH2)4-]、ペンタメチレン基[-(CH2)5-]等が挙げられる。
該分岐鎖状の脂肪族炭化水素基は、炭素原子数が2~10であることが好ましく、炭素原子数3~6がより好ましく、炭素原子数3又は4がさらに好ましく、炭素原子数3が最も好ましい。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等のアルキルメチレン基;-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-等のアルキルエチレン基;-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-等のアルキルトリメチレン基;-CH(CH3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2-等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素原子数1~5の直鎖状のアルキル基が好ましい。
該構造中に環を含む脂肪族炭化水素基としては、環構造中にヘテロ原子を含む置換基を含んでもよい環状の脂肪族炭化水素基(脂肪族炭化水素環から水素原子2個を除いた基)、前記環状の脂肪族炭化水素基が直鎖状又は分岐鎖状の脂肪族炭化水素基の末端に結合した基、前記環状の脂肪族炭化水素基が直鎖状又は分岐鎖状の脂肪族炭化水素基の途中に介在する基などが挙げられる。前記の直鎖状又は分岐鎖状の脂肪族炭化水素基としては前記と同様のものが挙げられる。
環状の脂肪族炭化水素基は、炭素原子数が3~20であることが好ましく、炭素原子数3~12であることがより好ましい。
環状の脂肪族炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから2個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数3~6のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから2個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数7~12のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等が挙げられる。
前記置換基としてのアルキル基としては、炭素原子数1~5のアルキル基が好ましく、メチル基、エチル基、プロピル基、n-ブチル基、tert-ブチル基であることが最も好ましい。
前記置換基としてのアルコキシ基としては、炭素原子数1~5のアルコキシ基が好ましく、メトキシ基、エトキシ基、n-プロポキシ基、iso-プロポキシ基、n-ブトキシ基、tert-ブトキシ基がより好ましく、メトキシ基、エトキシ基が最も好ましい。
前記置換基としてのハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられ、フッ素原子が好ましい。
前記置換基としてのハロゲン化アルキル基としては、前記アルキル基の水素原子の一部又は全部が前記ハロゲン原子で置換された基が挙げられる。
環状の脂肪族炭化水素基は、その環構造を構成する炭素原子の一部がヘテロ原子を含む置換基で置換されてもよい。該ヘテロ原子を含む置換基としては、-O-、-C(=O)-O-、-S-、-S(=O)2-、-S(=O)2-O-が好ましい。
該芳香族炭化水素基は、芳香環を少なくとも1つ有する炭化水素基である。
この芳香環は、4n+2個のπ電子をもつ環状共役系であれば特に限定されず、単環式でも多環式でもよい。芳香環の炭素原子数は5~30であることが好ましく、炭素原子数5~20がより好ましく、炭素原子数6~15がさらに好ましく、炭素原子数6~12が特に好ましい。ただし、該炭素原子数には、置換基における炭素原子数を含まないものとする。芳香環として具体的には、ベンゼン、ナフタレン、アントラセン、フェナントレン等の芳香族炭化水素環;前記芳香族炭化水素環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環等が挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。芳香族複素環として具体的には、ピリジン環、チオフェン環等が挙げられる。
芳香族炭化水素基として具体的には、前記芳香族炭化水素環又は芳香族複素環から水素原子2つを除いた基(アリーレン基又はヘテロアリーレン基);2以上の芳香環を含む芳香族化合物(例えばビフェニル、フルオレン等)から水素原子2つを除いた基;前記芳香族炭化水素環又は芳香族複素環から水素原子1つを除いた基(アリール基又はヘテロアリール基)の水素原子の1つがアルキレン基で置換された基(例えば、ベンジル基、フェネチル基、1-ナフチルメチル基、2-ナフチルメチル基、1-ナフチルエチル基、2-ナフチルエチル基等のアリールアルキル基におけるアリール基から水素原子をさらに1つ除いた基)等が挙げられる。前記のアリール基又はヘテロアリール基に結合するアルキレン基の炭素原子数は、1~4であることが好ましく、炭素原子数1~2であることがより好ましく、炭素原子数1であることが特に好ましい。
前記置換基としてのアルキル基としては、炭素原子数1~5のアルキル基が好ましく、メチル基、エチル基、プロピル基、n-ブチル基、tert-ブチル基であることが最も好ましい。
前記置換基としてのアルコキシ基、ハロゲン原子及びハロゲン化アルキル基としては、前記環状の脂肪族炭化水素基が有する水素原子を置換する置換基として例示したものが挙げられる。
上記の中でも、Ra050は、構造中に環を含む脂肪族炭化水素基が好ましく、環構造中にヘテロ原子を含む置換基を含んでもよい環状の脂肪族炭化水素基がより好ましく、多環式基又は単環式基である、置換基を有してもよい脂環式炭化水素基がさらに好ましい。
あるいは、上記の中でも、Ra050は、芳香族炭化水素基が好ましい。
La0における2価の連結基としては、酸素原子(エーテル結合:-O-)、エステル結合(-C(=O)-O-)、オキシカルボニル基(-O-C(=O)-)、アミド結合(-C(=O)-NH-)、カルボニル基(-C(=O)-)、カーボネート結合(-O-C(=O)-O-)等の非炭化水素系の酸素原子含有連結基;該非炭化水素系の酸素原子含有連結基とアルキレン基との組み合わせ等が挙げられる。この組み合わせに、さらにスルホニル基(-SO2-)が連結されていてもよい。
かかる2価の連結基としては、例えば下記一般式(L-al-1)~(L-al-8)でそれぞれ表される連結基が挙げられる。なお、下記一般式(L-al-1)~(L-al-8)において、上記式(a5-1)中のRa050と結合するのが、下記一般式(L-al-1)~(L-al-8)中のV’101である。
V’101およびV’102におけるアルキレン基として、具体的には、メチレン基[-CH2-];-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等のアルキルメチレン基;エチレン基[-CH2CH2-];-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-等のアルキルエチレン基;トリメチレン基(n-プロピレン基)[-CH2CH2CH2-];-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-等のアルキルトリメチレン基;テトラメチレン基[-CH2CH2CH2CH2-];-CH(CH3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2-等のアルキルテトラメチレン基;ペンタメチレン基[-CH2CH2CH2CH2CH2-]等が挙げられる。
また、V’101又はV’102における前記アルキレン基における一部のメチレン基が、炭素原子数5~10の2価の脂肪族環式基で置換されていてもよい。当該脂肪族環式基は、前記式(a1-r-1)中のRa’3の環状の脂肪族炭化水素基(単環式の脂肪族炭化水素基、多環式の脂肪族炭化水素基)から水素原子をさらに1つ除いた2価の基が好ましく、シクロへキシレン基、1,5-アダマンチレン基または2,6-アダマンチレン基がより好ましい。
Ya0における2価の連結基としては、特に限定されないが、置換基を有してもよい2価の炭化水素基、ヘテロ原子を含む2価の連結基等が好適に挙げられる。
Ya0における、置換基を有してもよい2価の炭化水素基、ヘテロ原子を含む2価の連結基については、上記Yax1における2価の連結基として例示した、置換基を有してもよい2価の炭化水素基、ヘテロ原子を含む2価の連結基と同様である。
上記の中でも、Ya0としては、直鎖若しくは分岐鎖状のアルキレン基、又は単結合が好ましく、単結合がより好ましい。
Ra051及びRa052におけるフッ素化アルキル基としては、それぞれ、炭素数1~5の直鎖状若しくは分岐鎖状のフッ素化アルキル基が好ましく、トリフルオロメチル基がより好ましい。
前記式(a5-1)中、SO3 -に隣接する炭素原子に結合するRa051及びRa052のうち、少なくとも一方はフッ素原子であることが、酸強度の観点から好ましい。
前記式(a5-1)中、M’m+は、m価のオニウムカチオンを表す。この中でも、M’m+は、スルホニウムカチオン、ヨードニウムカチオンが好ましい。mは、1以上の整数である。
R201~R207におけるアルキル基としては、鎖状又は環状のアルキル基であって、炭素原子数1~30のものが好ましい。
R201~R207におけるアルケニル基としては、炭素原子数が2~10であることが好ましい。
R201~R207、およびR210が有していてもよい置換基としては、例えば、アルキル基、ハロゲン原子、ハロゲン化アルキル基、カルボニル基、シアノ基、アミノ基、アリール基、下記の一般式(ca-r-1)~(ca-r-7)でそれぞれ表される基等が挙げられる。
該環式基は、環状の炭化水素基であることが好ましく、該環状の炭化水素基は、芳香族炭化水素基であってもよく、脂肪族炭化水素基であってもよい。脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。また、脂肪族炭化水素基は、飽和であってもよく、不飽和であってもよく、通常は飽和であることが好ましい。
R’201における芳香族炭化水素基が有する芳香環として具体的には、ベンゼン、フルオレン、ナフタレン、アントラセン、フェナントレン、ビフェニル、又はこれらの芳香環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環などが挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。
R’201における芳香族炭化水素基として具体的には、前記芳香環から水素原子を1つ除いた基(アリール基:例えばフェニル基、ナフチル基など)、前記芳香環の水素原子の1つがアルキレン基で置換された基(例えばベンジル基、フェネチル基、1-ナフチルメチル基、2-ナフチルメチル基、1-ナフチルエチル基、2-ナフチルエチル基等のアリールアルキル基など)等が挙げられる。前記アルキレン基(アリールアルキル基中のアルキル鎖)の炭素原子数は、1~4であることが好ましく、炭素原子数1~2がより好ましく、炭素原子数1が特に好ましい。
この構造中に環を含む脂肪族炭化水素基としては、脂環式炭化水素基(脂肪族炭化水素環から水素原子を1個除いた基)、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の末端に結合した基、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の途中に介在する基などが挙げられる。
前記脂環式炭化水素基は、炭素原子数が3~20であることが好ましく、3~12であることがより好ましい。
前記脂環式炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから1個以上の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数3~6のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから1個以上の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数7~30のものが好ましい。中でも、該ポリシクロアルカンとしては、アダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等の架橋環系の多環式骨格を有するポリシクロアルカン;ステロイド骨格を有する環式基等の縮合環系の多環式骨格を有するポリシクロアルカンがより好ましい。
直鎖状の脂肪族炭化水素基としては、直鎖状のアルキレン基が好ましく、具体的には、メチレン基[-CH2-]、エチレン基[-(CH2)2-]、トリメチレン基[-(CH2)3-]、テトラメチレン基[-(CH2)4-]、ペンタメチレン基[-(CH2)5-]等が挙げられる。
分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等のアルキルメチレン基;-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-等のアルキルエチレン基;-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-等のアルキルトリメチレン基;-CH(CH3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2-等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素原子数1~5の直鎖状のアルキル基が好ましい。
B”としては、炭素原子数1~5のアルキレン基または-O-が好ましく、炭素原子数1~5のアルキレン基がより好ましく、メチレン基がさらに好ましい。
置換基としてのアルキル基としては、炭素原子数1~5のアルキル基が好ましく、メチル基、エチル基、プロピル基、n-ブチル基、tert-ブチル基が最も好ましい。
置換基としてのアルコキシ基としては、炭素原子数1~5のアルコキシ基が好ましく、メトキシ基、エトキシ基、n-プロポキシ基、iso-プロポキシ基、n-ブトキシ基、tert-ブトキシ基がより好ましく、メトキシ基、エトキシ基が最も好ましい。
置換基としてのハロゲン原子としては、フッ素原子が好ましい。
置換基としてのハロゲン化アルキル基としては、炭素原子数1~5のアルキル基、たとえばメチル基、エチル基、プロピル基、n-ブチル基、tert-ブチル基等の水素原子の一部または全部が前記ハロゲン原子で置換された基が挙げられる。
置換基としてのカルボニル基は、環状の炭化水素基を構成するメチレン基(-CH2-)を置換する基である。
R’201の鎖状のアルキル基としては、直鎖状又は分岐鎖状のいずれでもよい。
直鎖状のアルキル基としては、炭素原子数が1~20であることが好ましく、炭素原子数1~15であることがより好ましく、炭素原子数1~10が最も好ましい。
分岐鎖状のアルキル基としては、炭素原子数が3~20であることが好ましく、炭素原子数3~15であることがより好ましく、炭素原子数3~10が最も好ましい。具体的には、例えば、1-メチルエチル基、1-メチルプロピル基、2-メチルプロピル基、1-メチルブチル基、2-メチルブチル基、3-メチルブチル基、1-エチルブチル基、2-エチルブチル基、1-メチルペンチル基、2-メチルペンチル基、3-メチルペンチル基、4-メチルペンチル基などが挙げられる。
R’201の鎖状のアルケニル基としては、直鎖状又は分岐鎖状のいずれでもよく、炭素原子数が2~10であることが好ましく、炭素原子数2~5がより好ましく、炭素原子数2~4がさらに好ましく、炭素原子数3が特に好ましい。直鎖状のアルケニル基としては、例えば、ビニル基、プロペニル基(アリル基)、ブチニル基などが挙げられる。分岐鎖状のアルケニル基としては、例えば、1-メチルビニル基、2-メチルビニル基、1-メチルプロペニル基、2-メチルプロペニル基などが挙げられる。
鎖状のアルケニル基としては、上記の中でも、直鎖状のアルケニル基が好ましく、ビニル基、プロペニル基がより好ましく、ビニル基が特に好ましい。
R210におけるアリール基としては、炭素原子数6~20の無置換のアリール基が挙げられ、フェニル基、ナフチル基が好ましい。
R210におけるアルキル基としては、鎖状又は環状のアルキル基であって、炭素原子数1~30のものが好ましい。
R210におけるアルケニル基としては、炭素原子数が2~10であることが好ましい。
R210における、置換基を有してもよい-SO2-含有環式基としては、「-SO2-含有多環式基」が好ましく、上記一般式(b5-r-1)で表される基がより好ましい。
以下の式中、Rαは、水素原子、メチル基又はトリフルオロメチル基を示す。m及びM’m+は、上記一般式(a5-1)中のm及びM’m+と同様である。
(A1)成分が構成単位(a5)を有する場合、(A1)成分中の構成単位(a5)の割合は、(A1)成分を構成する全構成単位の合計(100モル%)に対して、5~25モル%が好ましく、10~20モル%がより好ましく、12~20モル%がさらに好ましい。
構成単位(a5)の割合が、前記の好ましい範囲の下限値以上であることにより、更なる高感度化、解像性の向上を実現しやすくなる。一方、前記の好ましい範囲の上限値以下であることにより、他の構成単位とのバランスをとりやすくなる。
構成単位(a8)は、下記一般式(a8-1)で表される化合物から誘導される構成単位である。
重合性基含有基としては、例えば、化学式:C(RX11)(RX12)=C(RX13)-Yax0-で表される基が好適に挙げられる。
この化学式中、RX11、RX12及びRX13は、それぞれ、水素原子、炭素原子数1~5のアルキル基又は炭素原子数1~5のハロゲン化アルキル基であり、Yax0は、単結合または2価の連結基である。
Yax2とW2とが形成する縮合環は、置換基を有してもよい。
下記の式中、Rαは、水素原子、メチル基又はトリフルオロメチル基を示す。
(A1)成分における構成単位(a8)の割合は、(A1)成分を構成する全構成単位の合計(100モル%)に対して、0~50モル%であることが好ましく、0~30モル%であることがより好ましい。
あるいは、かかる(A1)成分は、構成単位(a1)を誘導するモノマーと、任意の構成単位(例えば、構成単位(a10等)を誘導するモノマーと、を重合溶媒に溶解し、ここに、上記のようなラジカル重合開始剤を加えて重合し、その後、脱保護反応を行うことにより製造することができる。
なお、重合の際に、例えば、HS-CH2-CH2-CH2-C(CF3)2-OHのような連鎖移動剤を併用して用いることにより、末端に-C(CF3)2-OH基を導入してもよい。このように、アルキル基の水素原子の一部がフッ素原子で置換されたヒドロキシアルキル基が導入された共重合体は、現像欠陥の低減やLER(ラインエッジラフネス:ライン側壁の不均一な凹凸)の低減に有効である。
(A1)成分のMwがこの範囲の好ましい上限値以下であると、レジストとして用いるのに充分なレジスト溶剤への溶解性があり、この範囲の好ましい下限値以上であると、耐ドライエッチング性やレジストパターン断面形状が良好である。
(A1)成分の分散度(Mw/Mn)は、特に限定されず、1.0~4.0が好ましく、1.0~3.0がより好ましく、1.0~2.0が特に好ましい。なお、Mnは数平均分子量を示す。
本実施形態のレジスト組成物は、(A)成分として、前記(A1)成分に該当しない、酸の作用により現像液に対する溶解性が変化する基材成分(以下「(A2)成分」という。)を併用してもよい。
(A2)成分としては、特に限定されず、化学増幅型レジスト組成物用の基材成分として従来から知られている多数のものから任意に選択して用いればよい。
(A2)成分は、高分子化合物又は低分子化合物の1種を単独で用いてもよく2種以上を組み合わせて用いてもよい。
本実施形態のレジスト組成物は、さらに、露光により酸を発生する酸発生剤成分(B)を含有することが好ましい。
(B)成分としては、特に限定されず、これまで化学増幅型レジスト組成物用の酸発生剤として提案されているものを用いることができる。
このような酸発生剤としては、ヨードニウム塩やスルホニウム塩などのオニウム塩系酸発生剤、オキシムスルホネート系酸発生剤;ビスアルキル又はビスアリールスルホニルジアゾメタン類、ポリ(ビススルホニル)ジアゾメタン類などのジアゾメタン系酸発生剤;ニトロベンジルスルホネート系酸発生剤、イミノスルホネート系酸発生剤、ジスルホン系酸発生剤など多種のものが挙げられる。
・(b-1)成分におけるアニオン
式(b-1)中、R101は、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基である。
該環式基は、環状の炭化水素基であることが好ましく、該環状の炭化水素基は、芳香族炭化水素基であってもよく、脂肪族炭化水素基であってもよい。脂肪族炭化水素基は、芳香族性を持たない炭化水素基を意味する。また、脂肪族炭化水素基は、飽和であることが好ましい。
R101における芳香族炭化水素基が有する芳香環として具体的には、ベンゼン、フルオレン、ナフタレン、アントラセン、フェナントレン、ビフェニル、又はこれらの芳香環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環などが挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。
R101における芳香族炭化水素基として具体的には、前記芳香環から水素原子を1つ除いた基(アリール基:例えば、フェニル基、ナフチル基など)、前記芳香環の水素原子の1つがアルキレン基で置換された基(例えば、ベンジル基、フェネチル基、1-ナフチルメチル基など)等が挙げられる。前記アルキレン基(アリールアルキル基中のアルキル鎖)の炭素原子数は、1~4であることが好ましく、1~2であることがより好ましく、1であることが特に好ましい。
この構造中に環を含む脂肪族炭化水素基としては、脂環式炭化水素基(脂肪族炭化水素環から水素原子を1個除いた基)、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の末端に結合した基、脂環式炭化水素基が直鎖状または分岐鎖状の脂肪族炭化水素基の途中に介在する基などが挙げられる。
前記脂環式炭化水素基は、炭素原子数が3~20であることが好ましく、3~12であることがより好ましい。
前記脂環式炭化水素基は、多環式基であってもよく、単環式基であってもよい。単環式の脂環式炭化水素基としては、モノシクロアルカンから1個以上の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素原子数3~6のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。多環式の脂環式炭化水素基としては、ポリシクロアルカンから1個以上の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素原子数7~30のものが好ましい。中でも、該ポリシクロアルカンとしては、アダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等の架橋環系の多環式骨格を有するポリシクロアルカン;ステロイド骨格を有する環式基等の縮合環系の多環式骨格を有するポリシクロアルカンがより好ましい。
脂環式炭化水素基に結合してもよい、分岐鎖状の脂肪族炭化水素基は、炭素原子数が2~10であることが好ましく、3~6がより好ましく、3又は4がさらに好ましく、3が最も好ましい。分岐鎖状の脂肪族炭化水素基としては、分岐鎖状のアルキレン基が好ましく、具体的には、-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等のアルキルメチレン基;-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-等のアルキルエチレン基;-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-等のアルキルトリメチレン基;-CH(CH3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2-等のアルキルテトラメチレン基などのアルキルアルキレン基等が挙げられる。アルキルアルキレン基におけるアルキル基としては、炭素原子数1~5の直鎖状のアルキル基が好ましい。
置換基としてのアルキル基としては、炭素原子数1~5のアルキル基が好ましい。
置換基としてのアルコキシ基としては、炭素原子数1~5のアルコキシ基が好ましく、メトキシ基、エトキシ基、n-プロポキシ基、iso-プロポキシ基、n-ブトキシ基、tert-ブトキシ基がより好ましく、メトキシ基、エトキシ基が最も好ましい。
置換基としてのハロゲン原子としては、フッ素原子、臭素原子、ヨウ素原子が好ましい。
置換基としてのハロゲン化アルキル基としては、炭素原子数1~5のアルキル基、例えばメチル基、エチル基、プロピル基、n-ブチル基、tert-ブチル基等の水素原子の一部または全部が前記ハロゲン原子で置換された基が挙げられる。
置換基としてのカルボニル基は、環状の炭化水素基を構成するメチレン基(-CH2-)を置換する基である。
前記縮合環式基の置換基としてのアルキル基、アルコキシ基、ハロゲン原子、ハロゲン化アルキル基は、上記R101における環式基の置換基として挙げたものと同様のものが挙げられる。
前記縮合環式基の置換基としての芳香族炭化水素基としては、芳香環から水素原子を1つ除いた基(アリール基:例えば、フェニル基、ナフチル基など)、前記芳香環の水素原子の1つがアルキレン基で置換された基(例えば、ベンジル基、フェネチル基、1-ナフチルメチル基、2-ナフチルメチル基、1-ナフチルエチル基、2-ナフチルエチル基等のアリールアルキル基など)、上記式(r-hr-1)~(r-hr-6)でそれぞれ表される複素環式基等が挙げられる。
前記縮合環式基の置換基としての脂環式炭化水素基としては、シクロペンタン、シクロヘキサン等のモノシクロアルカンから1個の水素原子を除いた基;アダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等のポリシクロアルカンから1個の水素原子を除いた基;前記一般式(a2-r-1)~(a2-r-7)でそれぞれ表されるラクトン含有環式基;前記一般式(b5-r-1)~(b5-r-4)でそれぞれ表される-SO2-含有環式基;前記式(r-hr-7)~(r-hr-16)でそれぞれ表される複素環式基等が挙げられる。
R101の鎖状のアルキル基としては、直鎖状又は分岐鎖状のいずれでもよい。
直鎖状のアルキル基としては、炭素原子数が1~20であることが好ましく、1~15であることがより好ましく、1~10が最も好ましい。
分岐鎖状のアルキル基としては、炭素原子数が3~20であることが好ましく、3~15であることがより好ましく、3~10が最も好ましい。具体的には、例えば、1-メチルエチル基、1-メチルプロピル基、2-メチルプロピル基、1-メチルブチル基、2-メチルブチル基、3-メチルブチル基、1-エチルブチル基、2-エチルブチル基、1-メチルペンチル基、2-メチルペンチル基、3-メチルペンチル基、4-メチルペンチル基などが挙げられる。
R101の鎖状のアルケニル基としては、直鎖状又は分岐鎖状のいずれでもよく、炭素原子数が2~10であることが好ましく、2~5がより好ましく、2~4がさらに好ましく、3が特に好ましい。直鎖状のアルケニル基としては、例えば、ビニル基、プロペニル基(アリル基)、ブチニル基などが挙げられる。分岐鎖状のアルケニル基としては、例えば、1-メチルビニル基、2-メチルビニル基、1-メチルプロペニル基、2-メチルプロペニル基などが挙げられる。
鎖状のアルケニル基としては、上記の中でも、直鎖状のアルケニル基が好ましく、ビニル基、プロペニル基がより好ましく、ビニル基が特に好ましい。
Y101が酸素原子を含む2価の連結基である場合、該Y101は、酸素原子以外の原子を含有してもよい。酸素原子以外の原子としては、例えば炭素原子、水素原子、硫黄原子、窒素原子等が挙げられる。
酸素原子を含む2価の連結基としては、例えば下記一般式(y-al-1)~(y-al-7)でそれぞれ表される連結基が挙げられる。なお、下記一般式(y-al-1)~(y-al-7)において、上記式(b-1)中のR101と結合するのが、下記一般式(y-al-1)~(y-al-7)中のV’101である。
V’101およびV’102におけるアルキレン基として、具体的には、メチレン基[-CH2-];-CH(CH3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-等のアルキルメチレン基;エチレン基[-CH2CH2-];-CH(CH3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-等のアルキルエチレン基;トリメチレン基(n-プロピレン基)[-CH2CH2CH2-];-CH(CH3)CH2CH2-、-CH2CH(CH3)CH2-等のアルキルトリメチレン基;テトラメチレン基[-CH2CH2CH2CH2-];-CH(CH3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2-等のアルキルテトラメチレン基;ペンタメチレン基[-CH2CH2CH2CH2CH2-]等が挙げられる。
また、V’101又はV’102における前記アルキレン基における一部のメチレン基が、炭素原子数5~10の2価の脂肪族環式基で置換されていてもよい。当該脂肪族環式基は、前記式(a1-r-1)中のRa’3の環状の脂肪族炭化水素基(単環式の脂肪族炭化水素基、多環式の脂肪族炭化水素基)から水素原子をさらに1つ除いた2価の基が好ましく、シクロへキシレン基、1,5-アダマンチレン基または2,6-アダマンチレン基がより好ましい。
R”103における置換基を有してもよい鎖状のアルケニル基は、前記式(b-1)中のR101における鎖状のアルケニル基として例示した基であることが好ましい。
式(b-2)中、R104、R105は、それぞれ独立に、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、または置換基を有してもよい鎖状のアルケニル基であり、それぞれ、式(b-1)中のR101と同様のものが挙げられる。ただし、R104、R105は、相互に結合して環を形成していてもよい。
R104、R105は、置換基を有してもよい鎖状のアルキル基が好ましく、直鎖状若しくは分岐鎖状のアルキル基、又は直鎖状若しくは分岐鎖状のフッ素化アルキル基であることがより好ましい。
該鎖状のアルキル基の炭素原子数は、1~10であることが好ましく、より好ましくは炭素原子数1~7、さらに好ましくは炭素原子数1~3である。R104、R105の鎖状のアルキル基の炭素原子数は、上記炭素原子数の範囲内において、レジスト用溶剤への溶解性も良好である等の理由により、小さいほど好ましい。また、R104、R105の鎖状のアルキル基においては、フッ素原子で置換されている水素原子の数が多いほど、酸の強度が強くなり、また、250nm以下の高エネルギー光や電子線に対する透明性が向上するため好ましい。前記鎖状のアルキル基中のフッ素原子の割合、すなわちフッ素化率は、好ましくは70~100%、さらに好ましくは90~100%であり、最も好ましくは、全ての水素原子がフッ素原子で置換されたパーフルオロアルキル基である。
式(b-2)中、V102、V103は、それぞれ独立に、単結合、アルキレン基、またはフッ素化アルキレン基であり、それぞれ、式(b-1)中のV101と同様のものが挙げられる。
式(b-2)中、L101、L102は、それぞれ独立に単結合又は酸素原子である。
式(b-3)中、R106~R108は、それぞれ独立に、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、それぞれ、式(b-1)中のR101と同様のものが挙げられる。
式(b-3)中、L103~L105は、それぞれ独立に、単結合、-CO-又は-SO2-である。
前記の式(b-1)、式(b-2)、式(b-3)中、M’m+は、m価のオニウムカチオンを表す。この中でも、スルホニウムカチオン、ヨードニウムカチオンが好ましい。mは、1以上の整数である。
前記の式(b-1)、式(b-2)、式(b-3)中におけるM’m+としては、前記式(a5-1)におけるM’m+と同様である。
レジスト組成物中、(B)成分の含有量は、(A)成分100質量部に対して、50質量部未満が好ましく、10~40質量部がより好ましい。
(B)成分の含有量を、前記の好ましい範囲とすることで、パターン形成が十分に行われる。また、レジスト組成物の各成分を有機溶剤に溶解した際、均一な溶液が得られやすく、レジスト組成物としての保存安定性が良好となるため好ましい。
本実施形態のレジスト組成物は、(A)成分に加えて、露光により発生する酸をトラップ(すなわち、酸の拡散を制御)する塩基成分((D)成分)を含有してもよい。(D)成分は、レジスト組成物において露光により発生する酸をトラップするクエンチャー(酸拡散制御剤)として作用するものである。
(D)成分としては、例えば、露光により分解して酸拡散制御性を失う光崩壊性塩基(D1)(以下「(D1)成分」という。)、該(D1)成分に該当しない含窒素有機化合物(D2)(以下「(D2)成分」という。)等が挙げられる。これらの中でも、高感度化、ラフネス低減、塗布欠陥の発生の抑制の特性をいずれも高められやすいことから、光崩壊性塩基((D1)成分)が好ましい。
(D1)成分としては、露光により分解して酸拡散制御性を失うものであれば特に限定されず、下記一般式(d1-1)で表される化合物(以下「(d1-1)成分」という。)、下記一般式(d1-2)で表される化合物(以下「(d1-2)成分」という。)及び下記一般式(d1-3)で表される化合物(以下「(d1-3)成分」という。)からなる群より選ばれる1種以上の化合物が好ましい。
(d1-1)~(d1-3)成分は、レジスト膜の露光部においては分解して酸拡散制御性(塩基性)を失うためクエンチャーとして作用せず、レジスト膜の未露光部においてクエンチャーとして作用する。
・・アニオン部
式(d1-1)中、Rd1は、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、それぞれ前記R’201と同様のものが挙げられる。
これらのなかでも、Rd1としては、置換基を有してもよい芳香族炭化水素基、置換基を有してもよい脂肪族環式基、又は置換基を有してもよい鎖状のアルキル基が好ましい。これらの基が有していてもよい置換基としては、水酸基、オキソ基、アルキル基、アリール基、フッ素原子、フッ素化アルキル基、上記一般式(a2-r-1)~(a2-r-8)でそれぞれ表されるラクトン含有環式基、エーテル結合、エステル結合、またはこれらの組み合わせが挙げられる。エーテル結合やエステル結合を置換基として含む場合、アルキレン基を介していてもよく、この場合の置換基としては、上記式(y-al-1)~(y-al-5)でそれぞれ表される連結基が好ましい。なお、Rd1における芳香族炭化水素基、脂肪族環式基、又は鎖状のアルキル基が、置換基として、上記一般式(y-al-1)~(y-al-7)でそれぞれ表される連結基を有する場合、上記一般式(y-al-1)~(y-al-7)において、式(d3-1)中のRd1における芳香族炭化水素基、脂肪族環式基、又は鎖状のアルキル基を構成する炭素原子に結合するのが、上記一般式(y-al-1)~(y-al-7)中のV’101である。
前記芳香族炭化水素基としては、フェニル基、ナフチル基、ビシクロオクタン骨格を含む多環構造(ビシクロオクタン骨格とこれ以外の環構造とからなる多環構造)が好適に挙げられる。
前記脂肪族環式基としては、アダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等のポリシクロアルカンから1個以上の水素原子を除いた基であることがより好ましい。
前記鎖状のアルキル基としては、炭素原子数が1~10であることが好ましく、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の直鎖状のアルキル基;1-メチルエチル基、1-メチルプロピル基、2-メチルプロピル基、1-メチルブチル基、2-メチルブチル基、3-メチルブチル基、1-エチルブチル基、2-エチルブチル基、1-メチルペンチル基、2-メチルペンチル基、3-メチルペンチル基、4-メチルペンチル基等の分岐鎖状のアルキル基が挙げられる。
式(d1-1)中、Mm+は、m価の有機カチオンである。
Mm+の有機カチオンとしては、前記一般式(ca-1)~(ca-3)でそれぞれ表されるカチオンと同様のものが好適に挙げられ、前記一般式(ca-1)で表されるカチオンがより好ましく、前記式(ca-1-1)~(ca-1-84)でそれぞれ表されるカチオンがさらに好ましい。
(d1-1)成分は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
・・アニオン部
式(d1-2)中、Rd2は、置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、前記R’201と同様のものが挙げられる。
但し、Rd2における、S原子に隣接する炭素原子にはフッ素原子は結合していない(フッ素置換されていない)ものとする。これにより、(d1-2)成分のアニオンが適度な弱酸アニオンとなり、(D)成分としてのクエンチング能が向上する。
Rd2としては、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい脂肪族環式基であることが好ましく、置換基を有してもよい脂肪族環式基であることがより好ましい。
該脂肪族環式基としては、アダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等から1個以上の水素原子を除いた基(置換基を有してもよい);カンファーから1個以上の水素原子を除いた基であることがより好ましい。
式(d1-2)中、Mm+は、m価の有機カチオンであり、前記式(d1-1)中のMm+と同様である。
(d1-2)成分は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
・・アニオン部
式(d1-3)中、Rd3は置換基を有してもよい環式基、置換基を有してもよい鎖状のアルキル基、又は置換基を有してもよい鎖状のアルケニル基であり、前記R’201と同様のものが挙げられ、フッ素原子を含む環式基、鎖状のアルキル基、又は鎖状のアルケニル基であることが好ましい。中でも、フッ素化アルキル基が好ましく、前記Rd1のフッ素化アルキル基と同様のものがより好ましい。
なかでも、置換基を有してもよいアルキル基、アルコキシ基、アルケニル基、環式基であることが好ましい。
Rd4におけるアルキル基は、炭素原子数1~5の直鎖状又は分岐鎖状のアルキル基が好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。Rd4のアルキル基の水素原子の一部が水酸基、シアノ基等で置換されていてもよい。
Rd4におけるアルコキシ基は、炭素原子数1~5のアルコキシ基が好ましく、炭素原子数1~5のアルコキシ基として具体的には、メトキシ基、エトキシ基、n-プロポキシ基、iso-プロポキシ基、n-ブトキシ基、tert-ブトキシ基が挙げられる。なかでも、メトキシ基、エトキシ基が好ましい。
Yd1における2価の連結基としては、特に限定されないが、置換基を有してもよい2価の炭化水素基(脂肪族炭化水素基、芳香族炭化水素基)、ヘテロ原子を含む2価の連結基等が挙げられる。これらはそれぞれ、上記式(a2-1)中のYa21における2価の連結基についての説明のなかで挙げた、置換基を有してもよい2価の炭化水素基、ヘテロ原子を含む2価の連結基と同様のものが挙げられる。
Yd1としては、カルボニル基、エステル結合、アミド結合、アルキレン基又はこれらの組み合わせであることが好ましい。アルキレン基としては、直鎖状又は分岐鎖状のアルキレン基であることがより好ましく、メチレン基又はエチレン基であることがさらに好ましい。
式(d1-3)中、Mm+は、m価の有機カチオンであり、前記式(d1-1)中のMm+と同様である。
(d1-3)成分は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
レジスト組成物が(D1)成分を含有する場合、レジスト組成物中の(D1)成分の含有量は、(A)成分100質量部に対して、0.5~15質量部が好ましく、1~12質量部がより好ましく、2~10質量部がさらに好ましい。
(D1)成分全体のうち、(d1-1)成分の含有量は、50質量%以上であることが好ましく、70質量%以上であることが好ましく、90質量%以上であることがさらに好ましく、(D1)成分は化合物(d1-1)成分のみからなるものであってもよい。
前記の(d1-1)成分、(d1-2)成分の製造方法は、特に限定されず、公知の方法により製造することができる。
また、(d1-3)成分の製造方法は、特に限定されず、例えば、US2012-0149916号公報に記載の方法と同様にして製造される。
(D)成分としては、上記(D1)成分に該当しない含窒素有機化合物成分(以下「(D2)成分」という。)を含有してもよい。
(D2)成分としては、酸拡散制御剤として作用するもので、かつ、(D1)成分に該当しないものであれば特に限定されず、公知のものから任意に用いればよい。なかでも、脂肪族アミンが好ましく、この中でも特に第2級脂肪族アミンや第3級脂肪族アミンがより好ましい。
脂肪族アミンとは、1つ以上の脂肪族基を有するアミンであり、該脂肪族基は炭素原子数が1~12であることが好ましい。
脂肪族アミンとしては、アンモニアNH3の水素原子の少なくとも1つを、炭素原子数12以下のアルキル基もしくはヒドロキシアルキル基で置換したアミン(アルキルアミンもしくはアルキルアルコールアミン)又は環式アミンが挙げられる。
アルキルアミンおよびアルキルアルコールアミンの具体例としては、n-ヘキシルアミン、n-ヘプチルアミン、n-オクチルアミン、n-ノニルアミン、n-デシルアミン等のモノアルキルアミン;ジエチルアミン、ジ-n-プロピルアミン、ジ-n-ヘプチルアミン、ジ-n-オクチルアミン、ジシクロヘキシルアミン等のジアルキルアミン;トリメチルアミン、トリエチルアミン、トリ-n-プロピルアミン、トリ-n-ブチルアミン、トリ-n-ペンチルアミン、トリ-n-ヘキシルアミン、トリ-n-ヘプチルアミン、トリ-n-オクチルアミン、トリ-n-ノニルアミン、トリ-n-デシルアミン、トリ-n-ドデシルアミン等のトリアルキルアミン;ジエタノールアミン、トリエタノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、ジ-n-オクタノールアミン、トリ-n-オクタノールアミン等のアルキルアルコールアミンが挙げられる。これらの中でも、炭素原子数6~30のトリアルキルアミンがさらに好ましく、トリ-n-ペンチルアミン又はトリ-n-オクチルアミンが特に好ましい。
脂肪族単環式アミンとして、具体的には、ピペリジン、ピペラジン等が挙げられる。
脂肪族多環式アミンとしては、炭素原子数が6~10のものが好ましく、具体的には、1,5-ジアザビシクロ[4.3.0]-5-ノネン、1,8-ジアザビシクロ[5.4.0]-7-ウンデセン、ヘキサメチレンテトラミン、1,4-ジアザビシクロ[2.2.2]オクタン等が挙げられる。
芳香族アミンとしては、4-ジメチルアミノピリジン、ピロール、インドール、ピラゾール、イミダゾールまたはこれらの誘導体、トリベンジルアミン、2,6-ジイソプロピルアニリン、N-tert-ブトキシカルボニルピロリジン、2,6-ジ-tert-ブチルピリジン、2,6-ジ-tert-ブチルピリジン等が挙げられる。
レジスト組成物が(D2)成分を含有する場合、レジスト組成物中、(D2)成分の含有量は、(A)成分100質量部に対して、通常、0.01~5質量部の範囲で用いられる。上記範囲とすることにより、レジストパターン形状、引き置き経時安定性等が向上する。
本実施形態のレジスト組成物には、感度劣化の防止や、レジストパターン形状、引き置き経時安定性等の向上の目的で、任意の成分として、有機カルボン酸、並びにリンのオキソ酸及びその誘導体からなる群より選択される少なくとも1種の化合物(E)(以下「(E)成分」という)を含有させることができる。
有機カルボン酸として、具体的には、酢酸、マロン酸、クエン酸、リンゴ酸、コハク酸、安息香酸、サリチル酸等が挙げられ、その中でも、サリチル酸が好ましい。
リンのオキソ酸としては、リン酸、ホスホン酸、ホスフィン酸等が挙げられ、これらの中でも特にホスホン酸が好ましい。
レジスト組成物が(E)成分を含有する場合、(E)成分の含有量は、(A)成分100質量部に対して、0.01~5質量部が好ましく、0.05~3質量部がより好ましい。上記範囲とすることにより、リソグラフィー特性がより向上する。
本実施形態のレジスト組成物は、疎水性樹脂としてフッ素添加剤成分(以下「(F)成分」という)を含有する。(F)成分は、レジスト膜に撥水性を付与するために使用され、(A)成分とは別の樹脂として用いられることでリソグラフィー特性を向上させることができる。
本実施形態において、(F)成分は、下記一般式(f0-1)で表される化合物から誘導される構成単位(f0)を有する含フッ素高分子化合物(F0)を含有する。
構成単位(f0)は、下記一般式(f0-1)で表される化合物から誘導される構成単位である。
構成単位(f0)おいては、該重合性基における多重結合が開裂して主鎖を形成している。
上記式中、RX11~RX22は、それぞれ独立に、水素原子、炭素数1~5のアルキル基又は炭素数1~5のハロゲン化アルキル基である。上記式中、Rfx11及びRfx12は、それぞれ独立に、炭素数1~5のフッ素化アルキル基である。
Arにおける芳香環として具体的には、ベンゼン、フルオレン、ナフタレン、アントラセン、フェナントレン、ビフェニル、又はこれらの芳香環を構成する炭素原子の一部がヘテロ原子で置換された芳香族複素環などが挙げられる。芳香族複素環におけるヘテロ原子としては、酸素原子、硫黄原子、窒素原子等が挙げられる。なかでも、Arとしては、合成容易性の観点から、ベンゼン環が好ましい。
前記式(xf-r-1)中、m22は1~3の整数が好ましく、2又は3がより好ましい。
前記式(xf-r-1)中、レジスト組成物のレジスト溶剤への溶解性の観点から、m32は、0~3の整数が好ましく、0~2の整数がより好ましく、0又は1が更に好ましく、0が特に好ましい。
m32が2以上の整数の場合、複数のRf032はそれぞれ同じでもよく、異なってもよい。
なかでも、Lf022における2価の連結基としては、*1-C(=O)-O-*2が好ましい。式中、*1は式(xf-r-1)中のAr2と結合する結合手であり、*2は前記式(f0-1)中のArと結合する結合手である。
前記式(f0-1)中、Xfがヨウ素原子の場合、m1は1~3の整数が好ましく、2又は3がより好ましい。
前記式(f0-1)中、Xfがヨウ素原子を含有する置換基である場合、m1は1~3の整数が好ましく、1又は2がより好ましく、1が更に好ましい。
前記式(f0-1)中、レジスト組成物のレジスト溶剤への溶解性の観点から、m2は、0~3の整数が好ましく、0~2の整数がより好ましく、0又は1が更に好ましく、0が特に好ましい。
前記式(Lf01-01-2)及び(Lf01-01-3)中、Zにおける脂肪族環としては、ノルボルネン環又はシクロヘキサン環が好ましい。
前記式(Lf01-02-2)及び(Lf01-02-3)中、Zにおける脂肪族環としては、ノルボルネン環又はシクロヘキサン環が好ましい。
炭素数1~12の直鎖状のフッ素化アルキル基として、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基の水素原子の一部または全部がフッ素原子で置換された基が挙げられる。炭素数1~12の分岐鎖状のフッ素化アルキル基として、具体的には、1-メチルエチル基、1,1-ジメチルエチル基、1-メチルプロピル基、2-メチルプロピル基、1-メチルブチル基、2-メチルブチル基、3-メチルブチル基、1-エチルブチル基、2-エチルブチル基、1-メチルペンチル基、2-メチルペンチル基、3-メチルペンチル基、4-メチルペンチル基の水素原子の一部または全部がフッ素原子で置換された基が挙げられる。
炭化水素基としては、直鎖状もしくは分岐鎖状のアルキル基、又は環状の炭化水素基が挙げられる。
該直鎖状のアルキル基として、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基が挙げられる。
該分岐鎖状のアルキル基として、具体的には、1-メチルエチル基、1,1-ジメチルエチル基、1-メチルプロピル基、2-メチルプロピル基、1-メチルブチル基、2-メチルブチル基、3-メチルブチル基、1-エチルブチル基、2-エチルブチル基、1-メチルペンチル基、2-メチルペンチル基、3-メチルペンチル基、4-メチルペンチル基等が挙げられる。
単環式基である脂肪族炭化水素基としては、モノシクロアルカンから1個の水素原子を除いた基が好ましい。該モノシクロアルカンとしては、炭素数3~6のものが好ましく、具体的にはシクロペンタン、シクロヘキサン等が挙げられる。
多環式基である脂肪族炭化水素基としては、ポリシクロアルカンから1個の水素原子を除いた基が好ましく、該ポリシクロアルカンとしては、炭素数7~12のものが好ましく、具体的にはアダマンタン、ノルボルナン、イソボルナン、トリシクロデカン、テトラシクロドデカン等が挙げられる。
前記式(f0-1-1)中、m11は1~3の整数が好ましく、2又は3がより好ましい。
前記式(f0-1-1)中、Rf03は、前記式(f0-1)中のRf03と同様である。
前記式(f0-1-1)中、m21は、0~3の整数が好ましく、0~2の整数がより好ましく、0又は1が更に好ましく、0が特に好ましい。
前記式(f0-1-1)中、Rf011における炭素数1~12のフッ素化アルキル基は、前記式(f0-1)中のRf01における炭素数1~12のフッ素化アルキル基と同様であり、炭素数1~5のフッ素化アルキル基が好ましく、トリフルオロメチル基がより好ましい。
前記式(f0-1-1)中、Rf021におけるフッ素原子を有しても良い炭素数1~12の有機基は、前記式(f0-1)中のRf02におけるフッ素原子を有しても良い炭素数1~12の有機基と同様であり、炭素数1~12のフッ素化アルキル基であることが好ましく、炭素数1~5のフッ素化アルキル基がより好ましく、トリフルオロメチル基であることが更に好ましい。
前記式(f0-1-1)中、n11は1又は2が好ましく、1がより好ましい。
前記式(f0-1-2)中、Rf031及びRf032におけるヨウ素原子以外の置換基は、前記式(f0-1)中の前記式(f0-1)中のRf03におけるヨウ素原子以外の置換基と同様である。
前記式(f0-1-2)中、m12及びm32は、それぞれ独立に、0~3の整数が好ましく、0~2の整数がより好ましく、0又は1が更に好ましく、0が特に好ましい。
前記式(f0-1-2)中、m22は1~3の整数が好ましく、1又は2がより好ましく、1が更に好ましい。
前記式(f0-1-2)中、Lf021における(n1+1)価の連結基は、前記式(f0-1)中のLf01における(n1+1)価の連結基と同様であり、カルボニルオキシ基を含む有機基が好ましく、前記一般式(Lf01-01)~(Lf01-03)のいずれかで表される基がより好ましい。
前記式(f0-1-2)中、Rf012における炭素数1~12のフッ素化アルキル基は、前記式(f0-1)中のRf01における炭素数1~12のフッ素化アルキル基と同様であり、炭素数1~5のフッ素化アルキル基が好ましく、トリフルオロメチル基がより好ましい。
前記式(f0-1-2)中、Rf022におけるフッ素原子を有しても良い炭素数1~12の有機基は、前記式(f0-1)中のRf02におけるフッ素原子を有しても良い炭素数1~12の有機基と同様であり、炭素数1~12のフッ素化アルキル基であることが好ましく、炭素数1~5のフッ素化アルキル基がより好ましく、トリフルオロメチル基であることが更に好ましい。
前記式(f0-1-2)中、n21は1又は2が好ましく、1がより好ましい。
(F0)成分中の構成単位(f0)の割合は、(F0)成分を構成する全構成単位の合計(100モル%)に対して、40~90モル%が好ましく、45~85モル%がより好ましく、50~75モル%が更に好ましい。
構成単位(f0)の割合を上記の好ましい範囲の下限値以上とすることにより、感度を高めやすく、LWRを低減しやすい。一方、構成単位(f0)の割合を上記の好ましい範囲の上限値以下とすることにより、レジスト組成物の現像液に対する溶解性を向上し、現像後の欠陥特性が良好なパターンを形成しやすい。
(A1)成分は、上述した構成単位(a1)に加え、必要に応じてその他構成単位を有するものでもよい。
その他構成単位としては、例えば、酸の作用により極性が増大する酸分解性基を含む構成単位(f1);ラクトン含有環式基を含む構成単位(f2);前記一般式(a10-1)で表される構成単位(f3)などが挙げられる。
構成単位(f1)は、酸の作用により極性が増大する酸分解性基を含む構成単位であり、前記(A1)成分における構成単位(a1)と同様である。
なかでも、構成単位(f1)としては、前記一般式(a1-1)、(a1-2)又は(a1-3)で表される構成単位が好ましい。
(F0)成分が構成単位(f1)を含む場合、(F0)成分中の構成単位(f1)の割合は、(F0)成分を構成する全構成単位の合計(100モル%)に対して、1~60モル%が好ましく、5~55モル%がより好ましく、10~50モル%が更に好ましい。
構成単位(f1)の割合を、前記の好ましい範囲の下限値以上とすることによって、感度、解像性、ラフネス改善等のリソグラフィー特性が向上する。一方、構成単位(f1)の割合を、前記の好ましい範囲の上限値以下であると、他の構成単位とのバランスを取ることができ、種々のリソグラフィー特性が良好となる。
構成単位(f2)は、ラクトン含有環式基を含む構成単位であり、前記(A1)成分における構成単位(a2)と同様である。
なかでも、構成単位(f2)としては、前記一般式(a2-1)で表される構成単位が好ましい。
(F0)成分が構成単位(f2)を含む場合、(F0)成分中の構成単位(f2)の割合は、(F0)成分を構成する全構成単位の合計(100モル%)に対して、1~60モル%が好ましく、5~55モル%がより好ましく、10~50モル%が更に好ましい。
構成単位(f2)の割合を、前記の好ましい範囲の下限値以上とすることによって、レジスト組成物の現像液に対する溶解性が向上しやすい。一方、構成単位(f2)の割合を、前記の好ましい範囲の上限値以下とすることによって、他の構成単位とのバランスを取ることができ、種々のリソグラフィー特性が良好となりやすい。
構成単位(f3)は、前記一般式(a10-1)で表される構成単位であり、前記(A1)成分における構成単位(a10)と同様である。
(F0)成分が構成単位(f3)を含む場合、(F0)成分中の構成単位(f3)の割合は、(F0)成分を構成する全構成単位の合計(100モル%)に対して、1~40モル%が好ましく、1~35モル%がより好ましく、5~30モル%が更に好ましい。
構成単位(f3)の割合を、前記の好ましい範囲の下限値以上とすることによって、感度がより高められやすくなる。一方、構成単位(f3)の割合を、前記の好ましい範囲の上限値以下とすることによって、他の構成単位とのバランスをとりやすくなる。
あるいは、かかる(A1)成分は、構成単位(f0)を誘導するモノマーと、任意の構成単位(例えば、構成単位(f3)等)を誘導するモノマーと、を重合溶媒に溶解し、ここに、上記のようなラジカル重合開始剤を加えて重合し、その後、脱保護反応を行うことにより製造することができる。
(F0)成分の分散度(Mw/Mn)は、特に限定されず、1.0~4.0が好ましく、1.0~3.0がより好ましく、1.0~2.0が特に好ましい。なお、Mnは数平均分子量を示す。
(F)成分中の(F0)成分の割合は、(F)成分の総質量に対し、25質量%以上が好ましく、50質量%以上がより好ましく、75質量%以上がさらに好ましく、100質量%であってもよい。
本実施形態のレジスト組成物中、(F0)成分の含有量は、(A)成分100質量部に対して、0.1~30質量部が好ましく、0.3~25質量部がより好ましく、0.5~20質量部がさらに好ましく、0.9~17質量部が特に好ましい。
(F0)成分の含有量が、前記範囲の下限値以上であると、感度を高めやすく、LWRを低減しやすい。一方、(F0)成分の含有量が、上記の好ましい範囲の上限値以下とすることにより、レジスト組成物の現像液に対する溶解性を向上し、現像後の欠陥特性が良好なパターンを形成しやすい。
本実施形態のレジスト組成物は、レジスト材料を有機溶剤成分(以下「(S)成分」という)に溶解させて製造することができる。
本実施形態のレジスト組成物において、(S)成分は、1種単独で用いてもよく、2種以上の混合溶剤として用いてもよい。なかでも、PGMEA、PGME、γ-ブチロラクトン、EL、シクロヘキサノン、ジアセトンアルコールが好ましい。
(S)成分としては、PGMEA及びELの中から選ばれる少なくとも1種とγ-ブチロラクトンとの混合溶剤も好ましい。この場合、混合割合としては、前者と後者との質量比が、好ましくは70:30~95:5とされる。
(S)成分の使用量は、特に限定されず、基板等に塗布可能な濃度で、塗布膜厚に応じて適宜設定される。一般的にはレジスト組成物の固形分濃度が0.1~20質量%、好ましくは0.2~15質量%の範囲内となるように(S)成分は用いられる。
構成単位(f0)は、芳香環Ar上にヨウ素原子、又はヨウ素原子を含有する置換基を有する。ヨウ素原子は、波長13.5nmのEUVの吸収が大きい。そのため、構成単位(f0)は、露光中に2次電子が発生しやすい。露光により構成単位(f0)のAr上に存在するヨウ素原子から発生した2次電子は、(A1)成分中の構成単位(a5)、(B)成分等の露光により酸を発生する成分のカチオン部の分解を促進し、高感度化が図れ、解像性が高まると推測される。
一般的に、ヨウ素原子を含む成分をレジスト組成物中に導入すると、レジスト組成物の疎水性が高まり、現像液に対する溶解性が低下しやすい。しかしながら、構成単位(f0)は、フッ素アルコール構造を含む。そのため、レジスト組成物の親水性が向上し、現像液に対する溶解性が向上する結果、LWRや現像欠陥特性の改善に寄与していると推測される。
上記の効果が相まって、本実施形態のレジスト組成物は、高感度化が図れ、LWRが低減され、かつ、現像後の欠陥特性が良好なレジストパターンを形成できると推測される。
本発明の第2の態様に係るレジストパターン形成方法は、支持体上に、上述した本発明の第1の態様に係るレジスト組成物を用いてレジスト膜を形成する工程、前記レジスト膜を露光する工程、及び前記露光後のレジスト膜を現像してレジストパターンを形成する工程を有する方法である。
かかるレジストパターン形成方法の一実施形態としては、例えば以下のようにして行うレジストパターン形成方法が挙げられる。
次に、該レジスト膜に対し、例えば電子線描画装置、ArF露光装置等の露光装置を用いて、所定のパターンが形成されたマスク(マスクパターン)を介した露光またはマスクパターンを介さない電子線の直接照射による描画等による選択的露光を行った後、ベーク(ポストエクスポージャーベーク(PEB))処理を、例えば80~150℃の温度条件にて40~120秒間、好ましくは60~90秒間施す。
次に、前記レジスト膜を現像処理する。現像処理は、アルカリ現像プロセスの場合は、アルカリ現像液を用い、溶剤現像プロセスの場合は、有機溶剤を含有する現像液(有機系現像液)を用いて行う。
溶剤現像プロセスの場合、前記現像処理またはリンス処理の後に、パターン上に付着している現像液またはリンス液を、超臨界流体により除去する処理を行ってもよい。
現像処理後またはリンス処理後、乾燥を行う。また、場合によっては、上記現像処理後にベーク処理(ポストベーク)を行ってもよい。
液浸露光は、予めレジスト膜と露光装置の最下位置のレンズ間を、空気の屈折率よりも大きい屈折率を有する溶媒(液浸媒体)で満たし、その状態で露光(浸漬露光)を行う露光方法である。
液浸媒体としては、空気の屈折率よりも大きく、かつ、露光されるレジスト膜の屈折率よりも小さい屈折率を有する溶媒が好ましく、例えば、水、フッ素系不活性液体、シリコン系溶剤、炭化水素系溶剤等が挙げられる。
液浸媒体としては、水が好ましく用いられる。
溶剤現像プロセスで現像処理に用いる有機系現像液が含有する有機溶剤としては、(A)成分(露光前の(A)成分)を溶解し得るものであればよく、公知の有機溶剤の中から適宜選択できる。具体的には、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、ニトリル系溶剤、アミド系溶剤、エーテル系溶剤等の極性溶剤、炭化水素系溶剤等が挙げられる。
これらの有機溶剤は、いずれか1種を単独で用いてもよく、2種以上を併用してもよい。また、上記以外の有機溶剤や水と混合して用いてもよい。
本実施形態の含フッ素高分子化合物は、下記一般式(f0-1)で表される化合物から誘導される構成単位(f0)を有する。
本実施形態の含フッ素高分子化合物は、レジスト組成物に用いるフッ素添加剤成分として有用である。
本実施形態の化合物は、下記一般式(f0-1)で表される。
本実施形態の化合物の製造方法は特に限定されず、公知の方法を適宜組み合わせることにより製造することができる。
[中間体合成例1:中間体(H-1)の合成]
300mL三口フラスコに、1,1’-カルボニルジイミダゾール(CDI)(4.60g、28.4mmol)とアセトニトリル(30g)を投入した後に、2-ヒドロキシ-5-ヨード安息香酸(下記式(CA1)で表されるカルボン酸化合物)(6.7g、25.5mmol)をアセトニトリル(30g)に溶解させたものを30分かけて滴下し、1時間反応させた。その後、アルコール化合物(OH-1)(6.9g、30.6mmol)を投入し、65℃で3時間反応させた。冷却後、ヘプタン(200g)で3回洗浄した。その後、ロータリーエバポレーターを用いて濃縮し、濃縮物を再度ジクロロメタン(200g)に溶解させ、超純水(100g)で3回洗浄した。洗浄した有機層をロータリーエバポレーターを用いて濃縮し、中間体(H-1)を得た(9.6g、80.0%)。
カルボン酸化合物として下記化合物(CA1)~(CA4)のいずれかを用い、アルコール化合物として下記化合物(OH-1)~(OH-3)を用いた以外は、中間体合成例1と同様にして中間体(H-2)~(H-5)を得た。
アルコール化合物(OH-1)(5.7g、25.0mmol)、4-ビニルサリチル酸(4.1g、25.0mmol)、ジメチルアミノピリジン(DMAP)(0.4g、3.2mmol)をジクロロメタン150gに溶解し、その溶液にジイソプロピルカルボジイミド(DIC)(3.8g、30mmol)を添加した。室温で16時間撹拌した後、ろ過により不溶物を除去した。溶媒を留去後、カラムクロマトグラフィーで精製を行うことで中間体(H-6)を得た(7.9g、収率=85.0%)。
化合物(OH-1)を当モル量で化合物(OH-4)に変更した以外は中間体合成例6と同様にして、中間体(H-7)を得た。
2,6ジーヨド4-ビニルフェノール(11.1g、30.0mmol)をDMF30gに溶解し、その溶液に炭酸カリウム(5.1、37.0mmol)を添加し、続いて、ブロモ酢酸エチル(5.5g、33.0mmol)のDMF20g溶液を滴下して添加した。室温で3時間撹拌した後、TBME100gを加え、超純水100gで洗浄した。溶媒を留去後、得られた濃縮物にアセトニトリル50gに溶解し、5%水酸化ナトリウム水溶液35gを添加し、室温で16時間攪拌した。その後、5%クエン酸水溶液210gを30分かけて滴下し。析出物をろ過回収し、超純水100gで洗浄後に、減圧乾燥することにより中間体-H8を得た(11.0g、収率=85.0%)。
[合成例1:化合物(F0-01)の合成]
300mL三口フラスコに、中間体(H-1)(7.1g、15.0mmol)、トリエチルアミン(1.7g、15.5mmol)とアセトニトリル(30g)を投入し、5℃まで冷却後に、メタクリル酸クロリド(7.7g、16.0mmol)をアセトニトリル(30g)に溶解させたものを30分かけて滴下し、1時間反応させた。その後、1%NH3水溶液(50g)、ジクロロメタン(150g)を投入し、30分かけて攪拌した。有機層を回収し、超純水(100g)で洗浄した。溶媒を留去後、カラムクロマトグラフィーで精製を行うことでモノマー(F0-01)を得た(6.1g、収率:75.5%)
1H-NMR(dmso-d6、400MHz):δ(ppm)=8.05(s,OH,1H),7.57(d,I-ArH,1H),6.84(d,I-ArH,1H),6.73(d,I-ArH,1H),5.98-6.02(d,CH2,1H),5.64-5.68(d,CH2,1H),5.18-2.22(m,CH,1H),2.10-2.40(m,CH2,2H),1.88(d,CHCH3,3H),1.75(s, CH3, 3H)
中間体(H-1)を当モル量で中間体(H-2)~(H-4)に変更した以外は、合成例1と同様にして、化合物(F0-06)、化合物(F0-10)及び化合物(F0-11)を得た。
1H-NMR(dmso-d6、400MHz):δ(ppm)=8.32(d,I-ArH,1H),8.07(d,I-ArH,1H),8.05(s,OH,1H),5.98-6.02(d,CH2,1H),5.64-5.68(d,CH2,1H),5.18-2.22(m,CH,1H),2.10-2.40(m,CH2,2H),1.88(d,CHCH3,3H),1.75(s,CH3,3H)
1H-NMR(dmso-d6、400MHz):δ(ppm)=8.32(d,I-ArH,1H),8.07(d,I-ArH,1H),8.05(s,OH,1H),7.95(s,OH,1H),5.98-6.02(d,CH2,1H),5.64-5.68(d,CH2,1H),5.21-2.25(m,CH,1H),2.08-2.42(m,CH2+CH,5H),1.75(s,CH3,3H),1.62-1.68(m,CH2,1H),1.30-1.40(m,CH2,2H)
1H-NMR(dmso-d6、400MHz):δ(ppm)=8.12(d,I-ArH,1H),8.05(s,OH,1H),5.98-6.02(d,CH2,1H),5.64-5.68(d,CH2,1H),5.18-2.22(m,CH,1H),2.10-2.40(m,CH2,2H),1.88(d,CHCH3,3H),1.75(s,CH3,3H)
中間体(H-2)(9.0g、15.0mmol)、4-ビニル安息香酸(2.5g、16.0mmol)、ジメチルアミノピリジン(DMAP)(0.2g、1.6mmol)をジクロロメタン100gに溶解し、その溶液にジイソプロピルカルボジイミド(DIC)(2.5g、20mmol)を添加した。室温で16時間撹拌した後、ろ過により不溶物を除去した。溶媒を留去後、カラムクロマトグラフィーで精製を行うことで化合物(F0-21)を得た(8.4g、収率=77.0%)。
1H-NMR(dmso-d6、400MHz):δ(ppm)=8.32(d,I-ArH,1H),8.07(d,I-ArH,1H),8.05(s,OH,1H),7.88-7.92(m,ArH,2H),7.58-7.62(m,ArH,2H),6.56-6.63(dd,CH=CH2,1H),5.80-5.84(d,CH=CH2,1H),5.23-5.25(d,CH=CH2,1H),5.18-2.22(m,CH,1H),2.10-2.40(m,CH2,2H),1.88(d,CHCH3,3H)
中間体(H-2)を当モル量で中間体(H-3)~(H-5)に変更した以外は、合成例5と同様にして、化合物(F0-24)、化合物(F0-25)及び化合物(F0-26)を得た。
1H-NMR(dmso-d6、400MHz):δ(ppm)=8.32(d,I-ArH,1H),8.07(d,I-ArH,1H),7.88-7.92(m,ArH,2H),7.72-7.76(t,OH,1H),7.58-7.62(m,ArH,2H),6.56-6.63(dd,CH=CH2,1H),5.80-5.84(d,CH=CH2,1H),4.56-4.60(m,CH,1H),0.40-2.60(m,CH2+CH,14H)
1H-NMR(dmso-d6、400MHz):δ(ppm)=8.32(d,I-ArH,1H),8.07(d,I-ArH,1H),8.05(s,OH,1H),7.95(s,OH,1H),7.88-7.92(m,ArH,2H),7.58-7.62(m,ArH,2H),6.56-6.63(dd,CH=CH2,1H),5.80-5.84(d,CH=CH2,1H),5.21-2.25(m,CH+CH=CH2,2H),2.08-2.42(m,CH2+CH,5H),1.62-1.68(m,CH2,1H),1.30-1.40(m,CH2,2H)
1H-NMR(dmso-d6、400MHz):δ(ppm)=8.12(d,I-ArH,1H),8.05(s,OH,1H),7.88-7.92(m,ArH,2H),7.58-7.62(m,ArH,2H),6.56-6.63(dd,CH=CH2,1H),5.80-5.84(d,CH=CH2,1H),5.23-5.25(d,CH=CH2,1H),5.18-2.22(m,CH,1H),2.10-2.40(m,CH2,2H),1.88(d,CHCH3,3H)
中間体(H-6)(7.4g、20.0mmol)、3,5ジヨード安息香酸(7.5g、20.0mmol)、ジメチルアミノピリジン(DMAP)(0.2g、1.6mmol)をジクロロメタン100gに溶解し、その溶液にジイソプロピルカルボジイミド(DIC)(3.2g、25.4mmol)を添加した。室温で16時間撹拌した後、ろ過により不溶物を除去した。溶媒を留去後、カラムクロマトグラフィーで精製を行うことで化合物(F0-41)を得た(10.9g、収率=75.0%)。
1H-NMR(dmso-d6、400MHz):δ(ppm)=8.20(d,I-ArH,1H),8.05(s,OH,1H),8.00(d,I-ArH,2H),7.60-7.64(m,ArH,2H),7.08-7.12(m,ArH,1H),6.56-6.63(dd,CH=CH2,1H),5.80-5.84(d,CH=CH2,1H),5.23-5.25(d,CH=CH2,1H),5.18-2.22(m,CH,1H),2.10-2.40(m,CH2,2H),1.88(d,CHCH3,3H)
中間体(H-6)を当モル量で中間体(H-7)に変更した以外は合成例9と同様にして、化合物(F0-42)を得た。
1H-NMR(dmso-d6、400MHz):δ(ppm)=8.20(d,I-ArH,1H),8.15(s,OH,1H),8.00(d,I-ArH,2H),7.60-7.64(m,ArH,2H),7.08-7.12(m,ArH,1H),6.56-6.63(dd,CH=CH2,1H),5.80-5.84(d,CH=CH2,1H),5.27-5.31(m,CH,1H),5.23-5.25(d,CH=CH2,1H),2.12-2.32(m,CH2,2H),1.49-1.53(m,CH2+CH,3H),0.88-0.92(d,CH3,6H)
4-ビニルサリチル酸を当モル量で中間体(H-8)に変更した以外は中間体合成例6と同様にして化合物(F0-56)を得た。
1H-NMR(dmso-d6、400MHz):δ(ppm)=8.05(s,OH,1H),7.78-7.81(m,ArH,1H),7.51-7.54(m,ArH,1H),6.90-6.98(m,ArH,2H),6.02(d,CH2,1H),5.64-5.68(d,CH2,1H),5.18-2.22(m,CH,1H),2.10-2.40(m,CH2,2H),1.88(d,CHCH3,3H),1.75(s,CH3,3H)
高分子化合物(P-01)~(P-39)は、それぞれ、各高分子化合物を構成する構成単位を誘導するモノマーを、所定のモル比で用いて、ラジカル重合し、その後、必要に応じて脱保護反応を行うことにより得た。
得られた各高分子化合物について、それぞれ、重量平均分子量(Mw)及び分子量分散度(Mw/Mn)を、GPC測定(標準ポリスチレン換算)により求めた。結果を表1及び2に示す。
また、得られた各高分子化合物について、共重合組成比(構造式中の各構成単位の割合(モル比))を、カーボン13核磁気共鳴スペクトル(600MHz、13C-NMR)により求めた。結果を表1及び2に示す。
(実施例1~45、比較例1~4)
表3~5に示す各成分を混合して溶解し、各例のレジスト組成物をそれぞれ調製した。
(A1)-2:下記式(A1-2)で表される高分子化合物。GPC測定により求めた標準ポリスチレン換算の重量平均分子量(Mw)は6000、分子量分散度(Mw/Mn)1.55。13C-NMRにより求めた共重合組成比(構造式中の各構成単位の割合(モル比))はl/m=50/50。
(A1)-3:下記式(A1-3)で表される高分子化合物。GPC測定により求めた標準ポリスチレン換算の重量平均分子量(Mw)は5900、分子量分散度(Mw/Mn)1.54。13C-NMRにより求めた共重合組成比(構造式中の各構成単位の割合(モル比))はl/m=50/50。
(D1)-1:下記の化合物(D1-1)からなる酸拡散制御剤。
(F1)-1:下記式(F1-1)で表される高分子化合物。GPC測定により求めた標準ポリスチレン換算の重量平均分子量(Mw)は12,000、分子量分散度(Mw/Mn)1.50。13C-NMRにより求めた共重合組成比(構造式中の各構成単位の割合(モル比))はl/m=25/75。
(F1)-2:下記式(F1-2)で表される高分子化合物。GPC測定により求めた標準ポリスチレン換算の重量平均分子量(Mw)は12,200、分子量分散度(Mw/Mn)1.49。13C-NMRにより求めた共重合組成比(構造式中の各構成単位の割合(モル比))はl/m=25/75。
(F1)-3:下記式(F1-3)で表される高分子化合物。GPC測定により求めた標準ポリスチレン換算の重量平均分子量(Mw)は12,100、分子量分散度(Mw/Mn)1.50。13C-NMRにより求めた共重合組成比(構造式中の各構成単位の割合(モル比))はl/m=25/75。
(F1)-4:下記式(F1-4)で表される高分子化合物。GPC測定により求めた標準ポリスチレン換算の重量平均分子量(Mw)は12,100、分子量分散度(Mw/Mn)1.51。13C-NMRにより求めた共重合組成比(構造式中の各構成単位の割合(モル比))はl/m=25/75。
ヘキサメチルジシラザン(HMDS)処理を施した8インチシリコン基板上に、各例のレジスト組成物をそれぞれ、スピンナーを用いて塗布し、ホットプレート上で、温度110℃で60秒間のプレベーク(PAB)処理を行い、乾燥することにより、膜厚50nmのレジスト膜を形成した。
次に、前記レジスト膜に対し、電子線描画装置JEOL-JBX-9300FS(日本電子株式会社製)を用い、加速電圧100kVにて、ターゲットサイズをライン幅25nmの1:1ラインアンドスペースパターン(以下「LSパターン」)とする描画(露光)を行った。その後、110℃で60秒間の露光後加熱(PEB)処理を行った。次いで、23℃にて、2.38質量%テトラメチルアンモニウムヒドロキシド(TMAH)水溶液「NMD-3」(商品名、東京応化工業株式会社製)を用いて、60秒間のアルカリ現像を行った。
その後、純水を用いて15秒間水リンスを行った。その結果、ライン幅25nmの1:1のLSパターンが形成された。
上記<レジストパターンの形成>によってターゲットサイズのLSパターンが形成される最適露光量Eop(μC/cm2)を求めた。これを「Eop(μC/cm2)」として、表6~8に示した。
上記<レジストパターンの形成>で形成したLSパターンについて、LWRを示す尺度である3σを求めた。これを「LWR(nm)」として、表6~8に示した。
「3σ」は、走査型電子顕微鏡(加速電圧800V、商品名:S-9380、日立ハイテクノロジーズ社製)により、ラインの長手方向にラインポジションを400箇所測定し、その測定結果から求めた標準偏差(σ)の3倍値(3σ)(単位:nm)を示す。
該3σの値が小さいほど、ライン側壁のラフネスが小さく、より均一な幅のLSパターンが得られたことを意味する。
上記<レジストパターンの形成>で形成したLSパターンについて、表面欠陥観察装置(製品名:KLA2905、KLAテンコール社製)を用い、ウェーハ内トータルの欠陥数(全欠陥数)を測定した。欠陥のtargetとしては1um以上の大きさのものに限定し、1サンプルにつき10回測定し、その平均値の評価結果を「欠陥数」とし、比較例1の塗布膜表面の異物/欠陥の個数を1.0としたとき、下記の評価基準に従って評価した。
(評価基準)
A:0.5以下
B:0.5~1.0
C:1.0以上
Claims (7)
- 露光により酸を発生し、かつ、酸の作用により現像液に対する溶解性が変化するレジスト組成物であって、
酸の作用により現像液に対する溶解性が変化する樹脂成分(A1)と、
下記一般式(f0-1)で表される化合物から誘導される構成単位(f0)を有する含フッ素高分子化合物(F0)と、
を含有するレジスト組成物。
[式中、W1は重合性基である。Arは芳香環である。Xfは、ヨウ素原子、又はヨウ素原子を含有する置換基である。m1は、原子価が許容する限り、1以上の整数である。Lf01は、単結合又は(n1+1)価の連結基である。Rf01は、炭素数1~12のフッ素化アルキル基である。Rf02は、フッ素原子を有しても良い炭素数1~12の有機基又は水素原子である。n1は1~3の整数である。Rf03は、ヨウ素原子以外の置換基である。m2は、原子価が許容する限り、0以上の整数である。] - 前記構成単位(f0)が、下記一般式(f0-1-1)で表される化合物から誘導される構成単位(f01)及び下記一般式(f0-1-2)で表される化合物から誘導される構成単位(f02)からなる群より選ばれる少なくとも1種を含む、請求項1に記載のレジスト組成物。
[式中、W01は重合性基である。Arは芳香環である。Iは、ヨウ素原子である。m11は、原子価が許容する限り、1以上の整数である。Lf011は、単結合又は(n1+1)価の連結基である。Rf011は、炭素数1~12のフッ素化アルキル基である。Rf021は、フッ素原子を有しても良い炭素数1~12の有機基又は水素原子である。n11は1~3の整数である。Rf03は、ヨウ素原子以外の置換基である。m21は、原子価が許容する限り、0以上の整数である。]
[式中、W02は重合性基である。Ar1及びAr2は、それぞれ独立に、芳香環である。Rf031及びRf032は、それぞれ独立に、ヨウ素原子以外の置換基である。m12及びm32は、それぞれ独立に、原子価が許容する限り、0以上の整数である。Iは、ヨウ素原子である。m22は、原子価が許容する限り、1以上の整数である。Lf021は、単結合又は(n1+1)価の連結基である。Lf022は、2価の連結基である。Rf012は、炭素数1~12のフッ素化アルキル基である。Rf022は、フッ素原子を有しても良い炭素数1~12の有機基又は水素原子である。n21は1~3の整数である。] - 支持体上に、請求項1又は2に記載のレジスト組成物を用いてレジスト膜を形成する工程、前記レジスト膜を露光する工程、及び前記露光後のレジスト膜を現像してレジストパターンを形成する工程を有する、レジストパターン形成方法。
- 前記構成単位(f0)が、下記一般式(f0-1-1)で表される化合物から誘導される構成単位(f01)及び下記一般式(f0-1-2)で表される化合物から誘導される構成単位(f02)からなる群より選ばれる少なくとも1種を含む、請求項4に記載の含フッ素高分子化合物。
[式中、W01は重合性基である。Arは芳香環である。Iは、ヨウ素原子である。m11は、原子価が許容する限り、1以上の整数である。Lf011は、単結合又は(n1+1)価の連結基である。Rf011は、炭素数1~12のフッ素化アルキル基である。Rf021は、フッ素原子を有しても良い炭素数1~12の有機基又は水素原子である。n11は1~3の整数である。Rf03は、ヨウ素原子以外の置換基である。m21は、原子価が許容する限り、0以上の整数である。]
[式中、W02は重合性基である。Ar1及びAr2は、それぞれ独立に、芳香環である。Rf031及びRf032は、それぞれ独立に、ヨウ素原子以外の置換基である。m12及びm32は、それぞれ独立に、原子価が許容する限り、0以上の整数である。Iは、ヨウ素原子である。m22は、原子価が許容する限り、1以上の整数である。Lf021は、単結合又は(n1+1)価の連結基である。Lf022は、2価の連結基である。Rf012は、炭素数1~12のフッ素化アルキル基である。Rf022は、フッ素原子を有しても良い炭素数1~12の有機基又は水素原子である。n21は1~3の整数である。] - 下記一般式(f0-1-1)又は下記一般式(f0-1-2)で表される、請求項6に記載の化合物。
[式中、W01は重合性基である。Arは芳香環である。Iは、ヨウ素原子である。m11は、原子価が許容する限り、1以上の整数である。Lf011は、単結合又は(n1+1)価の連結基である。Rf011は、炭素数1~12のフッ素化アルキル基である。Rf021は、フッ素原子を有しても良い炭素数1~12の有機基又は水素原子である。n11は1~3の整数である。Rf03は、ヨウ素原子以外の置換基である。m21は、原子価が許容する限り、0以上の整数である。]
[式中、W02は重合性基である。Ar1及びAr2は、それぞれ独立に、芳香環である。Rf031及びRf032は、それぞれ独立に、ヨウ素原子以外の置換基である。m12及びm32は、それぞれ独立に、原子価が許容する限り、0以上の整数である。Iは、ヨウ素原子である。m22は、原子価が許容する限り、1以上の整数である。Lf021は、単結合又は(n1+1)価の連結基である。Lf022は、2価の連結基である。Rf012は、炭素数1~12のフッ素化アルキル基である。Rf022は、フッ素原子を有しても良い炭素数1~12の有機基又は水素原子である。n21は1~3の整数である。]
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|---|---|---|---|---|
| JP2005272304A (ja) * | 2004-03-22 | 2005-10-06 | Sumitomo Chemical Takeda Agro Co Ltd | フタル酸ジアミド誘導体およびその用途 |
| JP2020085917A (ja) * | 2018-11-15 | 2020-06-04 | 東京応化工業株式会社 | レジスト組成物及びレジストパターン形成方法 |
-
2023
- 2023-03-14 JP JP2023039556A patent/JP2024130062A/ja active Pending
-
2024
- 2024-03-13 KR KR1020257032273A patent/KR20250160955A/ko active Pending
- 2024-03-13 TW TW113109187A patent/TW202502722A/zh unknown
- 2024-03-13 WO PCT/JP2024/009783 patent/WO2024190825A1/ja not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005272304A (ja) * | 2004-03-22 | 2005-10-06 | Sumitomo Chemical Takeda Agro Co Ltd | フタル酸ジアミド誘導体およびその用途 |
| JP2020085917A (ja) * | 2018-11-15 | 2020-06-04 | 東京応化工業株式会社 | レジスト組成物及びレジストパターン形成方法 |
Non-Patent Citations (1)
| Title |
|---|
| AOYAMA ATSUSHI, ENDO-UMEDA KAORI, KISHIDA KENJI, OHGANE KENJI, NOGUCHI-YACHIDE TOMOMI, AOYAMA HIROSHI, ISHIKAWA MINORU, MIYACHI HI: "Design, Synthesis, and Biological Evaluation of Novel Transrepression-Selective Liver X Receptor (LXR) Ligands with 5,11-Dihydro-5-methyl-11-methylene-6 H -dibenz[ b , e ]azepin-6-one Skeleton", JOURNAL OF MEDICINAL CHEMISTRY, vol. 55, no. 17, 13 September 2012 (2012-09-13), US , pages 7360 - 7377, XP093211387, ISSN: 0022-2623, DOI: 10.1021/jm3002394 * |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202502722A (zh) | 2025-01-16 |
| JP2024130062A (ja) | 2024-09-30 |
| KR20250160955A (ko) | 2025-11-14 |
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