WO2022270230A1 - 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法 - Google Patents
感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法 Download PDFInfo
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Classifications
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/90—Carboxylic acid amides having nitrogen atoms of carboxamide groups further acylated
- C07C233/91—Carboxylic acid amides having nitrogen atoms of carboxamide groups further acylated with carbon atoms of the carboxamide groups bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/02—Monocyclic aromatic halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/63—Esters of sulfonic acids
- C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
- C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C311/03—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the sulfonamide groups bound to hydrogen atoms or to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
- C07C311/51—Y being a hydrogen or a carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/04—Thiosulfonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C62/18—Saturated compounds containing keto groups
- C07C62/24—Saturated compounds containing keto groups the keto group being part of a ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/68—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings containing halogen
- C07C63/70—Monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
- C07C65/05—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring o-Hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
- C07C65/05—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring o-Hydroxy carboxylic acids
- C07C65/10—Salicylic acid
-
- 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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers 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
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- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
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- G03F7/325—Non-aqueous compositions
Definitions
- the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and an electronic device manufacturing method.
- Examples of the pattern forming method include the following methods.
- An actinic ray-sensitive or radiation-sensitive resin film (hereinafter also referred to as a "resist film") formed using an actinic ray-sensitive or radiation-sensitive resin composition is exposed, and an area reflecting the exposure pattern It causes the resist film to change its solubility in the developer.
- development is performed using a developer (for example, an aqueous alkaline or organic solvent developer) to remove the exposed or non-exposed portions of the resist film to obtain a desired pattern.
- Patent Document 1 discloses a resist composition containing a quencher represented by the following chemical formula and a photoacid generator.
- the present inventors investigated the resist composition (actinic ray-sensitive or radiation-sensitive resin composition) described in Patent Document 1, and found that the quencher and photoacid specifically disclosed in Patent Document 1 It has been found that when a generator is used, there is room for improvement in the cross-sectional rectangularity of the pattern obtained by exposing and developing the resist film.
- an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition in which a pattern obtained has excellent cross-sectional rectangularity.
- Another object of the present invention is to provide a resist film, a pattern forming method, and an electronic device manufacturing method.
- the present inventor has completed the present invention as a result of diligent studies aimed at solving the above problems. That is, the inventors have found that the above problems can be solved by the following configuration.
- a radioactive resin composition [3]
- the anion site A of the structural site W is a site represented by any of formula (II)-1 and formulas (II)-3 to (II)-6 described later,
- [2 ] The actinic ray- or radiation-sensitive resin composition according to .
- [4] The actinic ray- or radiation-sensitive resin composition according to [2], wherein the anion site A in the structural site W is a site represented by formula (II)-1 described later.
- [5] The actinic ray- or radiation-sensitive resin composition according to any one of [1] to [4], wherein n in formula (1) is 2 to 5.
- R s are each independently —CO—OR S1 , —O—CO—R S1 , —O—CO—OR S1 , —SO 2 —R S1 , or The actinic ray- or radiation-sensitive resin composition according to any one of [ 1 ] to [5], wherein -SO 3 -R S1 represents a monovalent substituent.
- each R S independently represents -CO-OR S1 or -O-CO-R S1 , and R S1 represents a monovalent substituent [1]
- a method for manufacturing an electronic device including the pattern forming method according to [9] to [12].
- the present invention it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition in which the obtained pattern has excellent cross-sectional rectangularity. Moreover, the present invention can provide a resist film, a pattern forming method, and an electronic device manufacturing method relating to the actinic ray-sensitive or radiation-sensitive resin composition.
- the term “pattern cross-sectional rectangularity” refers to the use of a resist film formed on a substrate to form a line pattern with an average line width of 20 nm, and the cross-sectional shape of the line is measured using a length-measuring scanning electron microscope.
- the pattern line width La at the top of the pattern (the pattern surface on the side opposite to the substrate)
- the pattern line width Lb at the bottom of the pattern (the pattern surface on the side opposite to the substrate) were evaluated. say. Detailed measurement conditions will be described later.
- Organic group refers to a group containing at least one carbon atom.
- the notation not describing substitution or unsubstituted includes not only a group having no substituent but also a group having a substituent.
- an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- Alkyl group represents a linear or branched alkyl group.
- a "cycloalkyl group” represents a cyclic alkyl group.
- Substituents are monovalent substituents unless otherwise specified.
- the substituents include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as carbonyl, butoxycarbonyl and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy and benzoyloxy; acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl and methoxalyl acyl group; alkylsulfanyl group such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl group such
- actinic ray or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam). etc.
- Light means actinic rays or radiation.
- exposure means not only exposure by the emission line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also electron beams and ion beams. Also includes drawing with particle beams.
- " ⁇ " is used to mean including the numerical values described before and after it as a lower limit and an upper limit.
- the bonding direction of the divalent groups described herein is not limited.
- Y when Y is -COO-, Y may be -CO-O- or -O-CO- may Further, the above compound may be "X--CO--O--Z" or "X--O--CO--Z.”
- (Meth)acrylate stands for acrylate and methacrylate.
- (Meth)acrylic stands for acrylic and methacrylic.
- the mass average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (hereinafter also referred to as "molecular weight distribution") (Mw/Mn) of the resin were measured using a GPC (Gel Permeation Chromatography) device (HLC manufactured by Tosoh Corporation).
- GPC Gel Permeation Chromatography
- the resin composition ratio (molar ratio, mass ratio, etc.) is measured by 13 C-NMR (nuclear magnetic resonance).
- the acid dissociation constant (pKa) represents the pKa in an aqueous solution.
- pKa represents the pKa in an aqueous solution.
- Software Package 1 Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
- pKa can also be obtained by molecular orbital calculation.
- ACD/Labs Advanced Chemistry Development
- pKa can also be obtained by molecular orbital calculation.
- H + dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in literature, etc., and are not limited to this. .
- DFT density functional theory
- Gaussian 16 is an example.
- pKa means a value obtained by calculating a value based on a database of Hammett's substituent constants and known literature values using software package 1, but if pKa cannot be calculated by this method, We shall adopt the values obtained by Gaussian 16 based on DFT (Density Functional Theory).
- pKa means "pKa in aqueous solution", and when pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution” is used.
- Solid content means the components that form the resist film and does not include solvent. In addition, as long as it is a component that forms a resist film, it is regarded as a solid content even if its property is liquid.
- the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is represented by the formula (1) described later by irradiation with a resin having a group that decomposes under the action of an acid to generate a polar group and an actinic ray or radiation.
- An onium salt (I) that generates an acid consists of an anion site A and a cation site M, and has at least one structural site W that forms an acidic site represented by HA upon exposure to actinic rays or radiation ( II), and the acid dissociation constant derived from the acidic site represented by HA obtained by replacing the cationic site in the structural site W with H + is higher than the acid dissociation constant of the acid represented by formula (1).
- actinic ray-sensitive or radiation-sensitive resin composition is also referred to as "resist composition”.
- a resin having a group that decomposes under the action of an acid to generate a polar group is also referred to as an “acid-decomposable resin”.
- the acid dissociation constant derived from the acidic site represented by HA in which the cationic site in the structural site W is replaced with H 2 + is also referred to as the “acid dissociation constant of HA in the structural site W”.
- the mechanism by which the pattern obtained by exposing and developing the resist film with such a structure exhibits excellent cross-sectional rectangularity is not necessarily clear, but the present inventors presume as follows. .
- the onium salt (I) has a large interaction with the acid-decomposable resin contained in the resist composition, and suppresses diffusion of the acid generated in the exposed portion of the resist film to the unexposed portion. Furthermore, since the acid dissociation constant of the acidic site of the structural site W in the onium salt (II) contained in the resist composition of the present invention is larger than the acid dissociation constant of the acid generated from the onium salt (I), The onium salt (II) in the unexposed area can function as a quencher for the acid generated from the onium salt (I).
- the acid generated from the onium salt (I) is further suppressed from diffusing into the unexposed areas due to the action of the onium salt (II) in the unexposed areas.
- the resist film formed on the substrate is exposed and developed to obtain a pattern
- the acid generated from the exposed portion of the resist film does not diffuse, and the surface facing the substrate and the surface opposite to the substrate do not diffuse.
- the width of the pattern removed at the time of development becomes substantially the same, and the cross-sectional rectangularity of the pattern is excellent.
- the resist composition of the present invention will be described in detail below.
- the resist composition may be either a positive resist composition or a negative resist composition. Further, it may be either a resist composition for alkali development or a resist composition for organic solvent development.
- the resist composition may be a non-chemically amplified resist composition, or the resist composition may be combined with a mechanism as a chemically amplified resist composition.
- Various components of the resist composition are described in detail below.
- the onium salt (I) is an onium salt that generates an acid represented by the formula (1) described below upon exposure to actinic rays or radiation. Therefore, the onium salt (I) functions as a photoacid generator.
- An onium salt is a compound having an anion site and a cation site in its molecule. In the onium salt (I), the anion site is an anion derived from the acid represented by formula (1) described below. The acid represented by the formula (1) and the cation site of the onium salt (I) are described below.
- X represents —OH or —NH—SO 2 —R X.
- R X represents an alkyl group having at least one fluorine atom.
- Rf represents a fluorine atom or an alkyl group having at least one fluorine atom.
- Y represents a single bond, an oxygen atom, or a sulfur atom.
- Ar represents an n+1 valent aromatic ring group optionally having a substituent other than R 2 S.
- R S is -OR S1 , -CO-R S1 , -CO-OR S1 , -O-CO-R S1 , -O-CO-OR S1 , -SO 2 -R S1 , or , —SO 3 —R S1 .
- R S1 represents a monovalent substituent.
- m represents an integer of 1 or more.
- n represents an integer of 1 to 5;
- X represents —OH or —NH—SO 2 —R X.
- R X represents an alkyl group having at least one fluorine atom.
- the number of carbon atoms in the alkyl group portion of R 1 X is not particularly limited, and is preferably 1-6, more preferably 1-2.
- Alkyl groups have at least one fluorine atom. That is, at least one hydrogen atom of the alkyl group may be substituted with a fluorine atom, and all hydrogen atoms of the alkyl group may be substituted with fluorine atoms. Among them, it is preferable that all the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
- R X is preferably a perfluoroalkyl group.
- H in X is easily dissociated, and X forms an atomic group that acts as an acid. Therefore, the acid dissociation constant of the acid represented by formula (1) is the dissociation constant of H in X.
- the acid dissociation constant of the acid represented by formula (1) is not particularly limited as long as it is smaller than the acid dissociation constant of the acidic site of the structural site W of the onium salt (II), but is preferably 2.0 or less, and 0.5. The following is more preferable, and ⁇ 3.0 or less is even more preferable. Although the lower limit is not particularly limited, it may be -15.0 or more.
- Rf represents a fluorine atom or an alkyl group having at least one fluorine atom.
- Rf represents a fluorine atom or an alkyl group having at least one fluorine atom.
- the number of carbon atoms in the alkyl group portion of Rf is not particularly limited, preferably 1-6, more preferably 1-2.
- Alkyl groups have at least one fluorine atom. That is, at least one hydrogen atom of the alkyl group may be substituted with a fluorine atom, and all hydrogen atoms of the alkyl group may be substituted with fluorine atoms. Among them, it is preferable that all the hydrogen atoms of the alkyl group are substituted with fluorine atoms. That is, when Rf is an alkyl group having at least one fluorine atom, Rf is preferably a perfluoroalkyl group. Among them, Rf is preferably a fluorine atom.
- Y represents a single bond, an oxygen atom, or a sulfur atom.
- Y is preferably a single bond or an oxygen atom, more preferably an oxygen atom.
- Ar represents an n+1 valent aromatic ring group.
- the n+1 valent aromatic ring group corresponds to a group formed by removing n+1 hydrogen atoms from an aromatic ring.
- Ar represents a divalent aromatic group (arylene group or heteroarylene group).
- the aromatic ring group is not particularly limited, and the aromatic ring constituting the aromatic ring group may be monocyclic or polycyclic.
- Aromatic rings constituting the aromatic ring group include aromatic hydrocarbon rings and aromatic heterocycles.
- Aromatic hydrocarbon rings include benzene, naphthalene, anthracene, phenanthrene, and pyrene rings.
- Aromatic heterocycles include furan, pyrrole, pyrazole, imidazole, thiophene, oxazole, and thiazole rings.
- the aromatic ring constituting the aromatic ring group is polycyclic
- the polycyclic group may be a combination of an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
- Polycyclic rings include indole, isoindole, benzimidazole, purine, carbazole, benzofuran, isobenzofuran, benzothiophene, benzoxazole, and benzothiazole rings.
- the aromatic ring group is preferably an aromatic hydrocarbon ring, more preferably a benzene ring.
- Ar may have a substituent other than R 2 S.
- Substituents other than R 1 S include an alkyl group, and the alkyl group preferably has 1 to 5 carbon atoms.
- Alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, sec-butyl, and t-butyl groups. Among them, a methyl group is preferred.
- the above alkyl group may have a substituent.
- Substituents include substituent K, preferably a halogen atom.
- R S is -OR S1 , -CO-R S1 , -CO-OR S1 , -O-CO-R S1 , -O-CO-OR S1 , -SO 2 —R S1 or —SO 3 —R S1 .
- R S1 represents a monovalent substituent.
- R 1 S may be the same or different.
- R 2 S may combine with each other to form a ring.
- R S is -CO-R S1 , -CO-OR S1 , -O-CO-R S1 , -O-CO-OR S1 , -SO 2 - R S1 or -SO 3 -R S1 is preferred, and -CO-OR S1 , -O-CO-R S1 , -O-CO-OR S1 , -SO 2 -R S1 or -SO 3 -R S1 is more preferred, and -CO-OR S1 or -O-CO-R S1 is more preferred.
- R S1 is not particularly limited as long as it is a monovalent substituent, and examples thereof include substituent K. Specific examples include an alkyl group, a cycloalkyl group, an aryl group, each optionally having a substituent, and a combination thereof. Alkyl groups, cycloalkyl groups, and aryl groups, each of which may have a substituent, are described below.
- the optionally substituted alkyl group in R S1 may be linear or branched.
- the number of carbon atoms in the optionally substituted alkyl group is not particularly limited, preferably 1 to 8, more preferably 1 to 4.
- Examples of the alkyl group portion in the optionally substituted alkyl group include methyl group, ethyl group, propyl group, isopropyl group, sec-butyl group and t-butyl group.
- Examples of the substituent that the alkyl group may have include a substituent K, among which a halogen atom is preferred, and a fluorine atom is more preferred. When hydrogen atoms are substituted with halogen atoms, some or all of the hydrogen atoms in the alkyl group may be substituted.
- the optionally substituted cycloalkyl group in R S1 may be monocyclic or polycyclic.
- the number of carbon atoms in the optionally substituted cycloalkyl group is not particularly limited, preferably 4-20, more preferably 4-16.
- the cycloalkyl group portion of the optionally substituted cycloalkyl group includes, for example, a monocyclic cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and , a norbornyl group, a camphor residue, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and a polycyclic cycloalkyl group such as an adamantyl group.
- —(CH 2 )— in the cycloalkyl group is substituted with a divalent substituent.
- the divalent substituent substituting —(CH 2 )— in the cycloalkyl group is preferably —O—, —S—, —CO—, —OC—O—, or —CO—O—, and —O - is more preferred.
- the number of divalent substituents substituting —(CH 2 )— in the cycloalkyl group is preferably 1 to 3, more preferably 1.
- examples of the substituent that the cycloalkyl group may have include the substituent K, and among them, the alkyl group is preferable. Preferred embodiments and specific examples of the alkyl group are the same as those described for the alkyl group portion in the optionally substituted alkyl group.
- the optionally substituted aryl group in R S1 may be monocyclic or polycyclic.
- the aryl group which may have substituents may be a heteroaryl group which may have substituents and whose ring atoms include atoms other than carbon atoms.
- the number of carbon atoms in the optionally substituted aryl group is not particularly limited, and is preferably 6-20, more preferably 6-10.
- Specific examples of the aromatic ring portion constituting the aryl group which may have a substituent are the same as those of the aromatic ring in Ar. Among them, the aromatic ring portion constituting the aryl group which may have a substituent is preferably a benzene ring.
- Examples of the substituent that the aryl group may have include the substituent K, and among them, an alkyl group that may have a substituent is preferable.
- the number of carbon atoms in the optionally substituted alkyl group is not particularly limited, preferably 1 to 8, more preferably 1 to 4.
- Specific examples of the alkyl group optionally having substituent(s) are the same as the alkyl group optionally having substituent(s) described above, and preferred embodiments are also the same.
- the number of substituents in the optionally substituted aryl group is not particularly limited, it is preferably 1-3, more preferably 1-2.
- m represents an integer of 1 or more. m is preferably an integer of 1-5, more preferably an integer of 1-3.
- n represents an integer of 1-5.
- n is preferably an integer of 2 to 5, more preferably an integer of 2 to 3, and still more preferably 2, from the viewpoint that the effect of the present invention is more excellent.
- R S is -CO-O-R S1 or -O-CO-R S1 .
- the cationic site of the onium salt (I) is a structural site containing a positively charged atom or atomic group, and examples thereof include monovalent organic cations. Preferred embodiments of the organic cation are described below.
- the organic cation site of the onium salt (I) is preferably an organic cation represented by the formula (ZaI) (cation (ZaI)) or an organic cation represented by the formula (ZaII) (cation (ZaII)).
- R 201 , R 202 and R 203 each independently represent an organic group.
- the number of carbon atoms in the organic group as R 201 , R 202 and R 203 is generally 1-30, preferably 1-20.
- two of R 201 to R 203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, —CO—O—, an amide group or a carbonyl group.
- Groups formed by combining two of R 201 to R 203 include, for example, an alkylene group (eg, a butylene group and a pentylene group), and —CH 2 —CH 2 —O—CH 2 —CH 2 — is mentioned.
- Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), and organic cations represented by formula (ZaI-3b) (cation (ZaI-3b) ) and an organic cation represented by the formula (ZaI-4b) (cation (ZaI-4b)).
- Cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in formula (ZaI) above is an aryl group.
- R 201 to R 203 may be aryl groups, or part of R 201 to R 203 may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
- one of R 201 to R 203 may be an aryl group, and the remaining two of R 201 to R 203 may combine to form a ring structure, in which an oxygen atom, a sulfur atom, It may contain -CO-O-, an amide group or a carbonyl group.
- the group formed by bonding two of R 201 to R 203 includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, —CO—O—, an amide group and/or a carbonyl group. alkylene group (eg, butylene group, pentylene group or CH 2 —CH 2 —O—CH 2 —CH 2 —) which may be substituted.
- Arylsulfonium cations include, for example, triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations and aryldicycloalkylsulfonium cations.
- the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran and benzothiophene residues.
- the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
- the alkyl group or cycloalkyl group optionally possessed by the arylsulfonium cation is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms or a branched alkyl group having 3 to 15 carbon atoms.
- a cycloalkyl group is preferred, and more preferred are, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group and cyclohexyl group.
- the substituents that the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 may have are each independently an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 3 carbon atoms).
- aryl group eg, 6 to 14 carbon atoms
- alkoxy group eg, 1 to 15 carbon atoms
- cycloalkylalkoxy group eg, 1 to 15 carbon atoms
- halogen atom eg, fluorine, iodine
- hydroxyl group carboxy -CO-O-
- sulfinyl sulfonyl
- alkylthio phenylthio groups
- the above substituents may further have a substituent if possible.
- the above alkyl group may have a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. preferable.
- the above substituents form an acid-decomposable group by any combination.
- the acid-decomposable group is intended to be a group that is decomposed by the action of an acid to generate an acid group, and preferably has a structure in which the acid group is protected by a leaving group that is eliminated by the action of an acid.
- the above acid groups and leaving groups are described in detail in acid-decomposable resins.
- Cation (ZaI-2) is a cation in which R 201 to R 203 in formula (ZaI) each independently represents an organic group having no aromatic ring.
- the aromatic ring includes an aromatic ring containing a hetero atom.
- the organic group having no aromatic ring as R 201 to R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
- R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, and a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group or alkoxycarbonylmethyl groups are more preferred, and linear or branched 2-oxoalkyl groups are even more preferred.
- alkyl groups and cycloalkyl groups represented by R 201 to R 203 include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (eg, methyl, ethyl, propyl butyl group and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group and norbornyl group).
- R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, 1-5 carbon atoms), a hydroxyl group, a cyano group or a nitro group. It is also preferred that the substituents of R 201 to R 203 each independently form an acid-decomposable group by any combination of substituents.
- Cation (ZaI-3b) is a cation represented by formula (ZaI-3b).
- R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkyl represents a carbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group; R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (such as a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group or a aryl group.
- R x and R y each independently represent an alkyl group, cycloalkyl group, 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxycarbonylalkyl group, allyl group or vinyl group. It is also preferred that the substituents of R 1c to R 7c , R x and R y independently form an acid-decomposable group by any combination of substituents.
- R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may be bonded to each other to form a ring.
- the rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond or an amide bond.
- the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic hetero rings, and polycyclic condensed rings in which two or more of these rings are combined.
- the ring includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, more preferably a 5- or 6-membered ring.
- Examples of groups formed by bonding two or more of R 1c to R 5c , R 6c and R 7c and R x and R y include alkylene groups such as butylene and pentylene. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom.
- the group formed by combining R 5c and R 6c and R 5c and R x is preferably a single bond or an alkylene group.
- Alkylene groups include methylene and ethylene groups.
- R 1c to R 5c , R 6c , R 7c , R x , R y , and two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x and the ring formed by combining R x and R y with each other may have a substituent.
- Cation (ZaI-4b) is a cation represented by formula (ZaI-4b).
- l represents an integer of 0-2.
- r represents an integer of 0 to 8;
- R 13 is a group having a hydrogen atom, a halogen atom (e.g., fluorine atom, iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, or a cycloalkyl group (cycloalkyl group may be itself, or may be a group partially containing a cycloalkyl group). These groups may further have a substituent.
- a halogen atom e.g., fluorine atom, iodine atom, etc.
- R 14 is a hydroxyl group, a halogen atom (e.g., fluorine atom, iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group (may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. When there are a plurality of R 14 , each independently represents the above group such as a hydroxyl group.
- a halogen atom e.g., fluorine atom, iodine atom, etc.
- Each R 15 independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R 15 may be joined together to form a ring. When two R 15 are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, two R 15 are alkylene groups, preferably joined together to form a ring structure. The ring formed by combining the alkyl group, the cycloalkyl group, the naphthyl group, and the two R 15 groups may have a substituent.
- the alkyl groups for R 13 , R 14 and R 15 may be linear or branched.
- the number of carbon atoms in the alkyl group is preferably 1-10.
- the alkyl group is more preferably methyl group, ethyl group, n-butyl group or t-butyl group. It is also preferred that the substituents of R 13 to R 15 , R x and R y each independently form an acid-decomposable group by any combination of substituents.
- R 204 and R 205 each independently represent an aryl group, an alkyl group or a cycloalkyl group.
- the aryl group for R 204 and R 205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- the aryl group for R 204 and R 205 may be an aryl group having a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
- Skeletons of heterocyclic aryl groups include, for example, pyrrole, furan, thiophene, indole, benzofuran and benzothiophene.
- the alkyl group and cycloalkyl group of R 204 and R 205 are linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl or pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group or norbornyl group).
- the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
- substituents that the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may have include an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 to 15 carbon atoms). ), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups and phenylthio groups. It is also preferred that the substituents of R 204 and R 205 each independently form an acid-decomposable group by any combination of substituents.
- the molecular weight of the onium salt (I) is preferably 100-10000, more preferably 100-2500, even more preferably 100-1500.
- the content of the onium salt (I) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more, relative to the total solid content of the resist composition.
- the upper limit is preferably 70% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less, relative to the total solid content of the resist composition.
- Onium salt (I) may be used alone or in combination of two or more. When two or more are used, the total content is preferably within the range of the preferred content.
- the onium salt (II) consists of an anion site A and a cation site M, and has at least one structural site W that forms an acidic site represented by HA upon irradiation with an actinic ray or radiation.
- the acid dissociation constant derived from the acidic site represented by HA in which the cation site is replaced with H + (the acid dissociation constant of HA at the structural site W) is higher than the acid dissociation constant of the acid represented by the above formula (1). is also big.
- the onium salt (II) consists of an anionic site A Y and a cation site M Y , and the structural site Y forms an acidic site represented by HA Y upon exposure to actinic rays or radiation.
- the acid dissociation constant (the acid dissociation constant of HA Y in the structural site Y) derived from the acidic site represented by HA Y obtained by replacing the cation site M Y in the structural site Y with H + is given by the above formula (1).
- the acid dissociation constant is equal to or smaller than the acid dissociation constant of the acid represented by formula (1) above.
- Structural site W consists of anion site A and cation site M as described above.
- the onium salt (II) may have multiple structural moieties W.
- the anion site A and the cation site M of the structural site W will be described in detail.
- Anion site A is a structural site containing a negatively charged atom or group of atoms.
- the anion site A is not particularly limited as long as the acid dissociation constant of HA in the structural site W is larger than the acid dissociation constant of the acid represented by formula (1) above. Preferred embodiments of the anion site A are described below.
- the acid dissociation constant of HA at structural site W is, for example, 12.0 or less, preferably 10.0 or less.
- the lower limit of the acid dissociation constant is preferably -4.0 or more.
- the difference between the acid dissociation constant of the acid represented by formula (1) and the acid dissociation constant of HA at structural site W is preferably 1.0 or more, more preferably 1.5 or more.
- the anion site A of the structural site W is preferably a site represented by any one of formulas (II)-1 to (II)-6 from the viewpoint that the effects of the present invention are more excellent.
- * represents a bond.
- the anion site A of the structural site W is more preferably the site represented by formula (II)-1 or any one of formulas (II)-3 to (II)-6 in that the effects of the present invention are more excellent.
- a site represented by formula (II)-1 is more preferred.
- -Cation site M- Cationic site M is a structural site containing a positively charged atom or group of atoms.
- the cation site M is not particularly limited as long as it can form an acidic site in which the structural unit W is represented by HA by irradiation with actinic rays or radiation, and the definition and preferred embodiments are described in the cation site of the onium salt (I) above. As I said.
- Structural site Y consists of anionic site AY and cationic site MY as described above.
- the onium salt (II) may have multiple structural moieties Y.
- the anion site A Y and the cation site M Y of the structural site Y will be described in detail.
- Anion site A Y - Anionic moieties A Y are structural moieties containing negatively charged atoms or atomic groups.
- the anion site A to Y will be described below.
- the anionic moiety A Y includes, for example, —SO 3 ⁇ and —SO 2 —NH—SO 2 —R X. Note that R 1 X included in the structure shown as an example of the anion site A Y is the same as R 1 X described in formula (1) above.
- - cationic site M Y - Cationic site M Y is a structural site containing a positively charged atom or group of atoms.
- the cation site M Y is not particularly limited as long as the structural unit Y can form an acidic site represented by HA Y by irradiation with actinic rays or radiation. It is as described in
- Formula (II-A) M a + A a ⁇ ⁇ L a ⁇ R a M a + represents an organic cation.
- the organic cation represented by the formula (ZaI) (cation (ZaI)) or the organic cation represented by the formula (ZaII) (cation (ZaII)) is preferable.
- a a — represents a group represented by formulas (B-1) to (B-8).
- R x1 represents an organic group.
- R x1 is preferably a linear, branched or cyclic alkyl group or aryl group.
- the number of carbon atoms in the alkyl group is preferably 1-15, more preferably 1-10.
- the above alkyl group may have a substituent.
- a fluorine atom or a cyano group is preferable as a substituent.
- the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
- the alkyl group may have a carbon atom substituted with a carbonyl group.
- the aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- the aryl group may have a substituent.
- the substituent is preferably a fluorine atom, a perfluoroalkyl group (eg, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), or a cyano group.
- R X2 represents a hydrogen atom or a substituent other than a fluorine atom and a perfluoroalkyl group.
- substituents other than fluorine atoms and perfluoroalkyl groups represented by R X2 alkyl groups other than perfluoroalkyl groups (which may be linear, branched, or cyclic) are preferable.
- the number of carbon atoms in the alkyl group is preferably 1-15, more preferably 1-10.
- the alkyl group does not have a fluorine atom. That is, when the alkyl group has a substituent, it is preferably a substituent other than a fluorine atom.
- R XF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. However, at least one of the plurality of R XF1 represents a fluorine atom or a perfluoroalkyl group.
- the perfluoroalkyl group represented by R 1 XF1 preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.
- La represents a single bond or a divalent linking group.
- the divalent linking group represented by L a is not particularly limited, and examples include -CO-, -NH-, -O-, -S-, -SO-, -SO 2 -, and alkylene groups ( (preferably having 1 to 10 carbon atoms, which may be linear or branched). Moreover, the alkylene group may be substituted with a substituent (for example, a fluorine atom or the like).
- the monovalent organic group represented by R a is not particularly limited, and includes, for example, a fluoroalkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) and an organic group containing a cyclic structure. Among them, a cyclic organic group is preferable. Cyclic organic groups include, for example, alicyclic groups, aryl groups, and heterocyclic groups. Alicyclic groups may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
- polycyclic alicyclic groups examples include norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and polycyclic cycloalkyl groups such as adamantyl.
- alicyclic groups having a bulky structure with 7 or more carbon atoms such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.
- the carbon atom of the alicyclic group may be substituted with a carbonyl group.
- Aryl groups may be monocyclic or polycyclic.
- the aryl group includes, for example, a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
- a heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further suppress acid diffusion. Moreover, the heterocyclic group may or may not have aromaticity. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring.
- Non-aromatic heterocycles include, for example, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
- lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the resins described later.
- the heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.
- the cyclic organic group may have a substituent.
- substituents include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic, and spirocyclic). any group, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide groups, and sulfonate ester groups.
- carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic
- a compound represented by formula (II-B) is also preferred.
- a structure containing structural site W is formed by M b + and A b ⁇ in formula (II-B).
- Formula (II-B) (R b ) m ⁇ M b + ⁇ L b ⁇ A b ⁇ M b + represents a sulfur ion (S + ) or an iodine ion (I + ).
- m represents 1 or 2, and is 2 when M b + is a sulfur ion and 1 when it is an iodine atom.
- Each Rb independently represents an alkyl or alkenyl group optionally containing a heteroatom, an aryl group, or a heteroaryl group.
- two Rb 's may combine with each other to form a ring.
- the alkyl group or alkenyl group optionally containing a heteroatom represented by R b is not particularly limited, but for example, an alkyl having 1 to 20 carbon atoms in which —CH 2 — may be substituted with a heteroatom groups (preferably having 1 to 10 carbon atoms), and alkenyl groups having 1 to 20 carbon atoms (preferably having 2 to 10 carbon atoms) in which —CH 2 — may be substituted with a hetero atom.
- Heteroatoms include, for example, oxygen atoms, nitrogen atoms, sulfur atoms, and the like.
- the alkyl group or alkenyl group that may contain a heteroatom represented by Rb may be linear, branched, or cyclic.
- alkyl group or alkenyl group which may contain a heteroatom represented by Rb may have a substituent.
- substituents include an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. mentioned.
- the aryl group represented by Rb may be monocyclic or polycyclic.
- the aryl group includes, for example, phenyl group, naphthyl group, phenanthryl group, and anthryl group.
- the heteroaryl group represented by Rb may be monocyclic or polycyclic.
- the polycyclic type can further suppress acid diffusion. Examples of the aromatic heterocyclic ring constituting this heteroaryl group include furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring.
- the aryl group and heteroaryl group represented by Rb may have a substituent.
- this substituent include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic, and spirocyclic). any group, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide groups, and sulfonate ester groups.
- the divalent linking group represented by Lb is not particularly limited, and examples include -CO-, -NH-, -O-, -S-, -SO-, -SO 2 -, an alkylene group (preferably 1 to 10 carbon atoms, which may be linear or branched), and arylene groups (preferably 6 to 10 carbon atoms), one or more selected from the group, or a combination of two or more.
- the hydrogen atoms of the alkylene group and the arylene group may be substituted with a substituent (for example, a fluorine atom or the like).
- a b — represents the groups represented by formulas (B-1) to (B-8) described above.
- a compound represented by formula (Ia-1) is also preferred. At least one of the M 11 + A 11 - moiety and the A 12 - M 12 + moiety in formula (Ia-1) contains structural site W. M 11 + A 11 - - L 1 - A 12 - M 12 + (Ia-1) In formula (Ia-1), M 11 + and M 12 + each represent an organic cation. As the organic cation, the organic cation represented by the formula (ZaI) (cation (ZaI)) or the organic cation represented by the formula (ZaII) (cation (ZaII)) is preferable.
- a 11 - and A 12 - each independently represent a group represented by formulas (B-1) to (B-8).
- L 1 represents a divalent linking group.
- the divalent linking group represented by L 1 is not particularly limited, and examples include -CO-, -NH-, -O-, -S-, -SO-, -SO 2 -, an alkylene group (preferably 1 to 10 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably 5 to 20 carbon atoms, which may be monocyclic, polycyclic, or spirocyclic), and an arylene group ( Preferably, one or more or a combination of two or more selected from the group consisting of 6 to 10 carbon atoms.
- the hydrogen atoms of the alkylene group, cycloalkylene group, and arylene group may be substituted with a substituent (for example, a fluorine atom, etc.).
- onium salt (II) compounds represented by formulas (Ia-2) to (Ia-4) are also preferred. At least one of the M 22 + A 22 - portion, A 21a - M 21a + portion, and A 21b - M 21b + portion in formula (Ia-2) contains the structural site W. At least one of the M 42 + A 42 - portion, the A 41a - M 41a + portion, and the A 41b - M 41b + portion in formula (Ia-4) contains structural site W.
- M 22 + , M 21a + and M 21b + each represent an organic cation.
- the organic cation represented by the formula (ZaI) (cation (ZaI)) or the organic cation represented by the formula (ZaII) (cation (ZaII)) is preferable.
- a 21a - and A 21b - each independently represent a group represented by formulas (B-1) to (B-8).
- a 22 - represents a group represented by formulas (II)-1 to (II)-4.
- L 21 and L 22 each represent a divalent linking group.
- the divalent linking group represented by L 21 and L 22 is not particularly limited, and examples thereof include the groups described for Lb above. L21 and L22 may be the same or different.
- M 42 + , M 41a + and M 41b + each represent an organic cation.
- the organic cation represented by the formula (ZaI) (cation (ZaI)) or the organic cation represented by the formula (ZaII) (cation (ZaII)) is preferable.
- a 41a ⁇ , A 41b ⁇ , and A 42 ⁇ each independently represent groups represented by formulas (B-1) to (B-8).
- L 41 represents a trivalent linking group. Examples of trivalent organic groups include trivalent organic groups represented by formula (L3).
- LB represents a trivalent hydrocarbon ring group or a trivalent heterocyclic group. * represents a binding position.
- the hydrocarbon ring group may be either an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group.
- the number of carbon atoms contained in the hydrocarbon ring group is preferably 6-18, more preferably 6-14.
- the heterocyclic group may be either an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group.
- the heterocyclic ring is preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and further a 5- to 6-membered ring. preferable.
- LB is preferably a trivalent hydrocarbon ring group, more preferably a benzene ring group or an adamantane ring group.
- the benzene ring group or adamantane ring group may have a substituent.
- substituents include halogen atoms (preferably fluorine atoms).
- L B1 to L B3 each independently represent a single bond or a divalent linking group.
- divalent linking groups represented by L B1 to L B3 include —CO—, —NR—, —O—, —S—, —SO—, —SO 2 —, alkylene groups (preferably carbon Number 1 to 6, which may be linear or branched.), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), divalent Aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, a 5- to 6-membered ring is further preferred), a divalent aromatic heterocyclic group (preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure, more preferably
- the above R includes a hydrogen atom or a monovalent organic group.
- a monovalent organic group for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred.
- the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group and the divalent aromatic hydrocarbon ring group have a substituent.
- Substituents include, for example, halogen atoms (preferably fluorine atoms).
- divalent linking groups represented by L B1 to L B3 —CO—, —NR—, —O—, —S—, —SO—, —SO 2 —, even if having a substituent A good alkylene group or a divalent linking group combining these is preferred.
- the molecular weight of the onium salt (II) is preferably 100-10000, more preferably 100-2500, even more preferably 100-1500.
- the content of the onium salt (II) is preferably 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more, relative to the total solid content of the resist composition. .
- the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, relative to the total solid content of the resist composition.
- Onium salt (II) may be used alone or in combination of two or more. When two or more are used, the total content is preferably within the range of the preferred content.
- the total content of the onium salt (I) and the onium salt (II) is preferably 10% by mass or more, preferably 15% by mass or more, and 20% by mass or more with respect to the total solid content of the resist composition. More preferably, 30% by mass or more is even more preferable.
- the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, relative to the total solid content of the resist composition.
- the resist composition may contain a compound other than the onium salt (I) or the onium salt (II) that generates an acid upon exposure to actinic rays or radiation (other photoacid generator).
- the resist composition contains an acid-decomposable resin.
- the acid-decomposable resin is also simply referred to as "resin (A)".
- the acid-decomposable resin preferably has an acid-decomposable group.
- “Acid-decomposable group” means a group that is decomposed by the action of an acid to form a polar group.
- a mold pattern is preferably formed.
- the repeating units that the acid-decomposable resin may contain are described below.
- the acid-decomposable group preferably has a structure in which the polar group is protected with a leaving group that leaves under the action of an acid.
- the acid-decomposable resin preferably has a repeating unit having a group that is decomposed by the action of an acid to form a polar group.
- a resin having this repeating unit has an increased polarity under the action of an acid, so that the solubility in an alkaline developer increases and the solubility in an organic solvent decreases.
- an alkali-soluble group is preferable.
- Alkali-soluble groups include, for example, a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, an (alkylsulfonyl ) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group and tris ( Examples include acidic groups such as alkylsulfonyl)methylene groups, and alcoholic hydroxyl groups.
- the acid-decomposable group preferably has a structure in which the acid-
- Examples of the leaving group that leaves by the action of an acid include groups represented by formulas (Y1) to (Y4).
- Formula (Y1) -C(Rx 1 )(Rx 2 )(Rx 3 )
- Formula (Y3) —C(R 36 )(R 37 )(OR 38 )
- Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group ( linear or branched), aryl group (monocyclic or polycyclic), or heteroaryl group (monocyclic or polycyclic).
- Rx 1 to Rx 3 are alkyl groups (linear or branched)
- at least two of Rx 1 to Rx 3 are preferably methyl groups.
- Rx 1 to Rx 3 preferably each independently represent a linear or branched alkyl group, and Rx 1 to Rx 3 each independently represent a linear alkyl group. is more preferred.
- Rx 1 to Rx 3 may combine with each other to form a monocyclic or polycyclic ring.
- the alkyl groups of Rx 1 to Rx 3 include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
- the cycloalkyl groups represented by Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.
- the aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
- the heteroaryl groups represented by Rx 1 to Rx 3 are preferably heteroaryl groups having 4 to 10 carbon atoms, for example.
- a vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
- the ring formed by combining two of Rx 1 to Rx 3 is preferably a cycloalkyl group.
- the cycloalkyl group formed by combining two of Rx 1 to Rx 3 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca.
- a polycyclic cycloalkyl group such as a nyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
- the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring contains a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or vinylidene group may be substituted.
- a heteroatom such as an oxygen atom
- a heteroatom such as a carbonyl group
- vinylidene group vinylidene group
- one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
- Rx 1 is a methyl group or an ethyl group
- Rx 2 and Rx 3 combine to form the above-mentioned cycloalkyl group.
- a preferred embodiment is one.
- the resist composition is an EUV exposure resist composition
- the ring formed by combining two of (2) further has a fluorine atom or an iodine atom as a substituent.
- R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group.
- R 37 and R 38 may combine with each other to form a ring.
- Monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. It is also preferred that R 36 is a hydrogen atom.
- the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group.
- one or more of the methylene groups may be replaced with a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group. good.
- R 38 may combine with another substituent of the main chain of the repeating unit to form a ring.
- the group formed by bonding R 38 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
- the resist composition is a resist composition for EUV exposure
- the monovalent organic groups represented by R 36 to R 38 and the ring formed by combining R 37 and R 38 with each other are Furthermore, it is also preferable to have a fluorine atom or an iodine atom as a substituent.
- L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (e.g., a group combining an alkyl group and an aryl group).
- M represents a single bond or a divalent linking group.
- Q is an alkyl group optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
- one of the methylene groups may be replaced by a heteroatom such as an oxygen atom or a heteroatom-containing group such as a carbonyl group.
- L 1 and L 2 is preferably a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two of Q, M, and L1 may combine to form a ring (preferably a 5- or 6-membered ring).
- L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group.
- Secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, and tertiary alkyl groups include tert-butyl and adamantane groups.
- the Tg (glass transition temperature) and the activation energy are increased, so that the film strength can be ensured and fogging can be suppressed.
- the resist composition is, for example, a resist composition for EUV exposure
- the alkyl group, cycloalkyl group, aryl group, and a group combining these represented by L 1 and L 2 are further substituted It is also preferable to have a fluorine atom or an iodine atom as.
- the alkyl group, cycloalkyl group, aryl group, and aralkyl group contain a heteroatom such as an oxygen atom in addition to the fluorine atom and the iodine atom (i.e., the alkyl group, cycloalkyl group, Aryl groups and aralkyl groups, for example, in which one of the methylene groups is replaced by a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group, are also preferred.
- the resist composition is, for example, a resist composition for EUV exposure
- an alkyl group which may contain a heteroatom represented by Q an alkyl group which may contain a heteroatom represented by Q
- a cycloalkyl group which may contain a heteroatom, a heteroatom
- the heteroatom is selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom. It is also preferred that the heteroatom is
- Ar represents an aromatic ring group.
- Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
- Rn and Ar may combine with each other to form a non-aromatic ring.
- Ar is preferably an aryl group.
- the aromatic ring group represented by Ar and the alkyl group, cycloalkyl group and aryl group represented by Rn have fluorine as a substituent. It is also preferred to have an atom or an iodine atom.
- the ring member atoms adjacent to the ring member atoms directly bonded to the polar group (or residue thereof) do not have halogen atoms such as fluorine atoms as substituents.
- the leaving group that leaves by the action of an acid also includes a 2-cyclopentenyl group having a substituent (such as an alkyl group) such as a 3-methyl-2-cyclopentenyl group, and a 1,1,4 , 4-tetramethylcyclohexyl group having a substituent (such as an alkyl group) may also be used.
- a 2-cyclopentenyl group having a substituent such as an alkyl group
- a 1,1,4 , 4-tetramethylcyclohexyl group having a substituent such as an alkyl group
- repeating unit having an acid-decomposable group a repeating unit represented by formula (A) is also preferable.
- L 1 represents a divalent linking group optionally having a fluorine atom or an iodine atom
- R 1 is a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group optionally having a fluorine atom or an iodine atom , or represents an aryl group which may have a fluorine atom or an iodine atom
- R 2 represents a leaving group which may have a fluorine atom or an iodine atom after being eliminated by the action of an acid.
- at least one of L 1 , R 1 and R 2 has a fluorine atom or an iodine atom.
- L 1 represents a divalent linking group optionally having a fluorine atom or an iodine atom.
- the divalent linking group which may have a fluorine atom or an iodine atom includes -CO-, -O-, -S-, -SO-, -SO 2 -, a fluorine atom or an iodine atom. (eg, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, etc.), and a linking group in which a plurality of these are linked.
- L 1 is preferably -CO-, an arylene group, or an -arylene group - an alkylene group having a fluorine atom or an iodine atom -, and -CO- or an -arylene group - a fluorine atom or an iodine atom.
- An alkylene group with - is more preferable.
- a phenylene group is preferred as the arylene group.
- Alkylene groups may be linear or branched. Although the number of carbon atoms in the alkylene group is not particularly limited, it is preferably 1-10, more preferably 1-3.
- the total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.
- R 1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group optionally having a fluorine atom or an iodine atom, or an aryl group optionally having a fluorine atom or an iodine atom.
- Alkyl groups may be straight or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-10, more preferably 1-3. The total number of fluorine atoms and iodine atoms contained in the alkyl group having fluorine atoms or iodine atoms is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.
- the above alkyl group may contain a heteroatom such as an oxygen atom other than the halogen atom.
- R 2 represents a leaving group that leaves by the action of an acid and may have a fluorine atom or an iodine atom.
- the leaving group optionally having a fluorine atom or an iodine atom includes leaving groups represented by the above formulas (Y1) to (Y4) and having a fluorine atom or an iodine atom.
- a repeating unit having an acid-decomposable group a repeating unit represented by formula (AI) is also preferable.
- Xa 1 represents a hydrogen atom or an optionally substituted alkyl group.
- T represents a single bond or a divalent linking group.
- Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl ( monocyclic or polycyclic) group. However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. Two of Rx 1 to Rx 3 may combine to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).
- Examples of the optionally substituted alkyl group represented by Xa 1 include a methyl group and a group represented by -CH 2 -R 11 .
- R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.
- Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
- the divalent linking group of T includes an alkylene group, an aromatic ring group, a -COO-Rt- group and a -O-Rt- group.
- Rt represents an alkylene group or a cycloalkylene group.
- T is preferably a single bond or a -COO-Rt- group.
- Rt is preferably an alkylene group having 1 to 5 carbon atoms, a -CH 2 - group, a -(CH 2 ) 2 - group, or a -(CH 2 ) 3 - groups are more preferred.
- the alkyl groups of Rx 1 to Rx 3 include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
- Cycloalkyl groups for Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. is preferred.
- the aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
- a vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
- the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group.
- Polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are preferred. Among them, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred.
- a cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring contains a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or It may be substituted with a vinylidene group.
- Rx 1 is a methyl group or an ethyl group
- Rx 2 and Rx 3 are preferably combined to form the above-mentioned cycloalkyl group.
- substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms).
- the number of carbon atoms in the substituent is preferably 8 or less.
- the repeating unit represented by the formula (AI) includes an acid-decomposable (meth)acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T represents a single bond. ) is preferred.
- repeating units having an acid-decomposable group are shown below, but the present invention is not limited thereto.
- Xa 1 represents H, CH 3 , CF 3 or CH 2 OH
- Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.
- Resin (A) may have a repeating unit having an acid-decomposable group containing an unsaturated bond as the repeating unit having an acid-decomposable group.
- a repeating unit represented by formula (B) is preferable.
- Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group.
- L represents a single bond or a divalent linking group which may have a substituent.
- Ry 1 to Ry 3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group . However, at least one of Ry 1 to Ry 3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry 1 to Ry 3 may combine to form a monocyclic or polycyclic group (a monocyclic or polycyclic cycloalkyl group, cycloalkenyl group, etc.).
- the optionally substituted alkyl group represented by Xb includes, for example, a methyl group and a group represented by —CH 2 —R 11 .
- R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.
- Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
- Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, preferably an aromatic ring group.
- L is preferably -Rt-, -CO-, -COO-Rt-CO- or -Rt-CO-.
- Rt may have substituents such as halogen atoms, hydroxyl groups, and alkoxy groups. Aromatic groups are preferred.
- the alkyl groups represented by Ry 1 to Ry 3 include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
- Cycloalkyl groups represented by Ry 1 to Ry 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. Polycyclic cycloalkyl groups are preferred.
- the aryl group represented by Ry 1 to Ry 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
- a vinyl group is preferable as the alkenyl group for Ry 1 to Ry 3 .
- An ethynyl group is preferred as the alkynyl group for Ry 1 to Ry 3 .
- Cycloalkenyl groups represented by Ry 1 to Ry 3 are preferably monocyclic cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, which partially contain a double bond.
- the cycloalkyl group formed by combining two of Ry 1 to Ry 3 includes a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca.
- Polycyclic cycloalkyl groups such as a nyl group and an adamantyl group are preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
- a cycloalkyl group formed by combining two of Ry 1 to Ry 3 or a cycloalkenyl group for example, one of the methylene groups constituting the ring is a hetero atom such as an oxygen atom, a carbonyl group, or —SO 2 It may be substituted with a group containing a heteroatom such as a - group and a -SO 3 - group, a vinylidene group, or a combination thereof.
- one or more ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced with a vinylene group.
- Ry 1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group
- Ry 2 and Rx 3 combine to form the above-mentioned cycloalkyl
- a preferred embodiment forms a group or a cycloalkenyl group.
- substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms).
- the number of carbon atoms in the substituent is preferably 8 or less.
- the repeating unit represented by the formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester-based repeating unit (Xb represents a hydrogen atom or a methyl group, and L represents a —CO— group.
- repeating unit represented acid-decomposable hydroxystyrene tertiary alkyl ether-based repeating unit (repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), acid-decomposable styrene carboxylic acid tertiary ester It is a repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)).
- the content of the repeating unit having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and 30 mol% or more, based on the total repeating units in the resin (A). is more preferred.
- the upper limit thereof is preferably 80 mol % or less, more preferably 70 mol % or less, and particularly preferably 60 mol % or less, based on all repeating units in the resin (A).
- Xb and L1 represent any of the substituents and linking groups described above
- Ar represents an aromatic group
- R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, alkenyl group, hydroxyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR''' or -COOR''': R''' is alkyl having 1 to 20 carbon atoms group or fluorinated alkyl group), or a substituent such as a carboxyl group, and R′ is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or , represents a
- the content of repeating units having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all repeating units in the resin (A).
- the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly 60 mol% or less, relative to all repeating units in the resin (A). preferable.
- the resin (A) may contain at least one repeating unit selected from the group consisting of Group A below and/or at least one repeating unit selected from the group consisting of Group B below. good.
- Group A A group consisting of the following repeating units (20) to (29).
- the resin (A) preferably has an acid group, and preferably contains a repeating unit having an acid group, as described later.
- the definition of the acid group will be explained later along with preferred embodiments of repeating units having an acid group.
- the resin (A) When the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, the resin (A) preferably has at least one repeating unit selected from the group consisting of Group A above. Moreover, when the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom.
- the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom, and the resin (A) It may contain two types of a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom.
- the resin (A) preferably has a repeating unit having an aromatic group.
- the resin (A) When the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably has at least one repeating unit selected from the group consisting of Group B above. When the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably contains neither fluorine atoms nor silicon atoms. Moreover, when the resist composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably does not have an aromatic group.
- Resin (A) may have a repeating unit having an acid group.
- an acid group having a pKa of 13 or less is preferable.
- the acid dissociation constant of the acid group is preferably 13 or less, more preferably 3-13, even more preferably 5-10.
- the content of the acid group in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol/g. Among them, 0.8 to 6.0 mmol/g is preferable, 1.2 to 5.0 mmol/g is more preferable, and 1.6 to 4.0 mmol/g is even more preferable.
- the acid group is preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluoroalcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
- a fluoroalcohol group preferably a hexafluoroisopropanol group
- a sulfonic acid group preferably a sulfonamide group
- an isopropanol group preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluoroalcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
- one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluor
- the acid group is -C(CF 3 )(OH)-CF 2 - thus formed.
- one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF 3 )(OH)-CF 2 -.
- the repeating unit having an acid group is a repeating unit having a structure in which the polar group is protected by a leaving group that leaves under the action of an acid, and a repeating unit having a lactone group, a sultone group, or a carbonate group, which will be described later. are preferably different repeating units.
- a repeating unit having an acid group may have a fluorine atom or an iodine atom.
- repeating units having an acid group include the following repeating units.
- repeating unit having an acid group a repeating unit represented by the following formula (1) is preferable.
- A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
- R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group; In some cases they may be the same or different. When it has a plurality of R, they may jointly form a ring.
- a hydrogen atom is preferred as R.
- a represents an integer of 1 to 3;
- b represents an integer from 0 to (5-a).
- repeating units having an acid group examples include 1 or 2.
- R represents a hydrogen atom or a methyl group
- a represents 2 or 3.
- the content of repeating units having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 70 mol % or less, more preferably 65 mol % or less, and still more preferably 60 mol % or less, based on all repeating units in the resin (A).
- the resin (A) has neither an acid-decomposable group nor an acid group, apart from the above-described ⁇ repeating unit having an acid-decomposable group> and ⁇ repeating unit having an acid group>, and contains a fluorine atom and a bromine atom.
- it may have a repeating unit having an iodine atom (hereinafter also referred to as unit X).
- the ⁇ repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom or an iodine atom> referred to herein is a ⁇ repeating unit having a lactone group, a sultone group, or a carbonate group, which will be described later. It is preferably different from other types of repeating units belonging to Group A, such as ⁇ Repeating unit having a photoacid-generating group>.
- a repeating unit represented by formula (C) is preferable.
- L5 represents a single bond or an ester group.
- R9 represents a hydrogen atom or an alkyl group optionally having a fluorine atom or an iodine atom.
- R 10 may have a hydrogen atom, an alkyl group optionally having a fluorine atom or an iodine atom, a cycloalkyl group optionally having a fluorine atom or an iodine atom, a fluorine atom or an iodine atom represents an aryl group or a group combining these;
- repeating units having a fluorine atom or an iodine atom are shown below.
- the content of the unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 50 mol % or less, more preferably 45 mol % or less, and still more preferably 40 mol % or less, relative to all repeating units in the resin (A).
- the total content of repeating units containing at least one of a fluorine atom, a bromine atom and an iodine atom is preferably 10 mol% or more with respect to all repeating units of the resin (A). , more preferably 20 mol % or more, still more preferably 30 mol % or more, and particularly preferably 40 mol % or more.
- the upper limit is not particularly limited, it is, for example, 100 mol % or less with respect to all repeating units of the resin (A).
- the repeating unit containing at least one of a fluorine atom, a bromine atom and an iodine atom includes, for example, a repeating unit having a fluorine atom, a bromine atom or an iodine atom and having an acid-decomposable group, a fluorine atom, a bromine repeating units having an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom.
- Resin (A) may have a repeating unit (hereinafter also referred to as “unit Y”) having at least one selected from the group consisting of a lactone group, a sultone group and a carbonate group. It is also preferred that the unit Y does not have a hydroxyl group and an acid group such as a hexafluoropropanol group.
- the lactone group or sultone group may have a lactone structure or sultone structure.
- the lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure.
- the resin (A) has a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-21), or any one of the following formulas (SL1-1) to (SL1-3). It is preferable to have a repeating unit having a lactone group or a sultone group obtained by extracting one or more hydrogen atoms from ring member atoms of a sultone structure. Also, a lactone group or a sultone group may be directly bonded to the main chain. For example, ring member atoms of a lactone group or a sultone group may constitute the main chain of resin (A).
- the lactone structure or sultone structure may have a substituent (Rb 2 ).
- Preferred substituents (Rb 2 ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, and carboxyl groups. , halogen atoms, cyano groups, and acid-labile groups.
- n2 represents an integer of 0-4. When n2 is 2 or more, multiple Rb 2 may be different, and multiple Rb 2 may combine to form a ring.
- Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
- a halogen atom for Rb 0 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Rb 0 is preferably a hydrogen atom or a methyl group.
- Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these divalent groups represents Among them, Ab is preferably a single bond or a linking group represented by -Ab 1 -CO 2 -.
- Ab 1 is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group or norbornylene group.
- V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-21), or formulas (SL1-1) to (SL1- 3) represents a group obtained by removing one hydrogen atom from a ring member atom of the sultone structure represented by any one of 3).
- any optical isomer may be used.
- one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
- its optical purity (ee) is preferably 90 or more, more preferably 95 or more.
- a cyclic carbonate group is preferred.
- a repeating unit having a cyclic carbonate group a repeating unit represented by the following formula (A-1) is preferable.
- R A 1 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
- n represents an integer of 0 or more.
- R A 2 represents a substituent. When n is 2 or more, a plurality of R A 2 may be the same or different.
- A represents a single bond or a divalent linking group.
- the divalent linking group includes an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these. valence groups are preferred.
- Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.
- Rx represents a hydrogen atom, -CH 3 , -CH 2 OH or -CF 3 .
- the content of the unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, relative to all repeating units in the resin (A).
- the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, and particularly 60 mol% or less, relative to all repeating units in the resin (A). preferable.
- the resin (A) may have, as a repeating unit other than the above, a repeating unit having a group that generates an acid upon exposure to actinic rays or radiation (hereinafter also referred to as a "photoacid-generating group").
- Repeating units having a photoacid-generating group include repeating units represented by formula (4).
- R41 represents a hydrogen atom or a methyl group.
- L41 represents a single bond or a divalent linking group.
- L42 represents a divalent linking group.
- R40 represents a structural site that is decomposed by exposure to actinic rays or radiation to generate an acid in the side chain. Examples of repeating units having a photoacid-generating group are shown below.
- repeating unit represented by formula (4) includes, for example, repeating units described in paragraphs [0094] to [0105] of JP-A-2014-041327, and International Publication No. 2018/193954. Examples include repeating units described in paragraph [0094].
- the content of the repeating unit having a photoacid-generating group is preferably 1 mol % or more, more preferably 5 mol % or more, relative to all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 40 mol % or less, more preferably 35 mol % or less, and still more preferably 30 mol % or less, relative to all repeating units in the resin (A).
- Resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2).
- Repeating units represented by the following formulas (V-1) and (V-2) below are preferably different repeating units from the repeating units described above.
- R 6 and R 7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR:R represents an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
- the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
- n3 represents an integer of 0-6.
- n4 represents an integer of 0-4.
- X4 is a methylene group, an oxygen atom, or a sulfur atom.
- the repeating units represented by formula (V-1) or (V-2) are exemplified below. Examples of the repeating unit represented by formula (V-1) or (V-2) include repeating units described in paragraph [0100] of WO 2018/193954.
- the resin (A) preferably has a high glass transition temperature (Tg) from the viewpoint of suppressing excessive diffusion of generated acid or pattern collapse during development.
- Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C.
- the Tg is preferably 400° C. or less, more preferably 350° C. or less, from the viewpoint of excellent dissolution rate in the developer.
- Tg of repeating unit is calculated by the following method.
- the Tg of a homopolymer consisting only of each repeating unit contained in the polymer is calculated by the Bicerano method.
- the mass ratio (%) of each repeating unit to all repeating units in the polymer is calculated.
- the Tg at each mass ratio is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the Tg (° C.) of the polymer.
- the Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993).
- calculation of Tg by the Bicerano method can be performed using a polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).
- Methods for reducing the mobility of the main chain of the resin (A) include the following methods (a) to (e).
- (a) introduction of bulky substituents into the main chain (b) introduction of multiple substituents into the main chain (c) introduction of substituents that induce interaction between the resin (A) into the vicinity of the main chain ( d) Main Chain Formation in Cyclic Structure (e) Linking of Cyclic Structure to Main Chain
- the resin (A) preferably has a repeating unit exhibiting a homopolymer Tg of 130° C. or higher.
- the type of repeating unit exhibiting a homopolymer Tg of 130° C. or higher is not particularly limited as long as it is a repeating unit having a homopolymer Tg of 130° C. or higher calculated by the Bicerano method.
- the homopolymers correspond to repeating units exhibiting a homopolymer Tg of 130° C. or higher.
- a specific example of means for achieving the above (a) is a method of introducing a repeating unit represented by the formula (A) into the resin (A).
- RA represents a group containing a polycyclic structure.
- R x represents a hydrogen atom, a methyl group, or an ethyl group.
- a group containing a polycyclic structure is a group containing multiple ring structures, and the multiple ring structures may or may not be condensed.
- Specific examples of the repeating unit represented by formula (A) include those described in paragraphs [0107] to [0119] of WO2018/193954.
- a specific example of means for achieving the above (b) is a method of introducing a repeating unit represented by the formula (B) into the resin (A).
- R b1 to R b4 each independently represent a hydrogen atom or an organic group, and at least two or more of R b1 to R b4 represent an organic group.
- the type of the other organic group is not particularly limited.
- at least two of the organic groups have three or more constituent atoms excluding hydrogen atoms. is a substituent.
- Specific examples of the repeating unit represented by formula (B) include those described in paragraphs [0113] to [0115] of WO2018/193954.
- a specific example of means for achieving the above (c) is a method of introducing a repeating unit represented by the formula (C) into the resin (A).
- R c1 to R c4 each independently represent a hydrogen atom or an organic group, and at least one of R c1 to R c4 is hydrogen bonding hydrogen within 3 atoms from the main chain carbon It is a group containing atoms. Above all, it is preferable to have a hydrogen-bonding hydrogen atom within 2 atoms (closer to the main chain side) in order to induce interaction between the main chains of the resin (A).
- Specific examples of the repeating unit represented by formula (C) include those described in paragraphs [0119] to [0121] of WO2018/193954.
- a specific example of means for achieving (d) above is a method of introducing a repeating unit represented by the formula (D) into the resin (A).
- Cylic represents a group forming a main chain with a cyclic structure.
- the number of constituent atoms of the ring is not particularly limited.
- Specific examples of the repeating unit represented by formula (D) include those described in paragraphs [0126] to [0127] of WO2018/193954.
- a specific example of means for achieving (e) above is a method of introducing a repeating unit represented by formula (E) into the resin (A).
- each Re independently represents a hydrogen atom or an organic group.
- organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have substituents.
- Cylic is a cyclic group containing main chain carbon atoms. The number of atoms contained in the cyclic group is not particularly limited. Specific examples of the repeating unit represented by formula (E) include those described in paragraphs [0131] to [0133] of WO2018/193954.
- the resin (A) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups.
- the repeating unit having a lactone group, a sultone group, or a carbonate group that the resin (A) has include the repeating units described in the above ⁇ Repeating unit having a lactone group, sultone group, or carbonate group>.
- the preferable content is also as described in ⁇ Repeating unit having lactone group, sultone group, or carbonate group>.
- Resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves the adhesion to the substrate and the compatibility with the developer.
- a repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.
- a repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs [0081] to [0084] of JP-A-2014-098921.
- Resin (A) may have a repeating unit having an alkali-soluble group.
- the alkali-soluble group includes a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulphonylimide group, and an aliphatic alcohol substituted with an electron-withdrawing group at the ⁇ -position (e.g., a hexafluoroisopropanol group). Carboxyl groups are preferred.
- the resin (A) contains a repeating unit having an alkali-soluble group, the resolution for contact holes is increased. Repeating units having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP-A-2014-098921.
- Resin (A) may have a repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability. This can reduce the elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure.
- Such repeating units include, for example, repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.
- Resin (A) may have a repeating unit represented by formula (III) that has neither a hydroxyl group nor a cyano group.
- R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
- Ra represents a hydrogen atom, an alkyl group or a --CH 2 --O--Ra 2 group.
- Ra2 represents a hydrogen atom, an alkyl group or an acyl group. Examples of the repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group include those described in paragraphs [0087] to [0094] of JP-A-2014-098921.
- the resin (A) may have repeating units other than the repeating units described above.
- the resin (A) has repeating units selected from the group consisting of repeating units having an oxathian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. You may have Such repeating units are exemplified below.
- the resin (A) may contain various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. may have
- all of the repeating units are repeating units derived from a compound having an ethylenically unsaturated bond. It is preferably composed of units. In particular, it is also preferred that all of the repeating units are composed of (meth)acrylate repeating units. In this case, all repeating units may be methacrylate repeating units, all repeating units may be acrylate repeating units, or all repeating units may be methacrylate repeating units and acrylate repeating units. It is preferable that the acrylate type repeating unit is 50 mol % or less of the total repeating units.
- Resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
- the weight average molecular weight of the resin (A) is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, further preferably 5,000 as a polystyrene equivalent value by GPC method. ⁇ 15,000 is particularly preferred.
- the dispersity (molecular weight distribution) of the resin (A) is preferably 1 to 5, more preferably 1 to 3, still more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side walls of the resist pattern, and the better the roughness.
- the resin (A) content is preferably 40.0 to 99.9% by mass, more preferably 60.0 to 90.0% by mass, based on the total solid content of the resist composition.
- the resin (A) may be used singly or in combination.
- the resist composition may contain an acid diffusion control agent.
- the acid diffusion controller does not contain onium salt (II).
- the acid diffusion control agent traps the acid generated from the photoacid generator or the like during exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
- the type of acid diffusion controller is not particularly limited, and examples include basic compounds (CA), low-molecular-weight compounds (CB) having nitrogen atoms and groups that leave under the action of acids, and actinic rays or radiation. and a compound (CC) whose ability to control acid diffusion decreases or disappears upon irradiation.
- an onium salt compound (CD) which becomes a relatively weak acid with respect to the photoacid generator
- a basic compound (CE) whose basicity is reduced or lost by irradiation with actinic rays or radiation.
- specific examples of the basic compound (CA) include those described in paragraphs [0132] to [0136] of International Publication No. 2020/066824, and basicity is obtained by irradiation with actinic rays or radiation.
- Specific examples of the basic compound that decreases or disappears include those described in paragraphs [0137] to [0155] of WO 2020/066824, have a nitrogen atom, and Specific examples of the low-molecular compound (CB) having a leaving group include those described in paragraphs [0156] to [0163] of WO2020/066824, and onium having a nitrogen atom in the cation moiety. Specific examples of salt compounds (CE) include those described in paragraph [0164] of WO2020/066824. Further, specific examples of the onium salt compound (CD), which is a relatively weak acid with respect to the photoacid generator, include those described in paragraphs [0305] to [0314] of International Publication No. 2020/158337. .
- paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167A1 paragraphs [0095] to [0187] of US Patent Application Publication No. 2015/0004544A1
- paragraphs [0237190A1 and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 can be suitably used as acid diffusion control agents.
- the content of the acid diffusion control agent (if multiple types are present, the total) is 0.1 to 20.0 with respect to the total solid content of the resist composition. % by mass is preferable, 0.1 to 15.0% by mass is more preferable, 0.1 to 10.0% by mass is still more preferable, and 1.0 to 10.0% by mass is particularly preferable.
- the acid diffusion controller may be used alone or in combination of two or more.
- the resist composition may contain, in addition to the acid-decomposable resin, a hydrophobic resin different from the acid-decomposable resin.
- the hydrophobic resin is preferably designed so that it is unevenly distributed on the surface of the resist film. don't have to contribute. Effects of the addition of the hydrophobic resin include, for example, control of the static and dynamic contact angles of the resist film surface with respect to water, and suppression of outgassing.
- the hydrophobic resin preferably has one or more of a fluorine atom, a silicon atom, and a CH3 partial structure contained in the side chain portion of the resin. It is more preferable to have Moreover, the hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain. Hydrophobic resins include, for example, compounds described in paragraphs [0275] to [0279] of WO2020/004306.
- the resist composition contains a hydrophobic resin
- its content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the resist composition. 1 to 10% by mass is more preferable, and 0.1 to 8.0% by mass is particularly preferable.
- One type of hydrophobic resin may be used alone, or two or more types may be used. When two or more are used, the total content is preferably within the range of the preferred content.
- the resist composition may contain a surfactant.
- a surfactant When a surfactant is contained, it is possible to form a pattern with excellent adhesion and fewer development defects.
- the surfactant is preferably a fluorine-based and/or silicon-based surfactant.
- fluorine-based and/or silicon-based surfactants for example, surfactants disclosed in paragraphs [0218] and [0219] of WO2018/19395 can be used.
- the resist composition contains a surfactant, its content is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the resist composition.
- One type of surfactant may be used alone, or two or more types may be used. When two or more are used, the total content is preferably within the range of the preferred content.
- the resist composition may contain a solvent.
- Solvents are (M1) propylene glycol monoalkyl ether carboxylates, and (M2) the group consisting of propylene glycol monoalkyl ethers, lactate esters, acetate esters, alkoxypropionate esters, linear ketones, cyclic ketones, lactones and alkylene carbonates. It preferably contains at least one selected from This solvent may further contain components other than components (M1) and (M2).
- the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.
- the content of the solvent in the resist composition is preferably determined so that the solid content concentration is 30% by mass or less, more preferably 10% by mass or less, and 2% by mass or less. It is more preferable to define The lower limit is preferably determined so that the solid content concentration is 0.05% by mass or more, more preferably 0.1% by mass or more, and is determined to be 0.5% by mass or more. is more preferred. Within the above range, the coatability of the resist composition can be further improved.
- the solvent content is preferably 70 to 99.95% by mass, more preferably 90 to 99.9% by mass, even more preferably 98 to 99.5% by mass, relative to the total mass of the resist composition.
- a solvent may be used individually by 1 type, and may be used in 2 or more types. When two or more are used, the total content is preferably within the range of the preferred content.
- the resist composition contains a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber and/or a compound (alicyclic or aliphatic compound containing a carboxylic acid group) that promotes solubility in a developer. It may further contain:
- the resist composition may further contain a dissolution inhibiting compound.
- dissolution inhibiting compound as used herein means a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.
- the resist composition of the present invention is also suitably used as a photosensitive composition for EUV light.
- EUV light has a wavelength of 13.5 nm, which is shorter than ArF (wavelength 193 nm) light and the like, so the number of incident photons is smaller when exposed with the same sensitivity. Therefore, the influence of "photon shot noise", in which the number of photons stochastically varies, is large, leading to deterioration of LWR and bridging defects.
- photon shot noise there is a method of increasing the number of incident photons by increasing the amount of exposure, but this is a trade-off with the demand for higher sensitivity.
- the A value is preferably 0.120 or more. If the upper limit of the A value is too large, the EUV light and electron beam transmittance of the resist film will decrease, the optical image profile in the resist film will deteriorate, and as a result it will be difficult to obtain a good pattern shape, so the upper limit is 0. 0.240 or less is preferable, and 0.220 or less is more preferable.
- [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition
- [C ] represents the molar ratio of carbon atoms derived from the total solid content with respect to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition
- [N] is actinic ray-sensitive or radiation-sensitive Represents the molar ratio of nitrogen atoms derived from the total solid content to the total atoms of the total solid content in the resin composition
- [O] is the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition represents the molar ratio of oxygen atoms derived from the total solid content
- [F] is the mole of fluorine atoms derived from the total solid content with respect to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition represents
- the acid-decomposable resin and the salt B correspond to the solid content. That is, the total atoms of the total solid content correspond to the sum of all atoms derived from the acid-decomposable resin and all atoms derived from the salt B.
- [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content.
- the molar ratio of the sum of the hydrogen atoms derived from the acid-decomposable resin and the hydrogen atoms derived from the compound (1) to the total of all atoms derived from the compound (1).
- the A value can be calculated by calculating the contained atomic number ratio when the structure and content of the constituent components of the total solid content in the resist composition are known. Moreover, even if the constituent components are unknown, it is possible to calculate the constituent atomic number ratio of the resist film obtained by evaporating the solvent component of the resist composition by analytical methods such as elemental analysis. be.
- the procedure of the pattern forming method using the resist composition preferably includes the following steps.
- Step 1 Step of forming a resist film on a substrate using a resist composition
- Step 2 Step of exposing the resist film
- Step 3 Step of developing the exposed resist film with a developer
- Step 1 is a step of forming a resist film on a substrate using a resist composition.
- the definition of the resist composition is as described above.
- a method of forming a resist film on a substrate using a resist composition includes, for example, a method of coating the substrate with the resist composition.
- the pore size of the filter is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and even more preferably 0.03 ⁇ m or less.
- the filter is preferably made of polytetrafluoroethylene, polyethylene or nylon.
- the resist composition can be applied onto substrates such as those used in the manufacture of integrated circuit devices (eg, silicon, silicon dioxide coatings) by a suitable coating method such as a spinner or coater.
- the coating method is preferably spin coating using a spinner.
- the rotation speed for spin coating using a spinner is preferably 1000 to 3000 rpm.
- the substrate may be dried to form a resist film. If necessary, various base films (inorganic film, organic film, antireflection film) may be formed under the resist film.
- Heating can be carried out by means provided in at least one of the usual exposure machine and developing machine, and may be carried out using a hot plate or the like.
- the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
- the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, even more preferably 60 to 600 seconds.
- the film thickness of the resist film is preferably 10 to 120 nm from the point of being able to form fine patterns with higher precision.
- the film thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.
- a topcoat composition may be used to form a topcoat on the upper layer of the resist film. It is preferable that the topcoat composition does not mix with the resist film and can be uniformly coated on the upper layer of the resist film.
- the topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. can be formed. For example, it is preferable to form a top coat containing a basic compound as described in JP-A-2013-061648 on the resist film. Specific examples of basic compounds that the topcoat may contain include basic compounds that the resist composition may contain.
- the topcoat preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.
- Step 2 is a step of exposing the resist film.
- the exposure method include a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask.
- Actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams.
- the wavelength of far-ultraviolet light is preferably 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm.
- Specific examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser ( 157 nm), EUV light (13 nm), X-rays, and electron beams.
- baking is preferably performed before development. Baking accelerates the reaction of the exposed area, resulting in better sensitivity and pattern shape.
- the heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
- the heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, even more preferably 30 to 120 seconds. Heating can be carried out by a means provided in at least one of the usual exposing machine and developing machine, and may be carried out using a hot plate or the like. This process is also called post-exposure bake (PEB).
- PEB post-exposure bake
- Step 3 is a step of developing the exposed resist film using a developer to form a pattern.
- the developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an "organic developer").
- Examples of the developing method include a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), and a method of developing by standing the developer on the surface of the substrate for a certain period of time by raising the developer by surface tension (puddle method). method), a method of spraying the developer onto the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the substrate rotating at a constant speed (dynamic dispensing method). law). Further, after the step of developing, a step of stopping development may be performed while replacing the solvent with another solvent.
- the development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
- the temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.
- alkaline aqueous solution containing alkali As the alkaline developer.
- alkaline aqueous solutions include, for example, aqueous alkaline solutions containing quaternary ammonium salts typified by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines or cyclic amines. .
- the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Suitable amounts of alcohols, surfactants and the like may be added to the alkaline developer.
- the alkali concentration of the alkali developer is usually 0.1 to 20 mass %.
- the pH of the alkaline developer is usually 10.0 to 15.0.
- the content of water in the alkaline developer is preferably 51 to 99.95% by mass.
- the organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. is preferred.
- a plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water.
- the water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, relative to the total mass of the developer, and should be substantially free of water.
- the content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass, based on the total mass of the developer. % by weight is particularly preferred.
- the pattern forming method preferably includes a step of washing with a rinse after step 3.
- Pure water is an example of the rinse solution used in the rinse step after the step of developing with an alkaline developer.
- An appropriate amount of surfactant may be added to pure water.
- An appropriate amount of surfactant may be added to the rinse solution.
- the rinse solution used in the rinse step after the development step using the organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used.
- the rinse solution may contain at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. preferable.
- the method of the rinsing step is not particularly limited.
- a method of continuously discharging the rinsing liquid onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a tank filled with the rinsing liquid for a certain period of time.
- a method (dip method) and a method of spraying a rinse liquid onto the substrate surface can be mentioned.
- the pattern forming method of the present invention may include a heating step (Post Bake) after the rinsing step. In this step, the developing solution and the rinse solution remaining between the patterns and inside the patterns due to baking are removed.
- the heating step after the rinsing step is usually carried out at 40 to 250° C. (preferably 90 to 200° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 2 minutes).
- the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and the substrate) to form a pattern on the substrate.
- the method of processing the substrate (or the underlying film and the substrate) is not particularly limited, but the substrate (or the underlying film and the substrate) is dry-etched using the pattern formed in step 3 as a mask to form a pattern on the substrate.
- a method of forming is preferred. Dry etching is preferably oxygen plasma etching.
- Various materials used in the resist composition and the pattern forming method of the present invention contain impurities such as metals. preferably not included.
- the content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, and 100 mass ppt (parts per trillion) or less with respect to the total solid content of the resist composition or various materials. More preferably, 10 mass ppt or less is particularly preferable, and 1 mass ppt or less is most preferable.
- examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W and Zn are mentioned.
- a method of reducing impurities such as metals contained in various materials for example, a method of selecting a raw material with a low metal content as a raw material constituting various materials, a method of filtering the raw materials constituting various materials and a method of performing distillation under conditions in which contamination is suppressed as much as possible by, for example, lining the inside of the apparatus with Teflon (registered trademark).
- impurities may be removed with an adsorbent, or filter filtration and adsorbent may be used in combination.
- adsorbent known adsorbents can be used.
- inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
- Whether the metal impurities are sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing equipment.
- the content of the metal component contained in the cleaning liquid after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less.
- Conductive compounds are added to organic treatment liquids such as rinsing liquids in order to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge.
- Conductive compounds include, for example, methanol.
- the amount to be added is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable developing properties or rinsing properties.
- As the chemical pipe for example, SUS (stainless steel) or various pipes coated with antistatic polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used.
- filters and O-rings antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can also be used.
- the present invention also relates to an electronic device manufacturing method including the pattern forming method and an electronic device manufactured by this manufacturing method.
- the electronic device of the present invention is suitably mounted in electric/electronic equipment (household appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).
- reaction solution 2 Ethyl acetate (600 mL) was added to reaction solution 1, the organic phase was washed with 1N hydrochloric acid and water, and the solvent was distilled off to obtain a crude product of the following formula (I)-1-B. Subsequently, the crude product of (I)-1-B was dissolved in tetrahydrofuran (500 mL), 10% aqueous sodium hydrogen carbonate solution (500 mL) was added to the solution, and the mixture was stirred at 50° C. for 3 hours to give reaction solution 2. Obtained.
- Onium salts (I)-2 to (I)-18 were synthesized according to the method for synthesizing onium salt (I)-1.
- Onium salts (II)-1 to (II) to 18 were synthesized according to the method for synthesizing onium salt (I)-1.
- Table 1 shows the acid dissociation constants (pKa) derived from the acidic sites represented by HA in which the cationic sites in onium salt (I) and onium salt (II) are replaced with H 2 + .
- pKa indicates the value obtained using the software package 1 described above.
- the onium salt (II) has a plurality of acidic sites, the pKa of the acidic site derived from the constituent site W is shown.
- Resin A The resins (A-1 to A-34 (corresponding to acid-decomposable resins)) used in the preparation of the resist composition are shown below. Resins A-1 to A-34 were synthesized according to known methods. In Table 1, the “molar ratio” column shows the content (mol%) of each repeating unit with respect to all repeating units. In Table 1, the “Mw” column indicates the weight average molecular weight. In Table 1, the “Mw/Mn” column indicates the degree of dispersion.
- the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the resins A-1 to A-34 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). Also, the composition ratio (molar ratio) of the resin was measured by 13 C-NMR (Nuclear Magnetic Resonance).
- Acid diffusion control agent B Structures of the acid diffusion inhibitors (B-1 to B-4) used in the preparation of the resist composition are shown below.
- [Hydrophobic resin C] The hydrophobic resins C (C-1 to C-8) used in the preparation of the resist composition are shown below.
- the "molar ratio” column shows the content (mol%) of each repeating unit with respect to all repeating units.
- the "Mw” column indicates the weight average molecular weight.
- the "Mw/Mn” column indicates the degree of dispersion.
- the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the resins C-1 to C-8 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene).
- the composition ratio (molar ratio) of the resin was measured by 13 C-NMR (Nuclear Magnetic Resonance).
- Surfactants E used in the preparation of resist compositions are shown below.
- E-1 Megafac F176 (manufactured by DIC Corporation, fluorine-based surfactant)
- E-2 Megafac R08 (manufactured by DIC Corporation, fluorine- and silicon-based surfactant)
- E-3 PF656 (manufactured by OMNOVA, fluorine-based surfactant)
- Solvents F used in the preparation of resist compositions are shown below.
- F-1 Propylene glycol monomethyl ether acetate (PGMEA)
- F-2 Propylene glycol monomethyl ether (PGME)
- F-3 Propylene glycol monoethyl ether (PGEE)
- F-4 cyclohexanone
- F-5 cyclopentanone
- F-6 2-heptanone
- F-7 ethyl lactate
- F-8 ⁇ -butyrolactone
- F-9 propylene carbonate
- the description separated by "/” in the type column indicates that the substance contains multiple compounds
- the description separated by "/” in the mass% column indicates the content of multiple compounds. shown in order.
- the "onium salt (I)" of “Re-26” includes “(I)-1” and “(I)-14", and the contents are in order “13.0” and “13.0” It represents that it is mass%.
- the "% by mass” column shows the content (% by mass) of each solid content component with respect to the total solid content.
- the solid content refers to components excluding solvent.
- the “mixing ratio” column of "solvent” indicates the mixing ratio (mass ratio) of each solvent.
- ⁇ Cross-sectional rectangularity evaluation (part 1)> The resist patterns of Examples and Comparative Examples (Examples 1-1 to 1-35 and Comparative Examples 1-1 and 1-2) obtained by organic solvent development were evaluated according to the following procedure.
- the cross-sectional shape of the line pattern with an average line width of 20 nm in each example and each comparative example was observed with a length measurement scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), and the pattern at the bottom of the resist pattern.
- a line width Lb and a pattern line width La at the top of the resist pattern were measured.
- the cross-sectional rectangularity of the pattern shape was evaluated according to the following criteria. S is the best and E is the worst.
- Table 5 shows the evaluation results of cross-sectional rectangularity of Examples 1-1 to 1-35 and Comparative Examples 1-1 and 1-2 (alkali development).
- Table 6 shows the evaluation results of cross-sectional rectangularity of Examples 2-1 to 2-35 and Comparative Examples 2-1 and 2-2 (development with organic solvent).
- the notations "A" to "D” in the "requirement 1" column indicate the following cases for the onium salt (I) used in the resist composition.
- Onium salt (I) generates an acid represented by formula (1) above, and R S in formula (1) is —CO—OR S1 or —O—CO—R S1 and n is 2 to 5
- the onium salt (I) generates an acid represented by the above formula (1), and R S in formula (1) is —CO—R S1 , — represents CO—O—R S1 , —O—CO—R S1 , —O—CO—OR S1 , —SO 2 —R S1 , or —SO 3 —R S1 and n is 1; or when only one of R s in formula (1) represents —CO—OR S1 or —O—CO—R S1 and n is 2 to 5
- C onium salt ( I) generates an acid represented by formula (1) above, and R S in formula (1) represents —OR S1 D: onium salt (I) is represented by formula (1) above In Tables 5 and 6, the notations "A" to "C” in the column "Requirement 2" refer to the
- anion site A anion site showing pKa in Table 1
- B onium salt (II)
- the anion site A in the structural site W is a site represented by any one of formulas (II)-3 to (II)-6, and formula (II)-
- An anion site A an anion site showing pKa in Table 1) in structural site W in onium salt (II) is a site represented by formula (II)-2 , formula (II)-1, or when it is not a site represented by formulas (II)-3 to (II)-6
- the resist composition (actinic ray-sensitive or radiation-sensitive resin composition) of the present invention is excellent in cross-sectional rectangularity. From the comparison of Examples 1-3, 1-22, and 1-31, and Examples 2-3, 2-22, and 2-31 with other examples, the anion site in structural site W It was confirmed that when A is a moiety represented by any one of formulas (II)-1 to (II)-6, the effects of the present invention are more excellent.
- the anion site A in the structural site W is , the site represented by the above formula (II)-1, it was confirmed that the effects of the present invention are more excellent.
- R S is —CO—OR S1 , —O—CO—R S1 , —O—CO—OR S1 , —SO 2 —R S1 , or —SO 3 —R It was confirmed that when S1 is represented and R S1 represents a monovalent substituent, the effects of the present invention are more excellent.
- R S is -CO-OR S1 or -O-CO-R S1 and when R S1 represents a monovalent substituent, it was confirmed that the effects of the present invention are more excellent.
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Abstract
Description
感活性光線性又は感放射線性樹脂組成物を用いて形成された、感活性光線性又は感放射線性樹脂膜(以下、「レジスト膜」ともいう。)を露光し、露光パターンを反映した領域でレジスト膜に現像液に対する溶解性の変化を生じさせる。その後、現像液(例えば、アルカリ水溶系又は有機溶剤系現像液等)を用いて、現像を行い、レジスト膜における露光部又は非露光部を除去して、所望のパターンを得る。
また、本発明は、レジスト膜、パターン形成方法、及び、電子デバイスの製造方法を提供することを課題とする。
活性光線又は放射線の照射によって後述する式(1)で表される酸を発生するオニウム塩(I)と、
アニオン部位Aとカチオン部位Mとからなり、活性光線又は放射線の照射によってHAで表される酸性部位を形成する構造部位Wを少なくとも1つ有するオニウム塩(II)と、を含み、
構造部位W中のカチオン部位をH+に置き換えてなるHAで表される酸性部位に由来する酸解離定数が、式(1)で表される酸の酸解離定数よりも大きい、感活性光線又は感放射線性樹脂組成物。
〔2〕 上記構造部位Wの上記アニオン部位Aが、後述する式(II)-1~(II)-6のいずれかで表される部位である、〔1〕に記載の感活性光線又は感放射線性樹脂組成物。
〔3〕 上記構造部位Wの上記アニオン部位Aが、後述する式(II)-1、及び、式(II)-3~(II)-6のいずれかで表される部位である、〔2〕に記載の感活性光線又は感放射線性樹脂組成物。
〔4〕 上記構造部位W中の上記アニオン部位Aが、後述する式(II)-1で表される部位である、〔2〕に記載の感活性光線又は感放射線性樹脂組成物。
〔5〕 上記式(1)中のnが2~5である、〔1〕~〔4〕のいずれか1つに記載の感活性光線又は感放射線性樹脂組成物。
〔6〕 上記式(1)中、RSがそれぞれ独立に、-CO-ORS1、-O-CO-RS1、-O-CO-O-RS1、-SO2-RS1、又は、-SO3-RS1を表し、RS1が、1価の置換基を表す、〔1〕~〔5〕のいずれか1つに記載の感活性光線又は感放射線性樹脂組成物。
〔7〕 上記式(1)中、RSがそれぞれ独立に、-CO-ORS1、又は、-O-CO-RS1を表し、RS1が、1価の置換基を表す、〔1〕~〔6〕のいずれか1つに記載の感活性光線又は感放射線性樹脂組成物。
〔8〕 〔1〕~〔7〕のいずれか1つに記載の感活性光線性又は感放射線性樹脂組成物を用いて形成される、レジスト膜。
〔9〕 〔1〕~〔7〕のいずれか1つに記載の感活性光線性又は感放射線性樹脂組成物を用いて基板上にレジスト膜を形成するレジスト膜形成工程と、
上記レジスト膜を露光する露光工程と、
露光された上記レジスト膜に対して現像液を用いて現像する現像工程と、を有する、パターン形成方法。
〔10〕 上記露光工程においてEUV光により露光する、〔9〕に記載のパターン形成方法。
〔11〕 上記現像液が、有機溶剤を含む、〔9〕又は〔10〕に記載のパターン形成方法。
〔12〕 上記有機溶剤が、酢酸ブチルを含む、〔11〕に記載のパターン形成方法。
〔13〕 〔9〕~〔12〕に記載のパターン形成方法を含む、電子デバイスの製造方法。
また、本発明は、上記感活性光線性又は感放射線性樹脂組成物に関する、レジスト膜、パターン形成方法、及び、電子デバイスの製造方法を提供できる。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされる場合があるが、本発明はそのような実施態様に制限されない。
本明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
基(原子団)の表記について、本発明の趣旨に反しない限り、置換及び無置換を記していない表記は、置換基を有さない基と共に置換基を有する基をも包含する。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
「アルキル基」は、直鎖状又は分岐鎖状のアルキル基を表す。「シクロアルキル基」は、環状のアルキル基を表す。
置換基は、特段の断りがない限り、1価の置換基である。
置換基としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子等のハロゲン原子;メトキシ基、エトキシ基及びtert-ブトキシ基等のアルコキシ基;フェノキシ基及びp-トリルオキシ基等のアリールオキシ基;メトキシカルボニル基、ブトキシカルボニル基及びフェノキシカルボニル基等のアルコキシカルボニル基;アセトキシ基、プロピオニルオキシ基及びベンゾイルオキシ基等のアシルオキシ基;アセチル基、ベンゾイル基、イソブチリル基、アクリロイル基、メタクリロイル基及びメトキサリル基等のアシル基;メチルスルファニル基及びtert-ブチルスルファニル基等のアルキルスルファニル基;フェニルスルファニル基及びp-トリルスルファニル基等のアリールスルファニル基;アルキル基;シクロアルキル基;アリール基;ヘテロアリール基;水酸基;カルボキシ基;ホルミル基;スルホ基;シアノ基;アルキルアミノカルボニル基;アリールアミノカルボニル基;スルホンアミド基;シリル基;アミノ基;モノアルキルアミノ基;ジアルキルアミノ基;アリールアミノ基;アルキルチオ基;並びにこれらの組み合わせが挙げられる。明細書中では、これら置換基群を「置換基K」ともいう。
「光」とは、活性光線又は放射線を意味する。
「露光」とは、特段の断りがない限り、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線、X線、及び、EUV光等による露光のみならず、電子線及びイオンビーム等の粒子線による描画も含む。
「~」とはその前後に記載される数値を下限及び上限として含む意味で使用される。
本明細書において表記される2価の基の結合方向は、特段の断りがない限り、制限されない。例えば、「X-Y-Z」なる一般式で表される化合物中の、Yが-COO-である場合、Yは、-CO-O-であってもよく、-O-CO-であってもよい。また、上記化合物は「X-CO-O-Z」であってもよく「X-O-CO-Z」であってもよい。
(メタ)アクリルは、アクリル及びメタクリルを表す。
ソフトウェアパッケージ1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs)。
一方で、pKaは、分子軌道計算法によっても求められる。この具体的な方法としては、熱力学サイクルに基づいて、水溶液中におけるH+解離自由エネルギーを計算することで算出する手法が挙げられる。H+解離自由エネルギーの計算方法については、例えばDFT(密度汎関数法)により計算することができるが、他にも様々な手法が文献等で報告されており、これに制限されるものではない。なお、DFTを実施できるソフトウェアは複数存在するが、例えば、Gaussian16が挙げられる。
pKaとは、上述したとおり、ソフトウェアパッケージ1を用いて、ハメットの置換基定数及び公知文献値のデータベースに基づいた値を計算により求められる値を意味するが、この手法によりpKaが算出できない場合、DFT(密度汎関数法)に基づいてGaussian16により得られる値を採用するものとする。
また、pKaは、上述したとおり、「水溶液中でのpKa」を意味し、水溶液中でのpKaが算出できない場合、「ジメチルスルホキシド(DMSO)溶液中でのpKa」とする。
本発明の感活性光線性又は感放射線性樹脂組成物は、酸の作用により分解して極性基を生じる基を有する樹脂と、活性光線又は放射線の照射によって後述する式(1)で表される酸を発生するオニウム塩(I)と、アニオン部位Aとカチオン部位Mとからなり、活性光線又は放射線の照射によってHAで表される酸性部位を形成する構造部位Wを少なくとも1つ有するオニウム塩(II)と、を含み、構造部位W中のカチオン部位をH+に置き換えてなるHAで表される酸性部位に由来する酸解離定数が、式(1)で表される酸の酸解離定数よりも大きい。
以下、「感活性光線性又は感放射線性樹脂組成物」を「レジスト組成物」ともいう。
以下、「酸の作用により分解して極性基を生じる基を有する樹脂」を「酸分解性樹脂」ともいう。
以下、「構造部位W中のカチオン部位をH+に置き換えてなるHAで表される酸性部位に由来する酸解離定数」を「構造部位WのHAの酸解離定数」ともいう。
オニウム塩(I)は、レジスト組成物に含まれる酸分解性樹脂との相互作用が大きく、レジスト膜の露光部で発生した酸が未露光部へ拡散することが抑制される。更に、本発明のレジスト組成物に含まれるオニウム塩(II)における構造部位Wの酸性部位の酸解離定数は、オニウム塩(I)から発生する酸の酸解離定数よりも大きいため、レジスト膜の未露光部においてオニウム塩(II)は、オニウム塩(I)から発生した酸のクエンチャーとして機能しうる。従って、オニウム塩(I)から発生した酸は、未露光部のオニウム塩(II)の作用で、未露光部への拡散が更に抑制される。結果として、基板上に形成したレジスト膜を露光し、現像してパターンを得る際、レジスト膜の露光部から発生した酸が拡散せず、基板と対向する側の面と基板と反対側の面とで、現像時に除去されるパターンの幅がほぼ同一となり、パターンの断面矩形性に優れる。
レジスト組成物は、ポジ型レジスト組成物、及び、ネガ型レジスト組成物のいずれであってもよい。また、アルカリ現像用レジスト組成物、及び、有機溶剤現像用レジスト組成物のいずれであってもよい。
レジスト組成物は、非化学増幅型レジスト組成物であってもよく、レジスト組成物に化学増幅型レジスト組成物としての機構を併用してもよい。
以下、レジスト組成物の各種成分について詳述する。
オニウム塩(I)は、活性光線又は放射線の照射によって後述する式(1)で表される酸を発生するオニウム塩である。従って、オニウム塩(I)は、光酸発生剤として機能する。
なお、オニウム塩は、アニオン部位とカチオン部位とを分子内に持つ化合物である。オニウム塩(I)において、アニオン部位は後述する式(1)で表される酸由来のアニオンである。
以下、式(1)で表される酸、及び、オニウム塩(I)のカチオン部位について説明する。
式(1)を以下に示す。
Rfは、フッ素原子、又は、少なくとも1つのフッ素原子を有するアルキル基を表す。
Yは、単結合、酸素原子、又は、硫黄原子を表す。
Arは、RS以外の置換基を有していてもよい、n+1価の芳香環基を表す。
RSは、-O-RS1、-CO-RS1、-CO-O-RS1、-O-CO-RS1、-O-CO-O-RS1、-SO2-RS1、又は、-SO3-RS1を表す。RS1は、1価の置換基を表す。
mは、1以上の整数を表す。
nは、1~5の整数を表す。
以下、式(1)で表される酸についてそれぞれの要件を詳細に説明する。
RXのアルキル基部分の炭素数は特に制限されず、1~6が好ましく、1~2がより好ましい。
アルキル基は、少なくとも1つのフッ素原子を有する。つまり、アルキル基の少なくとも1つの水素原子がフッ素原子で置換されていればよく、アルキル基の水素原子が全てフッ素原子に置換されていてもよい。なかでも、アルキル基の水素原子が全てフッ素原子に置換されていていることが好ましい。すなわち、RXはパーフルオロアルキル基が好ましい。
なお、X中のHは解離しやすく、Xは酸として作用する原子団を形成する。従って、式(1)で表される酸の酸解離定数は、X中のHの解離定数である。式(1)で表される酸の酸解離定数は、オニウム塩(II)の構造部位Wの酸性部位の酸解離定数よりも小さければ特に制限されないが、2.0以下が好ましく、0.5以下がより好ましく、-3.0以下が更に好ましい。下限は特に制限されないが、-15.0以上が挙げられる。
Rfが少なくとも1つのフッ素原子を有するアルキル基である場合、Rfのアルキル基部分の炭素数は特に制限されず、1~6が好ましく、1~2がより好ましい。
アルキル基は、少なくとも1つのフッ素原子を有する。つまり、アルキル基の少なくとも1つの水素原子がフッ素原子で置換されていればよく、アルキル基の水素原子が全てフッ素原子に置換されていてもよい。なかでも、アルキル基の水素原子が全てフッ素原子に置換されていていることが好ましい。すなわち、Rfが少なくとも1つのフッ素原子を有するアルキル基である場合、Rfはパーフルオロアルキル基が好ましい。
なかでも、Rfはフッ素原子が好ましい。
Yは、単結合、又は、酸素原子が好ましく、酸素原子がより好ましい。
芳香環基は特に制限されず、芳香環基を構成する芳香環は単環であっても多環であってもよい。
芳香環基を構成する芳香環としては、芳香族炭化水素環及び芳香族複素環が挙げられる。芳香族炭化水素環としては、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、及び、ピレン環が挙げられる。芳香族複素環としては、フラン環、ピロール環、ピラゾール環、イミダゾール環、チオフェン環、オキサゾール環、及び、チアゾール環が挙げられる。
芳香環基を構成する芳香環が多環である場合、芳香族炭化水素環と芳香族複素環とを組み合わせた多環であってもよい。多環としては、インドール環、イソインドール環、ベンゾイミダゾール環、プリン環、カルバゾール環、ベンゾフラン環、イソベンゾフラン環、ベンゾチオフェン環、ベンゾオキサゾール環、及び、ベンゾチアゾール環が挙げられる。
なかでも、芳香環基は芳香族炭化水素環が好ましく、ベンゼン環が好ましい。
なお、Arは、RS以外の置換基を有していてもよい。RS以外の置換基としては、アルキル基が挙げられ、アルキル基の炭素数は、1~5が好ましい。アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、sec-ブチル基、及び、t-ブチル基が挙げられる。なかでも、メチル基が好ましい。
上記アルキル基は、置換基を有していてもよい。置換基としては、置換基Kが挙げられ、ハロゲン原子が好ましい。
nが2以上の場合、RSはそれぞれ同一であってもよく、それぞれ異なっていてもよい。また、nが2以上の場合、RSは互いに結合して環を形成していてもよい。
本発明の効果がより優れる点で、RSは、-CO-RS1、-CO-O-RS1、-O-CO-RS1、-O-CO-O-RS1、-SO2-RS1、又は、-SO3-RS1が好ましく、-CO-ORS1、-O-CO-RS1、-O-CO-O-RS1、-SO2-RS1、又は、-SO3-RS1が更に好ましく、-CO-O-RS1、又は、-O-CO-RS1がより好ましい。
置換基を有していてもよいアルキル基中のアルキル基部分としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、sec-ブチル基、及び、t-ブチル基等が挙げられる。
アルキル基が有していてもよい置換基としては、例えば置換基Kが挙げられ、なかでも、ハロゲン原子が好ましく、フッ素原子がより好ましい。水素原子がハロゲン原子で置換されている場合、アルキル基における水素原子は、一部が置換されていてもよく、すべてが置換されていてもよい。
置換基を有していてもよいシクロアルキル基のシクロアルキル基部分としては、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、及び、シクロヘプチル基等の単環のシクロアルキル基、並びに、ノルボルニル基、カンファー残基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が挙げられる。
シクロアルキル基における-(CH2)-が2価の置換基に置換されていることも好ましい。シクロアルキル基における-(CH2)-を置換する2価の置換基は、-O-、-S-、-CO-、-OC-O-、又は、-CO-O-が好ましく、-O-がより好ましい。シクロアルキル基における-(CH2)-を置換する2価の置換基の数は、1~3が好ましく、1がより好ましい。
また、シクロアルキル基が有していてもよい置換基としては、例えば置換基Kが挙げられ、なかでもアルキル基が好ましい。アルキル基の好適態様及び具体例は、置換基を有していてもよいアルキル基中のアルキル基部分で説明したものと同様である。
置換基を有していてもよいアリール基を構成する芳香環部分の具体例は、Arにおける芳香環と同様である。なかでも、置換基を有していてもよいアリール基を構成する芳香環部分は、ベンゼン環が好ましい。
アリール基が有していてもよい置換基としては、例えば置換基Kが挙げられ、なかでも置換基を有していてもよいアルキル基が好ましい。置換基を有していてもよいアルキル基における炭素数は特に制限されず、1~8が好ましく、1~4がより好ましい。
置換基を有していてもよいアルキル基の具体例は、上記の置換基を有していてもよいアルキル基と同様であり、好適態様も同様である。
置換基を有していてもよいアリール基における置換基の数は特に制限されないが、1~3が好ましく、1~2がより好ましい。
mは1~5の整数が好ましく、1~3の整数がより好ましい。
本発明の効果がより優れる点で、nは2~5の整数が好ましく、2~3の整数がより好ましく、2が更に好ましい。
また、nが2~3の整数であり、かつ、上記RSが-CO-O-RS1、又は、-O-CO-RS1である態様が好ましい。
オニウム塩(I)のカチオン部位は、正電荷を帯びた原子又は原子団を含む構造部位であり、例えば、電荷が1価の有機カチオンが挙げられる。以下、有機カチオンの好ましい態様について説明する。
オニウム塩(I)の有機カチオン部位は、式(ZaI)で表される有機カチオン(カチオン(ZaI))、又は、式(ZaII)で表される有機カチオン(カチオン(ZaII))が好ましい。
R201、R202及びR203としての有機基の炭素数は、通常1~30であり、1~20が好ましい。また、R201~R203のうち2つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、-CO-O-、アミド基又はカルボニル基を含んでいてもよい。R201~R203の内の2つが結合して形成する基としては、例えば、アルキレン基(例えば、ブチレン基及びペンチレン基)、及び、-CH2-CH2-O-CH2-CH2-が挙げられる。
カチオン(ZaI-1)は、上記式(ZaI)のR201~R203の少なくとも1つがアリール基である、アリールスルホニウムカチオンである。
アリールスルホニウムカチオンは、R201~R203の全てがアリール基であってもよいし、R201~R203の一部がアリール基であり、残りがアルキル基又はシクロアルキル基であってもよい。
また、R201~R203のうちの1つがアリール基であり、R201~R203のうちの残りの2つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、-CO-O-、アミド基又はカルボニル基を含んでいてもよい。R201~R203のうちの2つが結合して形成する基としては、例えば、1つ以上のメチレン基が酸素原子、硫黄原子、-CO-O-、アミド基及び/又はカルボニル基で置換されていてもよいアルキレン基(例えば、ブチレン基、ペンチレン基又はCH2-CH2-O-CH2-CH2-)が挙げられる。
アリールスルホニウムカチオンとしては、例えば、トリアリールスルホニウムカチオン、ジアリールアルキルスルホニウムカチオン、アリールジアルキルスルホニウムカチオン、ジアリールシクロアルキルスルホニウムカチオン及びアリールジシクロアルキルスルホニウムカチオンが挙げられる。
アリールスルホニウムカチオンが必要に応じて有しているアルキル基又はシクロアルキル基は、炭素数1~15の直鎖状アルキル基、炭素数3~15の分岐鎖状アルキル基又は炭素数3~15のシクロアルキル基が好ましく、例えば、メチル基、エチル基、プロピル基、n-ブチル基、sec-ブチル基、t-ブチル基、シクロプロピル基、シクロブチル基及びシクロヘキシル基等がより好ましい。
上記置換基は可能な場合更に置換基を有していてもよく、例えば、上記アルキル基が置換基としてハロゲン原子を有して、トリフルオロメチル基等のハロゲン化アルキル基となっていることも好ましい。
また、上記置換基は任意の組み合わせにより、酸分解性基を形成することも好ましい。
なお、酸分解性基とは、酸の作用により分解して酸基を生じる基を意図し、酸の作用により脱離する脱離基で酸基が保護された構造であることが好ましい。上記の酸基及び脱離基は、酸分解性樹脂で詳述する。
カチオン(ZaI-2)は、式(ZaI)におけるR201~R203が、それぞれ独立に、芳香環を有さない有機基を表すカチオンである。なお、芳香環とは、ヘテロ原子を含む芳香環も包含する。
R201~R203としての芳香環を有さない有機基は、一般的に炭素数1~30であり、炭素数1~20が好ましい。
R201~R203は、それぞれ独立に、アルキル基、シクロアルキル基、アリル基又はビニル基が好ましく、直鎖状又は分岐鎖状の2-オキソアルキル基、2-オキソシクロアルキル基又はアルコキシカルボニルメチル基がより好ましく、直鎖状又は分岐鎖状の2-オキソアルキル基が更に好ましい。
R201~R203は、ハロゲン原子、アルコキシ基(例えば炭素数1~5)、水酸基、シアノ基又はニトロ基によって更に置換されていてもよい。
また、R201~R203の置換基は、それぞれ独立に、置換基の任意の組み合わせにより、酸分解性基を形成することも好ましい。
カチオン(ZaI-3b)は、式(ZaI-3b)で表されるカチオンである。
R6c及びR7cは、それぞれ独立に、水素原子、アルキル基(t-ブチル基等)、シクロアルキル基、ハロゲン原子、シアノ基又はリール基を表す。
Rx及びRyは、それぞれ独立に、アルキル基、シクロアルキル基、2-オキソアルキル基、2-オキソシクロアルキル基、アルコキシカルボニルアルキル基、アリル基又はビニル基を表す。
また、R1c~R7c、並びに、Rx及びRyの置換基は、それぞれ独立に、置換基の任意の組み合わせにより、酸分解性基を形成することも好ましい。
上記環としては、芳香族又は非芳香族の炭化水素環、芳香族又は非芳香族のヘテロ環及びこれらの環が2つ以上組み合わされてなる多環縮合環が挙げられる。環としては、3~10員環が挙げられ、4~8員環が好ましく、5又は6員環がより好ましい。
R5cとR6c及びR5cとRxが結合して形成する基としては、単結合又はアルキレン基が好ましい。アルキレン基としては、メチレン基及びエチレン基が挙げられる。
カチオン(ZaI-4b)は、式(ZaI-4b)で表されるカチオンである。
R13は、水素原子、ハロゲン原子(例えば、フッ素原子、ヨウ素原子等)、水酸基、アルキル基、ハロゲン化アルキル基、アルコキシ基、カルボキシ基、アルコキシカルボニル基又はシクロアルキル基を有する基(シクロアルキル基そのものであってもよく、シクロアルキル基を一部に含む基であってもよい)を表す。これらの基は、更に置換基を有してもよい。
R14は、水酸基、ハロゲン原子(例えば、フッ素原子、ヨウ素原子等)、アルキル基、ハロゲン化アルキル基、アルコキシ基、アルコキシカルボニル基、アルキルカルボニル基、アルキルスルホニル基、シクロアルキルスルホニル基又はシクロアルキル基を有する基(シクロアルキル基そのものであってもよく、シクロアルキル基を一部に含む基であってもよい)を表す。これらの基は置換基を有してもよい。R14は、複数存在する場合、それぞれ独立して、水酸基等の上記基を表す。
R15は、それぞれ独立して、アルキル基、シクロアルキル基又はナフチル基を表す。2つのR15が互いに結合して環を形成してもよい。2つのR15が互いに結合して環を形成するとき、環骨格内に、酸素原子又は窒素原子等のヘテロ原子を含んでいてもよい。
一態様において、2つのR15がアルキレン基であり、互いに結合して環構造を形成することが好ましい。なお、上記アルキル基、上記シクロアルキル基及び上記ナフチル基、並びに、2つのR15が互いに結合して形成する環は置換基を有してもよい。
また、R13~R15、並びに、Rx及びRyの各置換基は、それぞれ独立に、置換基の任意の組み合わせにより、酸分解性基を形成するのも好ましい。
式(ZaII)中、R204及びR205は、それぞれ独立に、アリール基、アルキル基又はシクロアルキル基を表す。
R204及びR205のアリール基は、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。R204及びR205のアリール基は、酸素原子、窒素原子又は硫黄原子等を有するヘテロ環を有するアリール基であってもよい。ヘテロ環を有するアリール基の骨格としては、例えば、ピロール、フラン、チオフェン、インドール、ベンゾフラン及びベンゾチオフェンが挙げられる。
R204及びR205のアルキル基及びシクロアルキル基は、炭素数1~10の直鎖状アルキル基又は炭素数3~10の分岐鎖状アルキル基(例えば、メチル基、エチル基、プロピル基、ブチル基又はペンチル基)又は炭素数3~10のシクロアルキル基(例えばシクロペンチル基、シクロヘキシル基又はノルボルニル基)が好ましい。
オニウム塩(I)は1種単独で用いてもよく、2種以上で用いてもよい。2種以上使用する場合、その合計含有量が、上記好適含有量の範囲内であることが好ましい。
オニウム塩(II)は、アニオン部位Aとカチオン部位Mとからなり、活性光線又は放射線の照射によってHAで表される酸性部位を形成する構造部位Wを少なくとも1つ有し、構造部位W中のカチオン部位をH+に置き換えてなるHAで表される酸性部位に由来する酸解離定数(構造部位WのHAの酸解離定数)が、上記式(1)で表される酸の酸解離定数よりも大きい。
また、オニウム塩(II)は、構造部位W以外にも、アニオン部位AYとカチオン部位MYとからなり、活性光線又は放射線の照射によってHAYで表される酸性部位を形成する構造部位Yを更に有していてもよい。構造部位Y中のカチオン部位MYをH+に置き換えてなるHAYで表される酸性部位に由来する酸解離定数(構造部位YのHAYの酸解離定数)は、上記式(1)で表される酸の酸解離定数と同じか、又は、上記式(1)で表される酸の酸解離定数より小さい。
まず、構造部位W、及び、構造部位Yについて説明する。
構造部位Wは、上述したようにアニオン部位Aとカチオン部位Mとからなる。
オニウム塩(II)は構造部位Wを複数有していてもよい。
構造部位Wのアニオン部位A及びカチオン部位Mについて詳細に説明する。
アニオン部位Aは、負電荷を帯びた原子又は原子団を含む構造部位である。アニオン部位Aは、構造部位WのHAの酸解離定数が上記式(1)で表される酸の酸解離定数よりも大きければ特に制限されない。以下、アニオン部位Aの好ましい態様について説明する。
式(1)で表される酸の酸解離定数と構造部位WのHAの酸解離定数との差は、1.0以上が好ましく、1.5以上がより好ましい。
なお、式(II)-1~(II)-6中、*は結合手を表す。
カチオン部位Mは、正電荷を帯びた原子又は原子団を含む構造部位である。カチオン部位Mは、活性光線又は放射線の照射によって構造単位WがHAで表される酸性部位を形成することができれば特に制限されず、定義及び好適態様は上記オニウム塩(I)のカチオン部位で説明した通りである。
構造部位Yは、上述したようにアニオン部位AYとカチオン部位MYとからなる。
オニウム塩(II)は、構造部位Yを複数有していてもよい。
構造部位Yのアニオン部位AY及びカチオン部位MYについて詳細に説明する。
アニオン部位AYは、負電荷を帯びた原子又は原子団を含む構造部位である。アニオン部位AYの、構造部位Y中のカチオン部位MYをH+に置き換えてなるHAYで表される酸性部位に由来する酸解離定数は、上記式(1)で表される酸の酸解離定数と同じか、又は、上記式(1)で表される酸の酸解離定数より小さい。
以下、アニオン部位AYについて説明する。
カチオン部位MYは、正電荷を帯びた原子又は原子団を含む構造部位である。カチオン部位MYは、活性光線又は放射線の照射によって構造単位YがHAYで表される酸性部位を形成することができれば特に制限されず、定義及び好適態様は上記オニウム塩(I)のカチオン部位で説明した通りである。
オニウム塩(II)としては、式(II-A)で表される化合物が好ましい。なお、式(II-A)中のMa +Aa -部分が、構造部位Wを含む。
式(II-A) Ma +Aa --La-Ra
Ma +は、有機カチオンを表す。有機カチオンとしては、上述した、式(ZaI)で表される有機カチオン(カチオン(ZaI))、又は、式(ZaII)で表される有機カチオン(カチオン(ZaII))が好ましい。
Aa -は、式(B-1)~式(B-8)で表される基を表す。
Rx1としては、直鎖状、分岐鎖状、若しくは環状のアルキル基、又はアリール基が好ましい。
上記アルキル基の炭素数は1~15が好ましく、1~10がより好ましい。
上記アルキル基は、置換基を有していてもよい。置換基としては、フッ素原子、又はシアノ基が好ましい。上記アルキル基が置換基としてフッ素原子を有する場合、パーフルオロアルキル基であってもよい。
また、上記アルキル基は、炭素原子がカルボニル基で置換されていてもよい。
上記アリール基は、置換基を有していてもよい。置換基としては、フッ素原子、パーフルオロアルキル基(例えば、炭素数1~10が好ましく、炭素数1~6がより好ましい。)、又はシアノ基が好ましい。
RX2で表されるフッ素原子及びパーフルオロアルキル基以外の置換基としては、パーフルオロアルキル基以外のアルキル基(直鎖状、分岐鎖状、又は環状のいずれでもよい)が好ましい。
上記アルキル基の炭素数は1~15が好ましく、1~10がより好ましい。
上記アルキル基はフッ素原子を有さないのが好ましい。すなわち、上記アルキル基が置換基を有する場合、フッ素原子以外の置換基が好ましい。
RXF1で表されるパーフルオロアルキル基の炭素数は1~15が好ましく、1~10がより好ましく、1~6が更に好ましい。
Laで表される2価の連結基としては特に制限されず、例えば、-CO-、-NH-、-O-、-S-、-SO-、-SO2-、及び、アルキレン基(好ましくは炭素数1~10。直鎖状でも分岐鎖状でもよい)からなる群より選ばれる1種以上又は2種以上を組み合わせた基が挙げられる。
また、上記アルキレン基は、置換基(例えば、フッ素原子等)で置換されていてもよい。
環状の有機基としては、例えば、脂環基、アリール基、及び、複素環基が挙げられる。
脂環基は、単環式であってもよく、多環式であってもよい。単環式の脂環基としては、例えば、シクロペンチル基、シクロヘキシル基、及び、シクロオクチル基等の単環のシクロアルキル基が挙げられる。多環式の脂環基としては、例えば、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が挙げられる。なかでも、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の炭素数7以上の嵩高い構造を有する脂環基が好ましい。
なお、上記脂環基は、炭素原子がカルボニル基で置換されていてもよい。
複素環基は、単環式であってもよく、多環式であってもよい。多環式の方がより酸の拡散を抑制可能である。また、複素環基は、芳香族性を有していてもよいし、芳香族性を有していなくてもよい。芳香族性を有している複素環としては、例えば、フラン環、チオフェン環、ベンゾフラン環、ベンゾチオフェン環、ジベンゾフラン環、ジベンゾチオフェン環、及び、ピリジン環が挙げられる。芳香族性を有していない複素環としては、例えば、テトラヒドロピラン環、ラクトン環、スルトン環、及び、デカヒドロイソキノリン環が挙げられる。ラクトン環及びスルトン環の例としては、後述する樹脂において例示したラクトン構造及びスルトン構造が挙げられる。複素環基における複素環としては、フラン環、チオフェン環、ピリジン環、又はデカヒドロイソキノリン環が好ましい。
式(II-B) (Rb)m-Mb +-Lb-Ab -
Mb +は、硫黄イオン(S+)又はヨウ素イオン(I+)を表す。
mは、1又は2を表し、Mb +が硫黄イオンである場合には2であり、ヨウ素原子である場合には1である。
Rbは、各々独立に、ヘテロ原子を含んでいてもよいアルキル基若しくはアルケニル基、アリール基、又は、ヘテロアリール基を表す。なお、mが2の場合には、2つのRbは互いに結合して、環を形成していてもよい。
なお、Rbで表されるヘテロ原子を含んでいてもよいアルキル基又はアルケニル基は、直鎖状、分岐鎖状、及び環状のいずれであってもよい。
また、Rbで表されるヘテロ原子を含んでいてもよいアルキル基又はアルケニル基は、置換基を有していてもよい。この置換基としては、例えば、アリール基(炭素数6~14が好ましい)、水酸基、アルコキシ基、エステル基、アミド基、ウレタン基、ウレイド基、チオエーテル基、スルホンアミド基、及びスルホン酸エステル基が挙げられる。
Rbで表されるヘテロアリール基としては、単環式であってもよく、多環式であってもよい。多環式の方がより酸の拡散を抑制可能である。このヘテロアリール基を構成する芳香族複素環としては、例えば、フラン環、チオフェン環、ベンゾフラン環、ベンゾチオフェン環、ジベンゾフラン環、ジベンゾチオフェン環、及びピリジン環が挙げられる。
また、上記アルキレン基及びアリーレン基の水素原子は、置換基(例えば、フッ素原子等)で置換されていてもよい。
M11 + A11 --L1-A12 - M12 + (Ia-1)
式(Ia-1)中、M11 +及びM12 +は、それぞれ有機カチオンを表す。有機カチオンとしては、上述した、式(ZaI)で表される有機カチオン(カチオン(ZaI))、又は、式(ZaII)で表される有機カチオン(カチオン(ZaII))が好ましい。
式(Ia-1)中、A11 -及びA12 -は、それぞれ独立に、式(B-1)~式(B-8)で表される基を表す。
式(Ia-1)中、L1は2価の連結基を表す。L1で表される2価の連結基としては特に制限されず、例えば、-CO-、-NH-、-O-、-S-、-SO-、-SO2-、アルキレン基(好ましくは炭素数1~10。直鎖状でも分岐鎖状でもよい)、シクロアルキレン基(好ましくは炭素数5~20。単環、多環、及び、スピロ環のいずれでもよい)、及び、アリーレン基(好ましくは炭素数6~10)からなる群より選ばれる1種以上又は2種以上を組み合わせた基が挙げられる。
また、上記アルキレン基、シクロアルキレン基、及び、アリーレン基の水素原子は、置換基(例えば、フッ素原子等)で置換されていてもよい。
なお、式(Ia-2)中のM22 + A22 -部分、A21a - M21a +部分、及び、A21b - M21b +部分の少なくとも一つが構造部位Wを含む。
式(Ia-4)中のM42 + A42 -部分、A41a - M41a +部分、及び、A41b - M41b +部分の少なくとも一つが構造部位Wを含む。
式(Ia-2)中、A21a -及びA21b -は、それぞれ独立に、式(B-1)~式(B-8)で表される基を表す。A22 -は、式(II)-1~(II)-4で表される基を表す。
式(Ia-2)中、L21及びL22はそれぞれ2価の連結基を表す。L21及びL22で表される2価の連結基としては特に制限されず、例えば、上記Lbで説明した基が挙げられる。L21とL22とが同一であってもよく、異なっていてもよい。
式(Ia-4)中、A41a -、A41b -、及び、A42 -は、それぞれ独立に、式(B-1)~式(B-8)で表される基を表す。
式(Ia-4)中、L41は3価の連結基を表す。3価の有機基としては、例えば、式(L3)で表される3価の有機基が挙げられる。
LBとしては、3価の炭化水素環基が好ましく、ベンゼン環基又はアダマンタン環基がより好ましい。ベンゼン環基又はアダマンタン環基は、置換基を有していてもよい。置換基としては例えば、ハロゲン原子(好ましくはフッ素原子)が挙げられる。
また、上記アルキレン基、上記シクロアルキレン基、上記アルケニレン基、上記2価の脂肪族複素環基、2価の芳香族複素環基及び2価の芳香族炭化水素環基は、置換基を有していてもよい。置換基としては、例えば、ハロゲン原子(好ましくはフッ素原子)が挙げられる。
LB1~LB3で表される2価の連結基としては、-CO-、-NR-、-O-、-S-、-SO-、-SO2-、置換基を有していてもよいアルキレン基又はこれらを組み合わせた2価の連結基が好ましい。
オニウム塩(II)は1種単独で用いてもよく、2種以上で用いてもよい。2種以上使用する場合、その合計含有量が、上記好適含有量の範囲内であることが好ましい。
また、オニウム塩(I)とオニウム塩(II)との合計含有量は、レジスト組成物の全固形分に対して、10質量%以上が好ましく、15質量%以上が好ましく、20質量%以上がより好ましく、30質量%以上が更に好ましい。上限としては、レジスト組成物の全固形分に対して、80質量%以下が好ましく、70質量%以下がより好ましく、60質量%以下が更に好ましい。
レジスト組成物は、オニウム塩(I)又はオニウム塩(II)以外の、活性光線又は放射線の照射によって酸を発生する化合物(その他の光酸発生剤)を含んでいてもよい。
レジスト組成物は、酸分解性樹脂を含む。
以下、酸分解性樹脂を単に「樹脂(A)」ともいう。
酸分解性樹脂は、酸分解性基を有することが好ましい。「酸分解性基」とは、酸の作用により分解して極性基を生じる基を意味する。
本発明のパターン形成方法において、典型的には、現像液としてアルカリ現像液を採用した場合には、ポジ型パターンが好適に形成され、現像液として有機系現像液を採用した場合には、ネガ型パターンが好適に形成される。
以下、酸分解性樹脂が含み得る繰り返し単位について説明する。
酸分解性基は、酸の作用により脱離する脱離基で極性基が保護された構造を有することが好ましい。つまり、酸分解性樹脂は、酸の作用により分解し、極性基を生じる基を有する繰り返し単位を有することが好ましい。この繰り返し単位を有する樹脂は、酸の作用により極性が増大してアルカリ現像液に対する溶解度が増大し、有機溶剤に対する溶解度が減少する。
酸分解性基が酸の作用によって分解して生じる極性基としては、アルカリ可溶性基が好ましい。
アルカリ可溶性基としては、例えば、カルボキシ基、フェノール性水酸基、フッ素化アルコール基、スルホン酸基、リン酸基、スルホンアミド基、スルホニルイミド基、(アルキルスルホニル)(アルキルカルボニル)メチレン基、(アルキルスルホニル)(アルキルカルボニル)イミド基、ビス(アルキルカルボニル)メチレン基、ビス(アルキルカルボニル)イミド基、ビス(アルキルスルホニル)メチレン基、ビス(アルキルスルホニル)イミド基、トリス(アルキルカルボニル)メチレン基及びトリス(アルキルスルホニル)メチレン基等の酸性基、並びに、アルコール性水酸基が挙げられる。
上述したように、酸分解性基は、酸の作用により脱離する脱離基で極性基が保護された構造を有することが好ましい。
式(Y1):-C(Rx1)(Rx2)(Rx3)
式(Y2):-C(=O)OC(Rx1)(Rx2)(Rx3)
式(Y3):-C(R36)(R37)(OR38)
式(Y4):-C(Rn)(H)(Ar)
なかでも、Rx1~Rx3は、それぞれ独立に、直鎖状又は分岐鎖状のアルキル基を表すことが好ましく、Rx1~Rx3は、それぞれ独立に、直鎖状のアルキル基を表すことがより好ましい。
Rx1~Rx3の2つが互いに結合して、単環又は多環を形成してもよい。
Rx1~Rx3のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、及び、t-ブチル基等の炭素数1~5のアルキル基が好ましい。
Rx1~Rx3のシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基、並びに、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。
Rx1~Rx3のアリール基としては、例えば、炭素数6~10のアリール基が好ましく、例えば、フェニル基、ナフチル基、及び、アントリル基が挙げられる。
Rx1~Rx3のヘテロアリール基としては、例えば、炭素数4~10のヘテロアリール基が好ましい。
Rx1~Rx3のアルケニル基としては、ビニル基が好ましい。
Rx1~Rx3の2つが結合して形成される環としては、シクロアルキル基が好ましい。Rx1~Rx3の2つが結合して形成されるシクロアルキル基としては、シクロペンチル基、若しくは、シクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、若しくは、アダマンチル基等の多環のシクロアルキル基が好ましく、炭素数5~6の単環のシクロアルキル基がより好ましい。
Rx1~Rx3の2つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の1つが、酸素原子等のヘテロ原子、カルボニル基等のヘテロ原子を含む基、又はビニリデン基で置き換わっていてもよい。また、これらのシクロアルキル基は、シクロアルカン環を構成するエチレン基の1つ以上が、ビニレン基で置き換わっていてもよい。
一般式(Y1)又は一般式(Y2)で表される基は、例えば、Rx1がメチル基又はエチル基であり、Rx2とRx3とが結合して上述のシクロアルキル基を形成している態様が好ましい。
レジスト組成物が、例えば、EUV露光用レジスト組成物である場合、Rx1~Rx3で表されるアルキル基、シクロアルキル基、アルケニル基、アリール基、ヘテロアリール基、及び、Rx1~Rx3の2つが結合して形成される環は、更に、置換基として、フッ素原子又はヨウ素原子を有しているのも好ましい。
なお、上記アルキル基、シクロアルキル基、アリール基、及び、アラルキル基には、酸素原子等のヘテロ原子及び/又はカルボニル基等のヘテロ原子を含む基が含まれていてもよい。例えば、上記アルキル基、シクロアルキル基、アリール基、及び、アラルキル基において、メチレン基の1つ以上が、酸素原子等のヘテロ原子及び/又はカルボニル基等のヘテロ原子を含む基で置き換わっていてもよい。
また、R38は、繰り返し単位の主鎖が有する別の置換基と互いに結合して、環を形成してもよい。R38と繰り返し単位の主鎖が有する別の置換基とが互いに結合して形成する基は、メチレン基等のアルキレン基が好ましい。
レジスト組成物が、例えば、EUV露光用レジスト組成物である場合、R36~R38で表される1価の有機基、及び、R37とR38とが互いに結合して形成される環は、更に、置換基として、フッ素原子又はヨウ素原子を有しているのも好ましい。
Mは、単結合又は2価の連結基を表す。
Qは、ヘテロ原子を含んでいてもよいアルキル基、ヘテロ原子を含んでいてもよいシクロアルキル基、ヘテロ原子を含んでいてもよいアリール基、アミノ基、アンモニウム基、メルカプト基、シアノ基、アルデヒド基、又は、これらを組み合わせた基(例えば、アルキル基とシクロアルキル基とを組み合わせた基)を表す。
アルキル基及びシクロアルキル基は、例えば、メチレン基の1つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を含む基で置き換わっていてもよい。
なお、L1及びL2のうち一方は水素原子であり、他方はアルキル基、シクロアルキル基、アリール基、又は、アルキレン基とアリール基とを組み合わせた基であることが好ましい。
Q、M、及びL1の少なくとも2つが結合して環(好ましくは、5員若しくは6員環)を形成してもよい。
パターンの微細化の点では、L2が2級又は3級アルキル基であることが好ましく、3級アルキル基であることがより好ましい。2級アルキル基としては、イソプロピル基、シクロヘキシル基、及び、ノルボルニル基が挙げられ、3級アルキル基としては、tert-ブチル基、及び、アダマンタン基が挙げられる。これらの態様では、Tg(ガラス転移温度)及び活性化エネルギーが高くなるため、膜強度の担保に加え、かぶりの抑制ができる。
また、レジスト組成物が、例えば、EUV露光用レジスト組成物である場合、Qで表されるヘテロ原子を含んでいてもよいアルキル基、ヘテロ原子を含んでいてもよいシクロアルキル基、ヘテロ原子を含んでいてもよいアリール基、アミノ基、アンモニウム基、メルカプト基、シアノ基、アルデヒド基、及び、これらを組み合わせた基において、ヘテロ原子としては、フッ素原子、ヨウ素原子及び酸素原子からなる群から選択されるヘテロ原子であるのも好ましい。
レジスト組成物が、例えば、EUV露光用レジスト組成物である場合、Arで表される芳香環基、並びに、Rnで表されるアルキル基、シクロアルキル基、及び、アリール基は、置換基としてフッ素原子又はヨウ素原子を有しているのも好ましい。
L1は、フッ素原子又はヨウ素原子を有していてもよい2価の連結基を表す。フッ素原子又はヨウ素原子を有していてもよい2価の連結基としては、-CO-、-O-、-S-、-SO-、-SO2-、フッ素原子又はヨウ素原子を有していてもよい炭化水素基(例えば、アルキレン基、シクロアルキレン基、アルケニレン基、及び、アリーレン基等)、及び、これらの複数が連結した連結基が挙げられる。なかでも、L1としては、-CO-、アリーレン基、又は、-アリーレン基-フッ素原子若しくはヨウ素原子を有するアルキレン基-が好ましく、-CO-、又は、-アリーレン基-フッ素原子若しくはヨウ素原子を有するアルキレン基-がより好ましい。
アリーレン基としては、フェニレン基が好ましい。
アルキレン基は、直鎖状であっても、分岐鎖状であってもよい。アルキレン基の炭素数は特に制限されないが、1~10が好ましく、1~3がより好ましい。
フッ素原子又はヨウ素原子を有するアルキレン基に含まれるフッ素原子及びヨウ素原子の合計数は特に制限されないが、2以上が好ましく、2~10がより好ましく、3~6が更に好ましい。
アルキル基は、直鎖状であっても、分岐鎖状であってもよい。アルキル基の炭素数は特に制限されないが、1~10が好ましく、1~3がより好ましい。
フッ素原子又はヨウ素原子を有するアルキル基に含まれるフッ素原子及びヨウ素原子の合計数は特に制限されないが、1以上が好ましく、1~5がより好ましく、1~3が更に好ましい。
上記アルキル基は、ハロゲン原子以外の酸素原子等のヘテロ原子を含んでいてもよい。
Rx1~Rx3の2つが結合して、単環又は多環(単環又は多環のシクロアルキル基等)を形成してもよい。
Tは、単結合又は-COO-Rt-基が好ましい。Tが-COO-Rt-基を表す場合、Rtとしては、炭素数1~5のアルキレン基が好ましく、-CH2-基、-(CH2)2-基、又は、-(CH2)3-基がより好ましい。
Rx1~Rx3のシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。
Rx1~Rx3のアリール基としては、炭素数6~10のアリール基が好ましく、例えば、フェニル基、ナフチル基、及び、アントリル基が挙げられる。
Rx1~Rx3のアルケニル基としては、ビニル基が好ましい。
Rx1~Rx3の2つが結合して形成されるシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基が好ましい。また、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。なかでも、炭素数5~6の単環のシクロアルキル基が好ましい。
Rx1~Rx3の2つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の1つが、酸素原子等のヘテロ原子、カルボニル基等のヘテロ原子を含む基、又は、ビニリデン基で置き換わっていてもよい。また、これらのシクロアルキル基は、シクロアルカン環を構成するエチレン基の1つ以上が、ビニレン基で置き換わっていてもよい。
式(AI)で表される繰り返し単位は、例えば、Rx1がメチル基又はエチル基であり、Rx2とRx3とが結合して上述のシクロアルキル基を形成している態様が好ましい。
不飽和結合を含む酸分解性基を有する繰り返し単位としては、式(B)で表される繰り返し単位が好ましい。
Ry1~Ry3の2つが結合して、単環又は多環(単環又は多環のシクロアルキル基、シクロアルケニル基等)を形成してもよい。
Lとしては、-Rt-基、-CO-基、-COO-Rt-CO-基、又は、-Rt-CO-基が好ましい。Rtは、ハロゲン原子、水酸基、アルコキシ基等の置換基を有していてもよい。芳香族基が好ましい。
Ry1~Ry3のシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基、又はノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。
Ry1~Ry3のアリール基としては、炭素数6~10のアリール基が好ましく、例えば、フェニル基、ナフチル基、及び、アントリル基が挙げられる。
Ry1~Ry3のアルケニル基としては、ビニル基が好ましい。
Ry1~Ry3のアルキニル基としては、エチニル基が好ましい。
Ry1~Ry3のシクロアルケニル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基の一部に二重結合を含む構造が好ましい。
Ry1~Ry3の2つが結合して形成されるシクロアルキル基としては、シクロペンチル基、及び、シクロヘキシル基等の単環のシクロアルキル基、又は、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が好ましい。なかでも、炭素数5~6の単環のシクロアルキル基がより好ましい。
Ry1~Ry3の2つが結合して形成されるシクロアルキル基、又は、シクロアルケニル基は、例えば、環を構成するメチレン基の1つが、酸素原子等のヘテロ原子、カルボニル基、-SO2-基及び-SO3-基等のヘテロ原子を含む基、ビニリデン基、又は、それらの組み合わせで置き換わっていてもよい。また、これらのシクロアルキル基又はシクロアルケニル基は、シクロアルカン環又はシクロアルケン環を構成するエチレン基の1つ以上が、ビニレン基で置き換わっていてもよい。
式(B)で表される繰り返し単位は、例えば、Ry1がメチル基、エチル基、ビニル基、アリル基、又は、アリール基であり、Ry2とRx3とが結合して上述のシクロアルキル基又はシクロアルケニル基を形成している態様が好ましい。
A群:以下の(20)~(29)の繰り返し単位からなる群。
(20)後述する、酸基を有する繰り返し単位
(21)後述する、酸分解性基及び酸基のいずれも有さず、フッ素原子、臭素原子又はヨウ素原子を有する繰り返し単位
(22)後述する、ラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位(23)後述する、光酸発生基を有する繰り返し単位
(24)後述する、式(V-1)又は下記式(V-2)で表される繰り返し単位
(25)後述する、式(A)で表される繰り返し単位
(26)後述する、式(B)で表される繰り返し単位
(27)後述する、式(C)で表される繰り返し単位
(28)後述する、式(D)で表される繰り返し単位
(29)後述する、式(E)で表される繰り返し単位
B群:以下の(30)~(32)の繰り返し単位からなる群。
(30)後述する、ラクトン基、スルトン基、カーボネート基、水酸基、シアノ基、及びアルカリ可溶性基から選ばれる少なくとも1種類の基を有する繰り返し単位
(31)後述する、脂環式炭化水素構造を有し、酸分解性を示さない繰り返し単位
(32)後述する、水酸基及びシアノ基のいずれも有さない、式(III)で表される繰り返し単位
また、レジスト組成物がEUV用の感活性光線性又は感放射線性樹脂組成物として用いられる場合、樹脂(A)は、フッ素原子及びヨウ素原子の少なくとも一方を含むことが好ましい。樹脂(A)がフッ素原子及びヨウ素原子の両方を含む場合、樹脂(A)は、フッ素原子及びヨウ素原子の両方を含む1つの繰り返し単位を有していてもよいし、樹脂(A)は、フッ素原子を有する繰り返し単位とヨウ素原子を含む繰り返し単位との2種を含んでいてもよい。
また、レジスト組成物がEUV用の感活性光線性又は感放射線性樹脂組成物として用いられる場合、樹脂(A)が、芳香族基を有する繰り返し単位を有するのも好ましい。
レジスト組成物がArF用の感活性光線性又は感放射線性樹脂組成物として用いられる場合、樹脂(A)は上記B群からなる群から選択される少なくとも1種の繰り返し単位を有することが好ましい。
なお、レジスト組成物がArF用の感活性光線性又は感放射線性樹脂組成物として用いられる場合、樹脂(A)は、フッ素原子及び珪素原子のいずれも含まないことが好ましい。
また、レジスト組成物がArF用の感活性光線性又は感放射線性樹脂組成物として用いられる場合、樹脂(A)は、芳香族基を有さないことが好ましい。
樹脂(A)は、酸基を有する繰り返し単位を有していてもよい。
酸基としては、pKaが13以下の酸基が好ましい。上記酸基の酸解離定数は、13以下が好ましく、3~13がより好ましく、5~10が更に好ましい。
樹脂(A)が、pKaが13以下の酸基を有する場合、樹脂(A)中における酸基の含有量は特に制限されないが、0.2~6.0mmol/gの場合が多い。なかでも、0.8~6.0mmol/gが好ましく、1.2~5.0mmol/gがより好ましく、1.6~4.0mmol/gが更に好ましい。酸基の含有量が上記範囲内であれば、現像が良好に進行し、形成されるパターン形状に優れ、解像性にも優れる。
酸基としては、例えば、カルボキシル基、フェノール性水酸基、フッ化アルコール基(好ましくはヘキサフルオロイソプロパノール基)、スルホン酸基、スルホンアミド基、又はイソプロパノール基が好ましい。
また、上記ヘキサフルオロイソプロパノール基は、フッ素原子の1つ以上(好ましくは1~2つ)が、フッ素原子以外の基(アルコキシカルボニル基等)で置換されてもよい。酸基としては、このように形成された-C(CF3)(OH)-CF2-も好ましい。また、フッ素原子の1つ以上がフッ素原子以外の基に置換されて、-C(CF3)(OH)-CF2-を含む環を形成してもよい。
酸基を有する繰り返し単位は、上述の酸の作用により脱離する脱離基で極性基が保護された構造を有する繰り返し単位、及び後述するラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位とは異なる繰り返し単位であるのが好ましい。
酸基を有する繰り返し単位は、フッ素原子又はヨウ素原子を有していてもよい。
樹脂(A)は、上述した<酸分解性基を有する繰り返し単位>及び<酸基を有する繰り返し単位>とは別に、酸分解性基及び酸基のいずれも有さず、フッ素原子、臭素原子又はヨウ素原子を有する繰り返し単位(以下、単位Xともいう。)を有していてもよい。また、ここで言う<酸分解性基及び酸基のいずれも有さず、フッ素原子、臭素原子又はヨウ素原子を有する繰り返し単位>は、後述の<ラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位>、及び<光酸発生基を有する繰り返し単位>等の、A群に属する他の種類の繰り返し単位とは異なるのが好ましい。
なお、フッ素原子、臭素原子及びヨウ素原子の少なくとも1つを含む繰り返し単位としては、例えば、フッ素原子、臭素原子又はヨウ素原子を有し、かつ、酸分解性基を有する繰り返し単位、フッ素原子、臭素原子又はヨウ素原子を有し、かつ、酸基を有する繰り返し単位、及びフッ素原子、臭素原子又はヨウ素原子を有する繰り返し単位が挙げられる。
樹脂(A)は、ラクトン基、スルトン基、及びカーボネート基からなる群から選択される少なくとも1種を有する繰り返し単位(以下、「単位Y」ともいう。)を有していてもよい。
単位Yは、水酸基、及びヘキサフルオロプロパノール基等の酸基を有さないのも好ましい。
樹脂(A)は、下記式(LC1-1)~(LC1-21)のいずれかで表されるラクトン構造、又は下記式(SL1-1)~(SL1-3)のいずれかで表されるスルトン構造の環員原子から、水素原子を1つ以上引き抜いてなるラクトン基又はスルトン基を有する繰り返し単位を有することが好ましい。
また、ラクトン基又はスルトン基が主鎖に直接結合していてもよい。例えば、ラクトン基又はスルトン基の環員原子が、樹脂(A)の主鎖を構成してもよい。
Rb0のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられる。Rb0は、水素原子又はメチル基が好ましい。
Abは、単結合、アルキレン基、単環又は多環の脂環式炭化水素構造を有する2価の連結基、エーテル基、エステル基、カルボニル基、カルボキシル基、又はこれらを組み合わせた2価の基を表す。なかでも、Abとしては、単結合、又は-Ab1-CO2-で表される連結基が好ましい。Ab1は、直鎖状若しくは分岐鎖状のアルキレン基、又は単環若しくは多環のシクロアルキレン基であり、メチレン基、エチレン基、シクロヘキシレン基、アダマンチレン基、又はノルボルニレン基が好ましい。
Vは、式(LC1-1)~(LC1-21)のいずれかで表されるラクトン構造の環員原子から水素原子を1つ引き抜いてなる基、又は式(SL1-1)~(SL1-3)のいずれかで表されるスルトン構造の環員原子から水素原子を1つ引き抜いてなる基を表す。
環状炭酸エステル基を有する繰り返し単位としては、下記式(A-1)で表される繰り返し単位が好ましい。
樹脂(A)は、上記以外の繰り返し単位として、活性光線又は放射線の照射により酸を発生する基(以下、「光酸発生基」ともいう)を有する繰り返し単位を有していてもよい。
光酸発生基を有する繰り返し単位としては、式(4)で表される繰り返し単位が挙げられる。
光酸発生基を有する繰り返し単位を以下に例示する。
樹脂(A)は、下記式(V-1)、又は下記式(V-2)で表される繰り返し単位を有していてもよい。
下記式(V-1)、及び下記式(V-2)で表される繰り返し単位は上述の繰り返し単位とは異なる繰り返し単位であるのが好ましい。
n3は、0~6の整数を表す。
n4は、0~4の整数を表す。
X4は、メチレン基、酸素原子、又は硫黄原子である。
式(V-1)又は(V-2)で表される繰り返し単位を以下に例示する。
式(V-1)又は(V-2)で表される繰り返し単位としては、例えば、国際公開第2018/193954号の段落[0100]に記載された繰り返し単位が挙げられる。
樹脂(A)は、発生酸の過剰な拡散又は現像時のパターン崩壊を抑制できる点から、ガラス転移温度(Tg)が高い方が好ましい。Tgは、90℃より大きいことが好ましく、100℃より大きいことがより好ましく、110℃より大きいことが更に好ましく、125℃より大きいことが特に好ましい。なお、現像液への溶解速度が優れる点から、Tgは400℃以下が好ましく、350℃以下がより好ましい。
なお、本明細書において、樹脂(A)等のポリマーのガラス転移温度(Tg)(以下「繰り返し単位のTg」)は、以下の方法で算出する。まず、ポリマー中に含まれる各繰り返し単位のみからなるホモポリマーのTgを、Bicerano法によりそれぞれ算出する。次に、ポリマー中の全繰り返し単位に対する、各繰り返し単位の質量割合(%)を算出する。次に、Foxの式(Materials Letters 62(2008)3152等に記載)を用いて各質量割合におけるTgを算出して、それらを総和して、ポリマーのTg(℃)とする。
Bicerano法は、Prediction of polymer properties, Marcel Dekker Inc, New York(1993)に記載されている。また、Bicerano法によるTgの算出は、ポリマーの物性概算ソフトウェアMDL Polymer(MDL Information Systems, Inc.)を用いて行うことができる。
(a)主鎖への嵩高い置換基の導入
(b)主鎖への複数の置換基の導入
(c)主鎖近傍への樹脂(A)間の相互作用を誘発する置換基の導入
(d)環状構造での主鎖形成
(e)主鎖への環状構造の連結
なお、樹脂(A)は、ホモポリマーのTgが130℃以上を示す繰り返し単位を有することが好ましい。
なお、ホモポリマーのTgが130℃以上を示す繰り返し単位の種類は特に制限されず、Bicerano法により算出されるホモポリマーのTgが130℃以上である繰り返し単位であればよい。なお、後述する式(A)~式(E)で表される繰り返し単位中の官能基の種類によっては、ホモポリマーのTgが130℃以上を示す繰り返し単位に該当する。
式(A)で表される繰り返し単位の具体例としては、国際公開第2018/193954号の段落[0107]~[0119]に記載のものが挙げられる。
また、有機基の少なくとも1つが、繰り返し単位中の主鎖に直接環構造が連結している基である場合、他の有機基の種類は特に制限されない。
また、有機基のいずれも繰り返し単位中の主鎖に直接環構造が連結している基ではない場合、有機基の少なくとも2つ以上は、水素原子を除く構成原子の数が3つ以上である置換基である。
式(B)で表される繰り返し単位の具体例としては、国際公開第2018/193954号の段落[0113]~[0115]に記載のものが挙げられる。
式(C)で表される繰り返し単位の具体例としては、国際公開第2018/193954号の段落[0119]~[0121]に記載のものが挙げられる。
式(D)で表される繰り返し単位の具体例としては、国際公開第2018/193954号の段落[0126]~[0127]に記載のものが挙げられる。
「Cylic」は、主鎖の炭素原子を含む環状基である。環状基に含まれる原子数は特に制限されない。
式(E)で表される繰り返し単位の具体例としては、国際公開第2018/193954号の段落[0131]~[0133]に記載のものが挙げられる。
樹脂(A)は、ラクトン基、スルトン基、カーボネート基、水酸基、シアノ基、及びアルカリ可溶性基から選ばれる少なくとも1種類の基を有する繰り返し単位を有していてもよい。
樹脂(A)が有するラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位としては、上述した<ラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位>で説明した繰り返し単位が挙げられる。好ましい含有量も上述した<ラクトン基、スルトン基、又はカーボネート基を有する繰り返し単位>で説明した通りである。
水酸基又はシアノ基を有する繰り返し単位は、水酸基又はシアノ基で置換された脂環式炭化水素構造を有する繰り返し単位であることが好ましい。
水酸基又はシアノ基を有する繰り返し単位は、酸分解性基を有さないことが好ましい。水酸基又はシアノ基を有する繰り返し単位としては、特開2014-098921号公報の段落[0081]~[0084]に記載のものが挙げられる。
アルカリ可溶性基としては、カルボキシル基、スルホンアミド基、スルホニルイミド基、ビスルスルホニルイミド基、及びα位が電子求引性基で置換された脂肪族アルコール(例えば、ヘキサフルオロイソプロパノール基)が挙げられ、カルボキシル基が好ましい。樹脂(A)がアルカリ可溶性基を有する繰り返し単位を含むことにより、コンタクトホール用途での解像性が増す。アルカリ可溶性基を有する繰り返し単位としては、特開2014-098921号公報の段落[0085]及び[0086]に記載のものが挙げられる。
樹脂(A)は、脂環式炭化水素構造を有し、酸分解性を示さない繰り返し単位を有してもよい。これにより液浸露光時にレジスト膜から液浸液への低分子成分の溶出が低減できる。このような繰り返し単位として、例えば、1-アダマンチル(メタ)アクリレート、ジアマンチル(メタ)アクリレート、トリシクロデカニル(メタ)アクリレート、又はシクロヘキシル(メタ)アクリレート由来の繰り返し単位が挙げられる。
樹脂(A)は、水酸基及びシアノ基のいずれも有さない、式(III)で表される繰り返し単位を有していてもよい。
Raは水素原子、アルキル基又は-CH2-O-Ra2基を表す。式中、Ra2は、水素原子、アルキル基又はアシル基を表す。
水酸基及びシアノ基のいずれも有さない、式(III)で表される繰り返し単位としては、特開2014-098921号公報の段落[0087]~[0094]に記載のものが挙げられる。
更に、樹脂(A)は、上述した繰り返し単位以外の繰り返し単位を有してもよい。
例えば樹脂(A)は、オキサチアン環基を有する繰り返し単位、オキサゾロン環基を有する繰り返し単位、ジオキサン環基を有する繰り返し単位、及びヒダントイン環基を有する繰り返し単位からなる群から選択される繰り返し単位を有していてもよい。
このような繰り返し単位を以下に例示する。
GPC法によりポリスチレン換算値として、樹脂(A)の重量平均分子量は、30,000以下が好ましく、1,000~30,000がより好ましく、3,000~30,000が更に好ましく、5,000~15,000が特に好ましい。
樹脂(A)の分散度(分子量分布)は、1~5が好ましく、1~3がより好ましく、1.2~3.0が更に好ましく、1.2~2.0が特に好ましい。分散度が小さいものほど、解像度、及びレジスト形状がより優れ、更に、レジストパターンの側壁がよりスムーズであり、ラフネス性にもより優れる。
樹脂(A)は、1種で使用してもよいし、複数併用してもよい。
レジスト組成物は、酸拡散制御剤を含んでいてもよい。
なお、酸拡散制御剤には、オニウム塩(II)を含めない。
酸拡散制御剤は、露光時に光酸発生剤等から発生する酸をトラップし、余分な発生酸による、未露光部における酸分解性樹脂の反応を抑制するクエンチャーとして作用するものである。
酸拡散制御剤の種類は特に制限されず、例えば、塩基性化合物(CA)、窒素原子を有し、酸の作用により脱離する基を有する低分子化合物(CB)、及び、活性光線又は放射線の照射により酸拡散制御能が低下又は消失する化合物(CC)が挙げられる。
化合物(CC)としては、光酸発生剤に対して相対的に弱酸となるオニウム塩化合物(CD)、及び、活性光線又は放射線の照射により塩基性が低下又は消失する塩基性化合物(CE)が挙げられる。
また、例えば、塩基性化合物(CA)の具体例としては、国際公開第2020/066824号の段落[0132]~[0136]に記載のものが挙げられ、活性光線又は放射線の照射により塩基性が低下又は消失する塩基性化合物(CE)の具体例としては、国際公開第2020/066824号の段落[0137]~[0155]に記載のものが挙げられ、窒素原子を有し、酸の作用により脱離する基を有する低分子化合物(CB)の具体例としては、国際公開第2020/066824号の段落[0156]~[0163]に記載のものが挙げられ、カチオン部に窒素原子を有するオニウム塩化合物(CE)の具体例としては、国際公開第2020/066824号公報の段落[0164]に記載のものが挙げられる。
また、光酸発生剤に対して相対的に弱酸となるオニウム塩化合物(CD)の具体例としては、国際公開第2020/158337号の段落[0305]~[0314]に記載のものが挙げられる。
酸拡散制御剤は、1種単独で用いてもよいし、2種以上を併用してもよい。
レジスト組成物は、上記酸分解性樹脂とは別に、酸分解性樹脂とは異なる疎水性樹脂を含んでいてもよい。
疎水性樹脂はレジスト膜の表面に偏在するように設計されることが好ましく、界面活性剤とは異なり、必ずしも分子内に親水基を有する必要はなく、極性物質及び非極性物質の均一な混合に寄与しなくてもよい。
疎水性樹脂の添加による効果として、例えば、水に対するレジスト膜表面の静的及び動的な接触角の制御、並びに、アウトガスの抑制が挙げられる。
疎水性樹脂としては、例えば、国際公開第2020/004306号公報の段落[0275]~[0279]に記載される化合物が挙げられる。
疎水性樹脂は、1種単独で用いてもよく、2種以上で用いてもよい。2種以上使用する場合、その合計含有量が、上記好適含有量の範囲内であることが好ましい。
レジスト組成物は、界面活性剤を含んでいてもよい。
界面活性剤を含む場合、密着性により優れ、現像欠陥のより少ないパターンを形成できる。
界面活性剤は、フッ素系及び/又はシリコン系界面活性剤が好ましい。
フッ素系及び/又はシリコン系界面活性剤としては、例えば、国際公開第2018/19395号公報の段落[0218]及び[0219]に開示された界面活性剤を使用できる。
レジスト組成物が界面活性剤を含む場合、その含有量は、レジスト組成物の全固形分に対して、0.0001~2質量%が好ましく、0.0005~1質量%がより好ましい。
界面活性剤は、1種単独で用いてもよく、2種以上で用いてもよい。2種以上使用する場合、その合計含有量が、上記好適含有量の範囲内であることが好ましい。
レジスト組成物は、溶剤を含んでいてもよい。
溶剤は、(M1)プロピレングリコールモノアルキルエーテルカルボキシレート、並びに、(M2)プロピレングリコールモノアルキルエーテル、乳酸エステル、酢酸エステル、アルコキシプロピオン酸エステル、鎖状ケトン、環状ケトン、ラクトン及びアルキレンカーボネートからなる群から選択される少なくとも1つの少なくとも一方を含んでいることが好ましい。なお、この溶剤は、成分(M1)及び(M2)以外の成分を更に含んでいてもよい。
その理由は必ずしも明らかではないが、これら溶剤は、上記樹脂の溶解性、沸点及び粘度のバランスが良いため、組成物膜の膜厚のムラ及びスピンコート中の析出物の発生等を抑制できることに起因していると本発明者らは考えている。
成分(M1)及び成分(M2)の詳細は、国際公開第2020/004306号公報の段落[0218]~[0226]に記載される。
溶剤の含有量は、レジスト組成物の全質量に対して、70~99.95質量%が好ましく、90~99.9質量%がより好ましく、98~99.5質量%が更に好ましい。
溶剤は、1種単独で用いてもよく、2種以上で用いてもよい。2種以上使用する場合、その合計含有量が、上記好適含有量の範囲内であることが好ましい。
レジスト組成物は、溶解阻止化合物、染料、可塑剤、光増感剤、光吸収剤及び/又は現像液に対する溶解性を促進させる化合物(カルボン酸基を含んだ脂環族若しくは脂肪族化合物)を更に含んでいてもよい。
EUV光は波長13.5nmであり、ArF(波長193nm)光等に比べて、より短波長であるため、同じ感度で露光された際の入射フォトン数が少ない。そのため、確率的にフォトンの数がばらつく“フォトンショットノイズ”の影響が大きく、LWRの悪化、及び、ブリッジ欠陥を招く。フォトンショットノイズを減らすには、露光量を大きくして入射フォトン数を増やす方法があるが、高感度化の要求とトレードオフとなる。
一般式(1):A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5)/([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127)
A値は0.120以上が好ましい。上限はA値が大きすぎる場合、レジスト膜のEUV光及び電子線透過率が低下し、レジスト膜中の光学像プロファイルが劣化し、結果として良好なパターン形状が得られにくくなるため、上限は0.240以下が好ましく、0.220以下がより好ましい。
例えば、レジスト組成物が酸分解性樹脂、塩B、及び、溶剤を含む場合、上記酸分解性樹脂、及び、塩Bが固形分に該当する。つまり、全固形分の全原子とは、上記酸分解性樹脂由来の全原子、及び、塩B由来の全原子の合計に該当する。例えば、[H]は、全固形分の全原子に対する、全固形分由来の水素原子のモル比率を表し、上記例に基づいて説明すると、[H]は、上記酸分解性樹脂由来の全原子、及び、上記化合物(1)由来の全原子の合計に対する、上記酸分解性樹脂由来の水素原子、及び、上記化合物(1)由来の水素原子の合計のモル比率を表すことになる。
上記レジスト組成物を用いたパターン形成方法の手順は以下の工程を有することが好ましい。
工程1:レジスト組成物を用いて、基板上にレジスト膜を形成する工程
工程2:レジスト膜を露光する工程
工程3:露光されたレジスト膜を現像液で現像する工程
以下、上記それぞれの工程の手順について詳述する。
工程1は、レジスト組成物を用いて、基板上にレジスト膜を形成する工程である。
レジスト組成物の定義は、上述のとおりである。
なお、塗布前にレジスト組成物を必要に応じてフィルターろ過することが好ましい。フィルターのポアサイズは、0.1μm以下が好ましく、0.05μm以下がより好ましく、0.03μm以下が更に好ましい。また、フィルターは、ポリテトラフルオロエチレン製、ポリエチレン製又はナイロン製が好ましい。
レジスト組成物の塗布後、基板を乾燥し、レジスト膜を形成してもよい。なお、必要により、レジスト膜の下層に、各種下地膜(無機膜、有機膜、反射防止膜)を形成してもよい。
トップコート組成物は、レジスト膜と混合せず、更にレジスト膜上層に均一に塗布できることが好ましい。トップコートは、特に制限されず、従来公知のトップコートを、従来公知の方法によって形成でき、例えば、特開2014-059543号公報の段落[0072]~[0082]の記載に基づいてトップコートを形成できる。
例えば、特開2013-061648号公報に記載されたような塩基性化合物を含むトップコートを、レジスト膜上に形成することが好ましい。トップコートが含み得る塩基性化合物の具体的な例は、レジスト組成物が含んでいてもよい塩基性化合物が挙げられる。
また、トップコートは、エーテル結合、チオエーテル結合、水酸基、チオール基、カルボニル結合、及び、エステル結合からなる群から選択される基又は結合を少なくとも1つ含む化合物を含むのも好ましい。
工程2は、レジスト膜を露光する工程である。
露光の方法としては、形成したレジスト膜に所定のマスクを通して活性光線又は放射線を照射する方法が挙げられる。
活性光線又は放射線としては、赤外光、可視光、紫外光、遠紫外光、極紫外光、X線、及び、電子線が挙げられる。
遠紫外光の波長としては、250nm以下が好ましく、220nm以下がより好ましく、1~200nmが更に好ましい。具体的には、KrFエキシマレーザー(248nm)、ArFエキシマレーザー(193nm)、F2エキシマレーザー(157nm)、EUV光(13nm)、X線、及び、電子ビームが挙げられる。
加熱温度は80~150℃が好ましく、80~140℃がより好ましく、80~130℃が更に好ましい。
加熱時間は10~1000秒が好ましく、10~180秒がより好ましく、30~120秒が更に好ましい。
加熱は通常の露光機及び現像機の少なくとも一方に備わっている手段で実施でき、ホットプレート等を用いて行ってもよい。
この工程は露光後ベーク(PEB:Post Exposure Bake)ともいう。
工程3は、現像液を用いて、露光されたレジスト膜を現像し、パターンを形成する工程である。
現像液は、アルカリ現像液であっても、有機溶剤を含む現像液(以下、「有機系現像液」ともいう。)であってもよい。
また、現像を行う工程の後に、他の溶剤に置換しながら、現像を停止する工程を実施してもよい。
現像時間は未露光部の樹脂が十分に溶解する時間であれば特に制限はなく、10~300秒が好ましく、20~120秒がより好ましい。
現像液の温度は0~50℃が好ましく、15~35℃がより好ましい。
有機系現像液に対する有機溶剤の含有量は、現像液の全質量に対して、50~100質量%が好ましく、80~100質量%がより好ましく、90~100質量%が更に好ましく、95~100質量%が特に好ましい。
上記パターン形成方法は、工程3の後に、リンス液を用いて洗浄する工程を含むことが好ましい。
リンス液には、界面活性剤を適当量添加してもよい。
また、本発明のパターン形成方法は、リンス工程の後に加熱工程(Post Bake)を含んでいてもよい。本工程により、ベークによりパターン間及びパターン内部に残留した現像液、及び、リンス液が除去される。また、本工程により、レジストパターンがなまされ、パターンの表面荒れが改善される効果もある。リンス工程の後の加熱工程は、通常40~250℃(好ましくは90~200℃)で、通常10秒間~3分間(好ましくは30秒間~2分間)行う。
基板(又は下層膜及び基板)の加工方法は特に制限されないが、工程3で形成されたパターンをマスクとして、基板(又は下層膜及び基板)に対してドライエッチングを行うことにより、基板にパターンを形成する方法が好ましい。ドライエッチングは、酸素プラズマエッチングが好ましい。
薬液配管としては、例えば、SUS(ステンレス鋼)又は帯電防止処理の施されたポリエチレン、ポリプロピレン若しくはフッ素樹脂(ポリテトラフルオロエチレン又はパーフルオロアルコキシ樹脂等)で被膜された各種配管を使用できる。フィルター及びO-リングに関しても同様に、帯電防止処理の施されたポリエチレン、ポリプロピレン又はフッ素樹脂(ポリテトラフルオロエチレン又はパーフルオロアルコキシ樹脂等)を使用できる。
また、本発明は、上記パターン形成方法を含む、電子デバイスの製造方法及びこの製造方法により製造された電子デバイスにも関する。
本発明の電子デバイスは、電気電子機器(家電、OA(Office Automation)、メディア関連機器、光学用機器及び通信機器等)に、好適に搭載されるものである。
以下の実施例に示す材料、使用量、割合、処理内容、及び、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更できる。従って、本発明の範囲は以下に示す実施例により限定的に解釈されるべきではない。
実施例及び比較例に用いたレジスト組成物に含まれる各成分を以下に示す。
レジスト組成物の調製に用いたオニウム塩(I)((I)-1~(I)-18)の構造を以下に示す。
下記式(I)-1-A(614.8g)をテトラヒドロフラン(600mL)に溶解させ、0℃に冷却して前駆体液1を得た。5-ヒドロキシイソフタル酸(62.4g)をテトラヒドロフラン(600mL)に溶解させ前駆体液2を得て、冷却した前駆体液1を0℃に保持したまま、前駆体液1に対して前駆体液2を滴下した。滴下終了後、反応混合物を室温まで昇温して2時間撹拌し、反応液1を得た。反応液1に酢酸エチル(600mL)を加え、有機相を1規定の塩酸及び水で洗浄した後、溶媒を留去して下記式(I)-1-Bの粗生成物を得た。続いて、(I)-1-Bの粗生成物をテトラヒドロフラン(500mL)に溶解し、溶解液に10%炭酸水素ナトリウム水溶液(500mL)を加え、50℃で3時間攪拌して反応液2を得た。反応液2に酢酸エチル(1000mL)を加えた後、反応液2から分液ロートで水相を除去し、更に酢酸エチルを留去して(I)-1-Cの粗生成物を得た。(I)-1-Cの粗生成物をジイソプロピルエーテルで晶析し、(I)-1-C(125g)を白色固体として得た(収率80%)。
レジスト組成物の調製に用いたオニウム塩(II)((II)-1~(II)-18)の構造を以下に示す。
表1中、pKaは、上記ソフトウェアパッケージ1を用いて求めた値を示す。なお、オニウム塩(II)において、酸性部位が複数存在する場合、上記構成部位Wに由来する酸性部位のpKaを示す。
レジスト組成物の調製に使用した樹脂(A-1~A-34(酸分解性樹脂に該当する))を以下に示す。樹脂A-1~A-34は、公知の方法に準じて合成したものを用いた。
表1中、「モル比」欄は、全繰り返し単位に対する、各繰り返し単位の含有量(モル%)を示す。
表1中、「Mw」欄は、重量平均分子量を示す。
表1中、「Mw/Mn」欄は、分散度を示す。
なお、樹脂A-1~A-34の重量平均分子量(Mw)及び分散度(Mw/Mn)はGPC(キャリア:テトラヒドロフラン(THF))により測定した(ポリスチレン換算量である)。また、樹脂の組成比(モル比率)は、13C-NMR(Nuclear Magnetic Resonance)により測定した。
レジスト組成物の調製に用いた酸拡散抑制剤(B-1~B-4)の構造を以下に示す。
レジスト組成物の調製に使用した疎水性樹脂C(C-1~C-8)を以下に示す。
表3中、「モル比」欄は、全繰り返し単位に対する、各繰り返し単位の含有量(モル%)を示す。
表3中、「Mw」欄は、重量平均分子量を示す。
表3中、「Mw/Mn」欄は、分散度を示す。
なお、樹脂C-1~C-8の重量平均分子量(Mw)及び分散度(Mw/Mn)はGPC(キャリア:テトラヒドロフラン(THF))により測定した(ポリスチレン換算量である)。また、樹脂の組成比(モル比率)は、13C-NMR(Nuclear Magnetic Resonance)により測定した。
レジスト組成物の調製に使用した界面活性剤E(E-1~E-3)を以下に示す。
E-1:メガファックF176(DIC(株)製、フッ素系界面活性剤)
E-2:メガファックR08(DIC(株)製、フッ素及びシリコン系界面活性剤)
E-3:PF656(OMNOVA社製、フッ素系界面活性剤)
レジスト組成物の調製に使用した溶剤F(F-1~F-9)を以下に示す。
F-1:プロピレングリコールモノメチルエーテルアセテート(PGMEA)
F-2:プロピレングリコールモノメチルエーテル(PGME)
F-3:プロピレングリコールモノエチルエーテル(PGEE)
F-4:シクロヘキサノン
F-5:シクロペンタノン
F-6:2-ヘプタノン
F-7:乳酸エチル
F-8:γ-ブチロラクトン
F-9:プロピレンカーボネート
下記表3に示す各成分を固形分濃度が2質量%になるように混合した。得られた混合液を、孔径0.02μmのポリエチレン製フィルターに通液させてろ過し、各レジスト組成物を調製した。
「固形分」とは、溶剤以外の全ての成分を意味する。
これらのレジスト組成物を、予めヘキサメチルジシラザン(HMDS)処理を施した6インチSi(シリコン)ウェハ上に、東京エレクトロン製スピンコーター「Mark8」を用いて塗布し、130℃、300秒間ホットプレート上で乾燥して、膜厚30nmのレジスト膜を得た。
ここで、1インチは、0.0254mである。
表3中、種類欄において「/」で区切られた記載は、当該物質として複数の化合物を含むことを示し、質量%欄において「/」で区切られた記載は、複数の化合物の含有量を順に示す。例えば、「Re-26」の「オニウム塩(I)」は、「(I)-1」及び「(I)-14」を含み、含有量が順に「13.0」及び「13.0」質量%であることを表す。
表3中、「質量%」欄は、全固形分に対する、各固形分成分の含有量(質量%)を示す。固形分とは、溶媒の除いた成分のことをいう。
表3中、「溶剤」の「混合比」欄は、各溶剤の混合比(質量比)を示す。
[EUV露光]
上記で得られたレジスト膜が塗布されたウェハを、Exitech社製EUV露光装置(Micro Exposure Tool、NA(開口数)0.3、Quadrupole、アウターシグマ0.68、インナーシグマ0.36)を用いてパターン露光を行った。露光マスクには、線幅20nmで1:1ラインアンドスペースパターンのものを使用した。
[有機溶剤現像]
露光したウェハを、ホットプレート上で90℃、60秒間加熱した後、酢酸n-ブチルで30秒間現像し、これをスピン乾燥し、ネガ型のレジストパターンを得た。
上記手順により、後段に示す表5に記載の実施例1-1~1-35、並びに、比較例1-1及び1-2のレジストパターンを得た。
[アルカリ現像]
露光したウェハを、ホットプレート上で100℃、90秒間加熱した後、2.38質量%のテトラメチルアンモニウムハイドロオキサイド(TMAH)水溶液に60秒間浸漬した後、水で30秒間リンスした。その後、回転数4000rpmでウェハを30秒間回転させた後、95℃で60秒間ベークを行って乾燥し、ポジ型のレジストパターンを得た。
上記手順により、後段に示す表6に記載の実施例2-1~2-35、並びに、比較例2-1及び2-2のレジストパターンを得た。
有機溶剤現像にて得られた各実施例及び各比較例(実施例1-1~1-35、並びに、比較例1-1及び1-2)のレジストパターンは、以下の手順に従って評価した。
得られた各実施例及び各比較例のライン幅が平均20nmのラインパターンの断面形状を測長走査型電子顕微鏡(SEM、日立製作所社製S-9380II)によって観察し、レジストパターンの底部におけるパターン線幅Lbと、レジストパターンの上部でのパターン線幅Laとを測定した。La/Lbの値を指標に、パターン形状の断面矩形性を下記の基準で評価した。Sが最も良好で、Eが最も不良である。実用上、D以上の評価が望ましい。
[評価基準]
S:1.00≦(La/Lb)≦1.01
A:1.01<(La/Lb)≦1.02
B:1.02<(La/Lb)≦1.03
C:1.03<(La/Lb)≦1.04
D:1.04<(La/Lb)≦1.05
E:1.05<(La/Lb)
アルカリ水溶液現像にて得られた各実施例及び各比較例(実施例2-1~2-35、並びに、比較例2-1及び2-2)のレジストパターンは、以下の手順に従って評価した。
得られた各実施例及び各比較例のライン幅が平均20nmのラインパターンの断面形状を測長走査型電子顕微鏡(SEM、日立製作所社製S-9380II)によって観察し、レジストパターンの底部におけるパターン線幅Lbと、レジストパターンの上部でのパターン線幅Laとを測定した。Lb/Laの値を指標に、パターン形状の断面矩形性を下記の基準で評価した。Sが最も良好で、Eが最も不良である。実用上、D以上の評価が望ましい。
[評価基準]
S:1.00≦(Lb/La)≦1.01
A:1.01<(Lb/La)≦1.02
B:1.02<(Lb/La)≦1.03
C:1.03<(Lb/La)≦1.04
D:1.04<(Lb/La)≦1.05
E:1.05<(Lb/La)
表5及び表6中、「要件1」欄における「A」~「D」の表記は、レジスト組成物に用いたオニウム塩(I)について、以下の場合であることを示す。
A:オニウム塩(I)が上記式(1)で表される酸を発生し、式(1)中のRSが、-CO-O-RS1、又は、-O-CO-RS1を表し、かつ、nが2~5の場合
B:オニウム塩(I)が上記式(1)で表される酸を発生し、式(1)中のRSが、-CO-RS1、-CO-O-RS1、-O-CO-RS1、-O-CO-O-RS1、-SO2-RS1、若しくは、-SO3-RS1を表し、かつ、nが1の場合、又は、式(1)中のRSの1つのみが-CO-O-RS1、又は、-O-CO-RS1を表し、かつ、nが2~5の場合
C:オニウム塩(I)が上記式(1)で表される酸を発生し、式(1)中のRSが、-O-RS1を表す場合
D:オニウム塩(I)が上記式(1)で表される酸を発生しない場合
表5及び表6中、「要件2」欄における「A」~「C」の表記は、レジスト組成物に用いたオニウム塩(II)について、以下の場合であることを示す。
A:オニウム塩(II)における構造部位W中のアニオン部位A(表1中のpKaを示すアニオン部)が、式(II)-1で表される部位である場合
B:オニウム塩(II)における構造部位W中のアニオン部位A(表1中のpKaを示すアニオン部)が、式(II)-3~(II)-6のいずれかで表される部位であり、式(II)-1で表される部位でない場合
C:オニウム塩(II)における構造部位W中のアニオン部位A(表1中のpKaを示すアニオン部)が、式(II)-2で表される部位であり、式(II)-1、又は、式(II)-3~(II)-6で表される部位でない場合
実施例1-3、1-22、及び、1-31、並びに、実施例2-3、2-22、及び、2-31と、他の実施例の比較から、構造部位W中のアニオン部位Aが、上記式(II)-1~(II)-6のいずれかで表される部位である場合、本発明の効果がより優れることが確認された。
実施例1-2、1-4、1-7~1-9、1-20、1-27、1-32、1-33、及び、1-35、並びに、実施例2-2、2-4、2-7~2-9、2-20、2-27、2-32、2-33、及び、2-35と、他の実施例の比較から、構造部位W中のアニオン部位Aが、上記式(II)-1で表される部位である場合、本発明の効果がより優れることが確認された。
実施例1-1~1-4、1-8、1-13、1-15、1-17、1-18、1-22、1-23、1-25~1-27、1-32、1-33、及び、1-35、並びに、実施例2-1~2-4、2-8、2-13、2-15、2-17、2-18、2-22、2-23、2-25~2-27、2-32、2-33、及び、2-35と、その他の実施例の比較から、上記式(1)中、nが2~5の場合、本発明の効果がより優れることが確認された。
実施例1-5、1-20、1-21、及び、1-31、並びに、実施例2-5、2-20、2-21、及び、2-31と、その他の実施例の比較から、上記式(1)中、RSが、-CO-ORS1、-O-CO-RS1、-O-CO-O-RS1、-SO2-RS1、又は、-SO3-RS1を表し、RS1が、1価の置換基を表す場合、本発明の効果がより優れることが確認された。
実施例1-2、1-4、1-8、1-27、1-32、1-33、及び、1-35、並びに、実施例2-2、2-4、2-8、2-27、2-32、2-33、及び、2-35とその他の実施例の比較から、上記式(1)中、RSが、-CO-ORS1、又は、-O-CO-RS1を表し、RS1が、1価の置換基を表す場合、本発明の効果がより優れることが確認された。
Claims (13)
- 酸の作用により分解して極性基を生じる基を有する樹脂と、
活性光線又は放射線の照射によって式(1)で表される酸を発生するオニウム塩(I)と、
アニオン部位Aとカチオン部位Mとからなり、活性光線又は放射線の照射によってHAで表される酸性部位を形成する構造部位Wを少なくとも1つ有するオニウム塩(II)と、を含み、
構造部位W中のカチオン部位をH+に置き換えてなるHAで表される酸性部位に由来する酸解離定数が、式(1)で表される酸の酸解離定数よりも大きい、感活性光線又は感放射線性樹脂組成物。
Rfは、フッ素原子、又は、少なくとも1つのフッ素原子を有するアルキル基を表す。 Yは、単結合、酸素原子、又は、硫黄原子を表す。
Arは、RS以外の置換基を有していてもよい、n+1価の芳香環基を表す。
RSは、それぞれ独立に、-O-RS1、-CO-RS1、-CO-O-RS1、-O-CO-RS1、-O-CO-O-RS1、-SO2-RS1、又は、-SO3-RS1を表す。RS1は、1価の置換基を表す。
mは、1以上の整数を表す。
nは、1~5の整数を表す。 - 前記構造部位Wの前記アニオン部位Aが、式(II)-1、及び、式(II)-3~(II)-6のいずれかで表される部位である、請求項2に記載の感活性光線又は感放射線性樹脂組成物。
- 前記構造部位W中の前記アニオン部位Aが、式(II)-1で表される部位である、請求項2に記載の感活性光線又は感放射線性樹脂組成物。
- 前記式(1)中のnが2~5である、請求項1~4のいずれか1項に記載の感活性光線又は感放射線性樹脂組成物。
- 前記式(1)中、RSがそれぞれ独立に、-CO-ORS1、-O-CO-RS1、-O-CO-O-RS1、-SO2-RS1、又は、-SO3-RS1を表し、RS1が、1価の置換基を表す、請求項1~5のいずれか1項に記載の感活性光線又は感放射線性樹脂組成物。
- 前記式(1)中、RSがそれぞれ独立に、-CO-ORS1、又は、-O-CO-RS1を表し、RS1が、1価の置換基を表す、請求項1~6のいずれか1項に記載の感活性光線又は感放射線性樹脂組成物。
- 請求項1~7のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物を用いて形成される、レジスト膜。
- 請求項1~7のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物を用いて基板上にレジスト膜を形成するレジスト膜形成工程と、
前記レジスト膜を露光する露光工程と、
露光された前記レジスト膜に対して現像液を用いて現像する現像工程と、を有する、パターン形成方法。 - 前記露光工程においてEUV光により露光する、請求項9に記載のパターン形成方法。
- 前記現像液が、有機溶剤を含む、請求項9又は10に記載のパターン形成方法。
- 前記有機溶剤が、酢酸ブチルを含む、請求項11に記載のパターン形成方法。
- 請求項9~12に記載のパターン形成方法を含む、電子デバイスの製造方法。
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