WO2017110352A1 - 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、及び、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、感活性光線性又は感放射線性膜、パターン形成方法、及び、電子デバイスの製造方法 Download PDFInfo
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
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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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—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
- 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
- G03F7/2006—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 using coherent light; using polarised light
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
Definitions
- the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method using these, and an electronic device manufacturing method. More specifically, the present invention relates to an actinic ray used for a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, a further photofabrication process, a lithographic printing plate, and an acid curable composition. The present invention relates to a light-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, and a pattern forming method and an electronic device manufacturing method using the same.
- the chemically amplified resist composition generates an acid in the exposed area by irradiation with radiation such as far ultraviolet light, and the acid-catalyzed reaction makes the active radiation irradiated and non-irradiated areas soluble in the developer. It is a pattern forming material that changes and forms a pattern on a substrate.
- a thick resist film having a thickness of 2 to 20 ⁇ m is formed using a specific resist composition, the thick resist film is selectively exposed, and then the thick resist film is developed to form a three-dimensional structure.
- a method of forming a resist pattern for creating a memory is known (see Patent Document 1).
- the present invention solves the above-mentioned problems, and in the case of forming a pattern from a thick resist film (for example, having a thickness of 1 ⁇ m or more), it achieves both excellent resolution and excellent exposure latitude at a high level.
- the actinic ray-sensitive or radiation-sensitive resin composition, the actinic ray-sensitive or radiation-sensitive film that can suppress roughness on the side wall of the resist pattern that may occur during etching, a pattern forming method, and these An object of the present invention is to provide a method for manufacturing the electronic device used.
- An actinic ray-sensitive or radiation-sensitive resin composition comprising: The solid content in the actinic ray-sensitive or radiation-sensitive resin composition is 20% by mass or more, The actinic ray-sensitive or radiation-sensitive resin composition, wherein a softening point of a resist pattern formed by the actinic ray-sensitive or radiation-sensitive resin composition is 130 ° C or higher and 170 ° C or lower.
- An actinic ray-sensitive or radiation-sensitive film having a thickness of 1 ⁇ m or more is formed on the substrate by the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10]
- a pattern is formed from a thick resist film (for example, having a thickness of 1 ⁇ m or more)
- excellent resolution and excellent exposure latitude are obtained in a high dimension.
- Actinic ray-sensitive or radiation-sensitive resin composition capable of suppressing roughness on the side wall of the resist pattern that may occur during etching, an actinic ray-sensitive or radiation-sensitive film, and a pattern forming method, and An electronic device manufacturing method using these can be provided.
- the notation that does not indicate substitution and non-substitution includes not only those having no substituent but also those having a substituent.
- the “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).
- active light or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB) and the like. .
- light means actinic rays or radiation.
- exposure in this specification means not only exposure with far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps and excimer lasers, but also electron beams, ion beams, etc. Drawing with particle beams is also included in the exposure.
- (meth) acrylate represents acrylate and methacrylate
- (meth) acryl represents acryl and methacryl.
- the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of the resin are measured by GPC (solvent) using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Tosoh Corporation).
- RI differential refractive index
- the glass transition temperature is measured by a thermal analyzer DSC Q1000 manufactured by TA Instruments.
- the viscosity is a viscosity at 25.0 ° C., and is measured by RE-85L manufactured by TOKI SANGYO.
- the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also simply referred to as the composition of the present invention) is a resin (A) having a glass transition temperature of 155 ° C. or higher, and a compound having a glass transition temperature of 150 ° C. or lower. (B) and an actinic ray-sensitive or radiation-sensitive resin composition containing a solvent (C), wherein the solid content in the actinic ray-sensitive or radiation-sensitive resin composition is 20% by mass.
- the softening point of the resist pattern formed by the actinic ray-sensitive or radiation-sensitive resin composition is 130 ° C. or higher and 170 ° C. or lower.
- the softening point of the resist pattern specifically refers to the softening point of an isolated space pattern having a space width of 10 ⁇ m, a pitch width of 100 ⁇ m, and a resist film portion thickness of 7.5 ⁇ m. Since the present invention has the above-described configuration, when a pattern is formed from a thick resist film (for example, having a thickness of 1 ⁇ m or more), excellent resolution and excellent exposure latitude are compatible at a high level. At the same time, the roughness on the side wall of the resist pattern that may occur during etching can be suppressed. The reason is not clear, but is presumed as follows.
- the thick film It becomes easy to apply a resist film (for example, having a thickness of 1 ⁇ m or more).
- the actinic ray-sensitive or radiation-sensitive resin composition contains a resin (A) having a glass transition temperature of 155 ° C. or higher.
- the resist film has a resist pattern (space width is 10 ⁇ m, pitch) because the actinic ray-sensitive or radiation-sensitive resin composition contains a resin (A) having a glass transition temperature of 155 ° C. or higher.
- the softening point of an isolated space pattern having a width of 100 ⁇ m and a resist film portion thickness of 7.5 ⁇ m is 130 ° C. or higher.
- the film quality of the isolated space pattern obtained is more than a certain degree of hardness, so that, for example, an isolated space pattern having a higher degree of fineness (shorter space width) than the above isolated space pattern is formed. In this case, it is presumed that an excellent exposure latitude was obtained.
- the actinic ray-sensitive or radiation-sensitive resin composition contains a compound (B) having a glass transition temperature of 150 ° C. or lower, and this is the main reason for resist patterns (space width is 10 ⁇ m, pitch The softening point of an isolated space pattern having a width of 100 ⁇ m and a resist film portion thickness of 7.5 ⁇ m is 170 ° C. or lower. Thereby, the film quality of the pattern obtained is not too hard (has a certain degree of flexibility). As a result, for example, even when an isolated space pattern or the like having a higher degree of fineness (shorter space width) than the above pattern is formed on the substrate and this substrate is etched, roughness is generated on the sidewall of the resist pattern.
- the actinic ray-sensitive or radiation-sensitive resin composition in the present invention contains a resin (A) having a glass transition temperature of 155 ° C. or higher and a compound (B) having a glass transition temperature of 150 ° C. or lower. Since the softening point is set to 170 ° C. or less, the roughness on the sidewall of the resist pattern that can occur during etching while achieving both excellent resolution and excellent exposure latitude at a high level. It is thought that this could be suppressed.
- the softening point of the resist pattern (isolated space pattern having a space width of 10 ⁇ m, a pitch width of 100 ⁇ m, and a resist film portion thickness of 7.5 ⁇ m) can be measured by the following procedure.
- a resist film portion formed from an actinic ray-sensitive or radiation-sensitive resin composition having a thickness of 7.5 ⁇ m is subjected to pattern exposure and development to have a space width of 10 ⁇ m and a pitch width of 100 ⁇ m.
- An isolated space pattern having a thickness of 7.5 ⁇ m is formed.
- the chip is heated at 150 ° C. for 60 seconds, the chip as sample B is heated at 155 ° C. for 60 seconds, and the chip as sample C is heated at 150 ° C. for 60 seconds.
- Each chip was cleaved.
- (3) The interface between the resist film part and the space part in the chip section is observed with a scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation), and the thickness of the resist film part (depth of the space part)
- the width of the space portion at a height of 20% from the surface (that is, the upper surface) of the resist film portion is 50% deep from the surface of the resist film portion.
- the minimum value of the temperature at which the shape of the resist film part has changed to a state where it becomes 1.2 times or more the space width of the space part is defined as the softening point (° C.).
- the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably for KrF exposure.
- the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may be a positive resist composition for alkali development or a negative resist composition for organic solvent development.
- the positive resist composition is preferably used.
- the composition according to the present invention is typically a chemically amplified resist composition.
- the composition of the present invention contains a resin (A) having a glass transition temperature of 155 ° C. or higher.
- the resin (A) is typically a resin that is decomposed by the action of an acid and changes in solubility in a developer, and increases in solubility in an alkali developer by the action of an acid, or by the action of an acid. It is preferable that the resin has a reduced solubility in a developer containing an organic solvent as a main component. It is preferable to have a group (hereinafter also referred to as “acid-decomposable group”) that generates
- the acid-decomposable group preferably has a structure in which a polar group is protected by a group that decomposes and leaves under the action of an acid.
- Polar groups include phenolic hydroxyl group, carboxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc.
- Examples thereof include an acidic group (a group that is dissociated in a 2.38% by mass tetramethylammonium hydroxide aqueous solution that has been used as a conventional resist developer), an alcoholic hydroxyl group, and the like.
- Preferred polar groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
- a preferable group as the acid-decomposable group is a group in which the hydrogen atom of these polar groups is substituted with a group capable of leaving by the action of an acid.
- the group capable of leaving by the action of an acid include —C (R 36 ) (R 37 ) (R 38 ), —C (R 36 ) (R 37 ) (OR 39 ), —C (R 01 ) ( R 02 ) (OR 39 ), —C (R 01 ) (R 02 ) —C ( ⁇ O) —O—C (R 36 ) (R 37 ) (R 38 ) or —CH (R 36 ) (Ar) Etc.
- R 36 to R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R 36 and R 37 may be bonded to each other to form a ring.
- R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- Ar represents an aryl group.
- the alkyl group as R 36 to R 39 , R 01 , or R 02 is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- A butyl group, a hexyl group, and an octyl group are mentioned.
- the cycloalkyl group as R 36 to R 39 , R 01 , or R 02 may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group.
- the monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
- the polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, such as an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, ⁇ -pinanyl group, tricyclodecanyl group, A tetracyclododecyl group and an androstanyl group are mentioned.
- a part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
- the aryl group as R 36 to R 39 , R 01 , R 02 , or Ar is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
- the aralkyl group as R 36 to R 39 , R 01 , or R 02 is preferably an aralkyl group having 7 to 12 carbon atoms, and for example, a benzyl group, a phenethyl group, and a naphthylmethyl group are preferable.
- the alkenyl group as R 36 to R 39 , R 01 , or R 02 is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group. .
- the ring that R 36 and R 37 may be bonded to each other may be monocyclic or polycyclic.
- the monocyclic type is preferably a cycloalkane structure having 3 to 8 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure.
- the polycyclic type is preferably a cycloalkane structure having 6 to 20 carbon atoms, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. Note that some of the carbon atoms in the ring structure may be substituted with a heteroatom such as an oxygen atom. Each of the above groups may have a substituent.
- substituents examples include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, and an acyloxy group. , Alkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.
- the acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.
- the repeating unit having an acid-decomposable group that can be contained in the resin (A) is preferably a repeating unit represented by the following general formula (AI).
- Xa 1 represents a hydrogen atom or an alkyl group.
- T represents a single bond or a divalent linking group.
- Rx 1 to Rx 3 each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). Two of Rx 1 to Rx 3 may combine to form a cycloalkyl group (monocyclic or polycyclic).
- the alkyl group represented by Xa 1 may or may not have a substituent, and examples thereof include a methyl group or 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, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. And more preferably a methyl group.
- Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or the like.
- Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like.
- 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, more preferably a —CH 2 — group, — (CH 2 ) 2 — group, or — (CH 2 ) 3 — group.
- the alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.
- Examples of the cycloalkyl group of Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group.
- Examples of the cycloalkyl group formed by combining two of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group
- a monocyclic cycloalkyl group such as a group is preferred.
- a monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
- 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 has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It may be replaced.
- the repeating unit represented by the general formula (AI) preferably has, for example, an embodiment in which Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-described cycloalkyl group.
- Each of the above groups may have a substituent.
- 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, an alkoxy group.
- substituents include carbonyl groups (having 2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferred.
- Rx and Xa 1 represent a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
- Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms.
- Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent.
- p represents 0 or a positive integer.
- Examples of the substituent containing a polar group represented by Z include a linear or branched alkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group, or a sulfonamide group, and a cycloalkyl group. Is an alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferable.
- the resin (A) preferably contains, for example, a repeating unit represented by the general formula (3) as the repeating unit represented by the general formula (AI).
- R 31 represents a hydrogen atom or an alkyl group.
- R 32 represents an alkyl group or a cycloalkyl group, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. And a cyclohexyl group.
- R 33 represents an atomic group necessary for forming a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which R 32 is bonded. In the alicyclic hydrocarbon structure, a part of carbon atoms constituting the ring may be substituted with a hetero atom or a group having a hetero atom.
- the alkyl group for R 31 may have a substituent, and examples of the substituent include a fluorine atom and a hydroxyl group.
- R 31 preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
- R 32 is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group or a cyclohexyl group, and more preferably a methyl group, an ethyl group, an isopropyl group or a tert-butyl group. .
- the monocyclic alicyclic hydrocarbon structure formed by R 33 together with the carbon atom is preferably a 3- to 8-membered ring, more preferably a 5- or 6-membered ring.
- examples of the hetero atom that can form the ring include an oxygen atom and a sulfur atom.
- examples of the group having a hetero atom include a carbonyl group and the like. Can be mentioned. However, the group having a hetero atom is preferably not an ester group (ester bond).
- the monocyclic alicyclic hydrocarbon structure formed by R 33 together with the carbon atom is preferably formed only from the carbon atom and the hydrogen atom.
- the repeating unit represented by the general formula (3) is preferably a repeating unit represented by the following general formula (3 ').
- R 31 and R 32 have the same meanings as in general formula (3).
- R 31 and R 32 have the same meanings as in general formula (3).
- the specific example of the repeating unit which has a structure represented by General formula (3) is given below, it is not limited to these.
- the content of the repeating unit having the structure represented by the general formula (3) is preferably 20 to 80 mol%, and preferably 25 to 75 mol% with respect to all the repeating units in the resin (A). Is more preferable, and it is still more preferable that it is 30 to 70 mol%.
- repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following general formula (A).
- R 01 , R 02 and R 03 each independently represent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- Ar 1 represents an aromatic ring group.
- R 03 represents an alkylene group and may be bonded to Ar 1 to form a 5-membered or 6-membered ring together with the —C—C— chain.
- n Y's each independently represent a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of Y represents a group capable of leaving by the action of an acid.
- n represents an integer of 1 to 4, preferably 1 to 2, and more preferably 1.
- the alkyl group as R 01 to R 03 is, for example, an alkyl group having 20 or less carbon atoms, and preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a hexyl group. 2-ethylhexyl group, octyl group or dodecyl group. More preferably, these alkyl groups are alkyl groups having 8 or less carbon atoms. In addition, these alkyl groups may have a substituent. As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R 01 to R 03 are preferable.
- the cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group.
- monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, and cyclohexyl group are exemplified.
- these cycloalkyl groups may have a substituent.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.
- the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group.
- the aromatic ring group as Ar 1 preferably has 6 to 14 carbon atoms, and examples thereof include a benzene ring, a toluene ring, and a naphthalene ring. In addition, these aromatic ring groups may have a substituent.
- Preferred examples of the group capable of leaving by the action of an acid as at least one of Y are those described above.
- the group capable of leaving by the action of an acid as at least one of Y is more preferably a structure represented by the following general formula (B).
- L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
- M represents a single bond or a divalent linking group.
- Q represents an alkyl group, a cycloalkyl group, a cycloaliphatic group, an aromatic ring group, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group.
- the cycloaliphatic group and the aromatic ring group may contain a hetero atom.
- At least two of Q, M, and L 1 may be bonded to each other to form a 5-membered or 6-membered ring.
- the alkyl group as L 1 and L 2 is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and An octyl group is mentioned.
- the cycloalkyl group as L 1 and L 2 is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and specific examples include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.
- the aryl group as L 1 and L 2 is, for example, an aryl group having 6 to 15 carbon atoms, and specific examples include a phenyl group, a tolyl group, a naphthyl group, and an anthryl group.
- the aralkyl group as L 1 and L 2 is, for example, an aralkyl group having 6 to 20 carbon atoms, and specific examples include a benzyl group and a phenethyl group.
- the divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group or octylene group), cycloalkylene group (for example, cyclopentylene group or cyclohexylene group). ), Alkenylene group (for example, ethylene group, propenylene group or butenylene group), arylene group (for example, phenylene group, tolylene group or naphthylene group), —S—, —O—, —CO—, —SO 2 —, — N (R 0) -, or a combination of two or more thereof.
- alkylene group for example, methylene group, ethylene group, propylene group, butylene group, hexylene group or octylene group
- cycloalkylene group for example, cyclopentylene group or cyclohexylene group.
- R 0 is a hydrogen atom or an alkyl group.
- the alkyl group as R 0 is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group. Can be mentioned.
- the alkyl group and cycloalkyl group as Q are the same as the above-described groups as L 1 and L 2 .
- Examples of the cyclic aliphatic group or aromatic ring group as Q include the cycloalkyl group and aryl group as L 1 and L 2 described above. These cycloalkyl group and aryl group are preferably groups having 3 to 15 carbon atoms.
- Examples of the cycloaliphatic group or aromatic ring group containing a hetero atom as Q include thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, And groups having a heterocyclic structure such as thiazole and pyrrolidone.
- the ring is not limited to these as long as it is a ring formed of carbon and a heteroatom, or a ring formed only of a heteroatom.
- Examples of the ring structure that can be formed by bonding at least two of Q, M, and L 1 to each other include a 5-membered or 6-membered ring structure in which these form a propylene group or a butylene group.
- This 5-membered or 6-membered ring structure contains an oxygen atom.
- Each group represented by L 1 , L 2 , M and Q in the general formula (B) may have a substituent.
- substituents include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, and an acyloxy group. , Alkoxycarbonyl group, cyano group and nitro group. These substituents preferably have 8 or less carbon atoms.
- the group represented by — (MQ) is preferably a group having 1 to 20 carbon atoms, more preferably a group having 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.
- the resin (A) may contain a repeating unit represented by the following general formula (BZ) as a repeating unit having an acid-decomposable group.
- AR represents an aryl group.
- Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
- Rn and AR may be bonded to each other to form a non-aromatic ring.
- R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.
- the aryl group for AR is preferably a group having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, an anthryl group, or a fluorene group, and more preferably a group having 6 to 15 carbon atoms.
- AR is a naphthyl group, anthryl group, or fluorene group
- the bonding position between the carbon atom to which Rn is bonded and AR is not particularly limited.
- this carbon atom may be bonded to the ⁇ -position of the naphthyl group or may be bonded to the ⁇ -position.
- AR when AR is an anthryl group, this carbon atom may be bonded to the 1-position, the 2-position, or the 9-position of the anthryl group.
- Each of the aryl groups as AR may have one or more substituents. Specific examples of such substituents include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and dodecyl group.
- a linear or branched alkyl group having 1 to 5 carbon atoms and an alkoxy group containing the alkyl group moiety are preferable, and a paramethyl group
- the aryl group as AR has a plurality of substituents
- at least two of the plurality of substituents may be bonded to each other to form a ring.
- the ring is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring.
- this ring may be a heterocycle containing a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.
- this ring may have a substituent.
- the repeating unit represented by general formula (BZ) contains two or more aromatic rings from a viewpoint of roughness performance.
- the number of aromatic rings contained in this repeating unit is usually preferably 5 or less, and more preferably 3 or less.
- AR preferably contains two or more aromatic rings, and AR is more preferably a naphthyl group or a biphenyl group.
- the number of aromatic rings possessed by AR is usually preferably 5 or less, and more preferably 3 or less.
- Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
- the alkyl group of Rn may be a straight chain alkyl group or a branched chain alkyl group.
- the alkyl group is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc. Examples thereof include those having 1 to 20 carbon atoms.
- the alkyl group of Rn preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms.
- Examples of the cycloalkyl group represented by Rn include those having 3 to 15 carbon atoms such as a cyclopentyl group and a cyclohexyl group.
- As the aryl group of Rn for example, those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthryl group are preferable.
- Each of the alkyl group, cycloalkyl group and aryl group as Rn may further have a substituent.
- substituents include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, a dialkylamino group, an alkylthio group, an arylthio group, an aralkylthio group, and a thiophenecarbonyloxy group.
- Thiophenemethylcarbonyloxy group and heterocyclic residues such as pyrrolidone residues.
- R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkyloxycarbonyl group as described above.
- Examples of the alkyl group and cycloalkyl group for R 1 include the same groups as those described above for Rn.
- Each of these alkyl groups and cycloalkyl groups may have a substituent. Examples of this substituent include the same as those described above for Rn.
- R 1 is an alkyl group or a cycloalkyl group having a substituent
- R 1 includes, for example, a trifluoromethyl group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group.
- the halogen atom for R 1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is particularly preferable.
- Rn and AR are preferably bonded to each other to form a non-aromatic ring, and in particular, roughness performance can be further improved.
- the non-aromatic ring that may be formed by bonding Rn and AR is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring.
- the non-aromatic ring may be an aliphatic ring or a heterocycle containing a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.
- the non-aromatic ring may have a substituent. As this substituent, the thing similar to having demonstrated previously about the further substituent which Rn may have is mentioned, for example.
- repeating unit represented by the general formula (BZ) are shown below, but are not limited thereto.
- the total content of the repeating units having an acid-decomposable group is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, based on all repeating units in the resin (A), 30 More preferably, it is ⁇ 80 mol%.
- the resin (A) preferably contains a repeating unit having a cyclic carbonate structure.
- This cyclic carbonate structure is a structure having a ring including a bond represented by —O—C ( ⁇ O) —O— as an atomic group constituting the ring.
- the ring containing a bond represented by —O—C ( ⁇ O) —O— as the atomic group constituting the ring is preferably a 5- to 7-membered ring, and most preferably a 5-membered ring.
- Such a ring may be condensed with another ring to form a condensed ring.
- the resin (A) may contain a repeating unit having a lactone structure or a sultone (cyclic sulfonate ester) structure.
- Any lactone group or sultone group can be used as long as it has a lactone structure or a sultone structure, but it is preferably a 5- to 7-membered lactone structure or a sultone structure, and a 5- to 7-membered lactone A structure in which another ring structure is condensed to form a bicyclo structure or a spiro structure in the structure or sultone structure is preferable.
- a lactone structure or a sultone structure may be directly bonded to the main chain.
- Preferred lactone structures or sultone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), and more preferably (LC1-4).
- the lactone structure portion or the sultone structure portion may or may not 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 2 to 8 carbon atoms, and carboxyl groups. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group.
- n 2 represents an integer of 0 to 4. When n 2 is 2 or more, a plurality of substituents (Rb 2 ) may be the same or different, and a plurality of substituents (Rb 2 ) may be bonded to form a ring. .
- repeating unit having a lactone structure or a sultone (cyclic sulfonic acid ester) structure are listed below, but the present invention is not limited thereto.
- Particularly preferred examples include the following repeating units.
- the repeating unit having a lactone group or a sultone group usually has an optical isomer, but any optical isomer may be used.
- One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
- the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.
- the resin (A) preferably has a repeating unit having a hydroxyl group or a cyano group other than those represented by the general formulas (AI) and (3). This improves the substrate adhesion and developer compatibility.
- the 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, and preferably has no acid-decomposable group.
- the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group.
- As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group a structure represented by the following general formula is preferred.
- the content of the repeating unit having a hydroxyl group or a cyano group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (A).
- Specific examples of the repeating unit having a hydroxyl group or a cyano group include the repeating unit disclosed in paragraph 0340 of US Patent Publication No. 2012/0135348, but the present invention is not limited thereto.
- the resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention may have a repeating unit having an alkali-soluble group.
- the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron-withdrawing group at the ⁇ -position. It is more preferable to have a repeating unit. By containing the repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased.
- the repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group.
- a repeating unit to which a soluble group is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is used at the time of polymerization and introduced at the end of the polymer chain. Both are preferable, and the linking group is monocyclic or polycyclic. It may have a cyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.
- the content of the repeating unit having an alkali-soluble group is preferably from 0 to 20 mol%, more preferably from 3 to 15 mol%, still more preferably from 5 to 10 mol%, based on all repeating units in the resin (A).
- Specific examples of the repeating unit having an alkali-soluble group include the repeating unit disclosed in paragraph 0344 of US Patent Publication No. 2012/0135348, but the present invention is not limited thereto.
- the resin (A) preferably has a repeating unit having a phenolic hydroxyl group as the repeating unit having an alkali-soluble group, and more preferably has a repeating unit derived from hydroxystyrene.
- a phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic ring group with a hydroxyl group.
- the aromatic ring is a monocyclic or polycyclic aromatic ring, for example, an aromatic carbon which may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring.
- a hydrogen ring or a heterocycle such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc.
- aromatic ring heterocycles Among these, a benzene ring and a naphthalene ring are preferable from the viewpoint of resolution, and a benzene ring is most preferable.
- the content of the repeating unit having a phenolic hydroxyl group is preferably from 30 to 90 mol%, more preferably based on all repeating units in the resin (A). Is 35 to 85 mol%, more preferably 40 to 80 mol%.
- repeating unit having a phenolic hydroxyl group examples include phenolic hydroxyl group, but the present invention is not limited thereto.
- the resin (A) of the present invention further has an alicyclic hydrocarbon structure that does not have a polar group (for example, the alkali-soluble group, hydroxyl group, cyano group, etc.) and has a repeating unit that does not exhibit acid decomposability. it can.
- a repeating unit include a repeating unit represented by the general formula (IV).
- R 5 represents a hydrocarbon group having at least one cyclic structure and having no polar group.
- Ra represents a hydrogen atom, an alkyl group, or a —CH 2 —O—Ra 2 group.
- Ra 2 represents a hydrogen atom, an alkyl group, or an acyl group.
- Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.
- the cyclic structure possessed by R 5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group.
- Examples of the monocyclic hydrocarbon group include cycloalkenyl having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and cycloalkyl groups having 3 to 12 carbon atoms and cyclohexenyl group.
- a preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferred examples include a cyclopentyl group and a cyclohexyl group.
- the polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group.
- the bridged cyclic hydrocarbon ring for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.)
- Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, tricyclo [4.3.1.1 2,5 ] undecane ring, tetracyclo [ 4.4.0.1 2,5 .
- the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene.
- a condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring is also included.
- Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group. These alicyclic hydrocarbon groups may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. It is done.
- Preferred halogen atoms include bromine, chlorine and fluorine atoms
- preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups.
- the alkyl group described above may further have a substituent, and examples of the substituent that may further include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. The group can be mentioned.
- Examples of the group in which the hydrogen atom is substituted include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group.
- Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms
- preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups.
- acyl groups include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl and pivaloyl groups, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.
- the resin (A) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. The content of is preferably 1 to 40 mol%, more preferably 2 to 20 mol%, based on all repeating units in the resin (A).
- repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability include the repeating unit disclosed in paragraph 0354 of US Published Patent Application No. 2012/0135348. However, the present invention is not limited to these.
- the resin (A) used in the composition of the present invention has a resolving power that is a general necessary characteristic of a resist, in addition to the above repeating structural unit, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and the like. It can have various repeating structural units for the purpose of adjusting heat resistance, sensitivity and the like. Examples of such a repeating structural unit include, but are not limited to, repeating structural units corresponding to the following monomers.
- a monomer for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.
- any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.
- the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general required performance of the resist. It is appropriately set to adjust the resolving power, heat resistance, sensitivity and the like.
- the resin (A) in the present invention can be synthesized according to a conventional method (for example, radical polymerization).
- a conventional method for example, radical polymerization
- a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours.
- the dropping polymerization method is added, and the dropping polymerization method is particularly preferable.
- reaction solvent examples include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt
- the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
- Polymerization is initiated using a commercially available radical initiator (azo initiator, peroxide, etc.) as the polymerization initiator.
- a commercially available radical initiator azo initiator, peroxide, etc.
- an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable.
- Preferable initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like.
- an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery.
- the concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass.
- the reaction temperature is usually 10 to 150 ° C., preferably 30 to 120 ° C., more preferably 60 to 100 ° C.
- the weight average molecular weight of the resin (A) of the present invention is preferably 18,000 or more, and more preferably 20,000 or more.
- the weight average molecular weight of the resin (A) is usually 200,000 or less, and preferably 100,000 or less.
- the glass transition temperature of the resin (A) can be more easily set to 155 ° C. or more, and a resist pattern (space width is 10 ⁇ m, pitch width is The softening point of the isolated space pattern (100 ⁇ m and resist film part thickness 7.5 ⁇ m) is more easily set to 130 ° C. or more.
- the degree of dispersion is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.1 to 2.0. Those in the range are used.
- Resin (A) may be used alone or in combination.
- the glass transition temperature of the resin (A) is 155 ° C. or higher, preferably 160 ° C. or higher, more preferably 165 ° C. or higher, and still more preferably 170 ° C. or higher. Moreover, it is preferable that the glass transition temperature of resin (A) is 200 degrees C or less, It is more preferable that it is 195 degrees C or less, It is still more preferable that it is 190 degrees C or less.
- the method for measuring the glass transition temperature is as described above.
- the resin (A) is not particularly limited as long as the glass transition temperature is 155 ° C. or higher, and as described above, such a resin has a repeating unit (particularly a phenolic hydroxyl group) that the resin (A) may have.
- the content of the repeating unit), the weight average molecular weight, and the like are within the above-described preferable ranges.
- the content of the resin (A) in the entire composition is preferably 50 to 90% by mass, more preferably 50 to 80% by mass, based on the total solid content of the composition.
- the softening point of the resist pattern isolated space pattern having a space width of 10 ⁇ m, a pitch width of 100 ⁇ m, and a resist film thickness of 7.5 ⁇ m
- it can be set to 130 ° C. or higher.
- composition of this invention contains the compound (B) whose glass transition temperature is 150 degrees C or less.
- a preferred embodiment of the compound (B) includes a resin.
- the resin as the compound (B) (hereinafter, simply referred to as “resin (B)”) include resins having the repeating units mentioned in the resin (A).
- the resin (B) is not particularly limited as long as the glass transition temperature is 150 ° C. or lower, but the content of the repeating unit having a phenolic hydroxyl group is 53 mol% or less with respect to all the repeating units of the resin (B). It is preferable that it is 50 mol% or less. Thereby, the glass transition temperature of resin (B) can be 150 degrees C or less suitably.
- the content thereof is preferably 10 mol% or more, more preferably 20 mol% or more, based on all repeating units of the resin (B). preferable.
- the resin (B) preferably has a repeating unit derived from hydroxystyrene as the repeating unit having a phenolic hydroxyl group.
- the weight average molecular weight of the resin (B) is preferably 1,000 to 18,000, more preferably 3,000 to 17,000, and preferably 5,000 to 16,000. Further preferred.
- the glass transition temperature of the resin (B) can be more reliably set to 150 ° C. or less, and a resist pattern (an isolated space pattern having a space width of 10 ⁇ m, a pitch width of 100 ⁇ m, and a resist film portion thickness of 7.5 ⁇ m).
- a resist pattern an isolated space pattern having a space width of 10 ⁇ m, a pitch width of 100 ⁇ m, and a resist film portion thickness of 7.5 ⁇ m).
- the preferred range of the degree of dispersion (molecular weight distribution) of the resin as the compound (B) of the present invention is the same as that described for the resin (A).
- a polyether compound is a compound having two or more ether bonds. According to the polyether-based compound, the requirement that the glass transition temperature is 150 ° C. or less can be suitably achieved.
- the polyether compound include compounds having a partial structure represented by the following general formula (1).
- R 11 represents an alkylene group which may have a substituent.
- the number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 15, more preferably 2 to 8, and still more preferably 2.
- the substituent is not particularly limited, but is preferably an alkyl group (preferably having 1 to 10 carbon atoms).
- n represents an integer of 2 or more. Among these, an integer of 2 to 20 is preferable.
- a plurality of R 11 may be the same or different.
- the average value of n is preferably 2 to 25, more preferably 2 to 10, and still more preferably 4 to 8.
- * represents a bond.
- the compound having a partial structure represented by the general formula (1) is preferably a compound represented by the following general formula (1-1) or the following general formula (1-2).
- R 11 in the general formula (1-1) specific examples and preferred embodiments are the same as R 11 in general formula (1).
- R 12 and R 13 each independently represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1-15.
- m represents an integer of 2 or more. m is preferably an integer of 2 to 20, and among them, it is more preferably 10 or less because DOF (Depth of focus) becomes larger.
- a plurality of R 11 may be the same or different.
- the average value of m is preferably 25 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 8 or less, because the DOF becomes larger.
- the lower limit is preferably 2 or more, and more preferably 4 or more. More specifically, the average value of m is preferably 2 to 25, more preferably 2 to 15, further preferably 2 to 8, and particularly preferably 4 to 8. Most preferably, it is 4-6.
- R 11 in the general formula (1-2) specific examples and preferred embodiments are the same as R 11 in general formula (1).
- the definition and preferred embodiment of m in the general formula (1-2) are the same as m in the general formula (1-1) described above.
- Examples of the compound represented by the general formula (1-2) include crown ether.
- the compound (B) is preferably a polyether compound having a group represented by the following general formula (a).
- the actinic ray-sensitive or radiation-sensitive film is softened.
- the solvent in the actinic ray-sensitive or radiation-sensitive resin composition is likely to volatilize during the formation of the actinic ray-sensitive or radiation-sensitive film, and the formed actinic ray-sensitive or radiation-sensitive film is formed.
- the amount of solvent remaining therein is further reduced.
- Such a resist pattern formed from an actinic ray-sensitive or radiation-sensitive film with a reduced amount of residual solvent can be removed from the resist pattern even if it is accommodated in a vacuum chamber during measurement by a length measuring SEM. Is difficult to volatilize. Therefore, it is presumed that the stress change accompanying the evaporation of the solvent from the resist pattern is less likely to occur in the resist pattern, and cracks are less likely to occur in the resist pattern.
- A represents an alkylene group which may have a substituent.
- a plurality of A may be the same as or different from each other.
- n ′ represents an integer of 2 or more. * Represents a bond.
- the polyether compound having a group represented by the general formula (a) may have one group represented by the general formula (a) or two or more groups.
- the polyether compound having a group represented by the general formula (a) is preferably a polyether compound represented by the following general formula (A).
- a and n ' are synonymous with the thing in the said general formula (a).
- R represents a hydrogen atom or a hydroxyl group.
- R is preferably a hydroxyl group.
- the boiling point of the polyether compound having the group represented by the general formula (a) is preferably 220 ° C. or higher, more preferably 300 ° C. or higher, and further preferably 350 ° C. or higher.
- the boiling point of the polyether compound having a group represented by the general formula (a) is typically 550 ° C. or lower.
- the ClogP value of the polyether compound having a group represented by the general formula (a) is preferably ⁇ 2.5 to ⁇ 0.3, more preferably ⁇ 2.5 to ⁇ 0.5. Is more preferable, and -2.5 to -1.0 is still more preferable.
- the ClogP value is a ClogP value of a monomer (compound having an unsaturated double bond group) corresponding to a repeating unit, which is described in Chem DrawUltra ver. It is a calculated value by 12.0.2.1076 (Cambridge Corporation).
- the polyether compound having a group represented by the general formula (a) is a compound represented by the general formula (A), and R in the general formula (A) is It is a compound having a hydroxyl group and a boiling point of 350 ° C. or higher.
- the molecular weight of the polyether compound is not particularly limited, but is preferably 100 to 5000, more preferably 150 to 3000, and further preferably 200 to 2000.
- the polyether compound preferably does not contain a basic moiety (for example, an amino group or a proton acceptor functional group described later).
- the pKa of the conjugate acid of the polyether compound is preferably 0 or less, more preferably -1 or less, further preferably -2 or less, and particularly preferably -3 or less.
- the lower limit value of pKa is, for example, ⁇ 15 or more.
- the pKa value is expressed as a value calculated by ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).
- the polyether compound does not have a functional group having a nitrogen atom having a lone electron pair with little contribution of ⁇ conjugation.
- the nitrogen atom having a lone electron pair with little contribution of ⁇ conjugation include a nitrogen atom having a partial structure represented by the following general formula.
- Examples of structures (compounds) having a functional group having a nitrogen atom with a lone electron pair with little contribution of ⁇ conjugation include a chain amide, a cyclic amide, an aromatic amine, a chain aliphatic amine, and a cyclic fat. Group amines can be mentioned.
- polyether-based compound examples include polyether-based compound, but the present invention is not limited to these.
- Compound (B) may be used alone or in combination.
- the glass transition temperature of compound (B) is 150 ° C. or lower.
- the glass transition temperature thereof is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 130 ° C. or higher.
- the compound (B) is not a resin (polymer)
- its glass transition temperature is preferably ⁇ 20 ° C. or higher, and preferably ⁇ 15 ° C. or higher.
- the glass transition temperature of the compound (B) is usually 0 ° C. or lower.
- the method for measuring the glass transition temperature is as described above.
- the compound (B) is not particularly limited as long as the glass transition temperature is 150 ° C. or lower.
- the repeating unit (B) that the resin (B) may have ( In particular, by selecting the content of the repeating unit having a phenolic hydroxyl group), the weight average molecular weight, and the like within the above-mentioned preferred ranges, and when the compound (B) is not a resin, the type of the compound is appropriately selected. (For example, by selecting a polyether compound as described above).
- the content of the compound (B) is preferably 1 to 50% by mass, more preferably 5 to 50% by mass, and more preferably 15 to 50% by mass with respect to the total solid content of the composition. More preferably, it is 50 mass%.
- the softening point of the resist pattern isolated space pattern having a space width of 10 ⁇ m, a pitch width of 100 ⁇ m, and a resist film portion thickness of 7.5 ⁇ m
- it can be set to 170 ° C. or lower.
- the difference between the glass transition temperature of the resin (A) and the glass transition temperature of the compound (B) is within a range of 50 to 60 ° C. Preferably, it is in the range of 40 to 50 ° C, more preferably in the range of 30 to 40 ° C.
- the present invention comprises an actinic ray-sensitive or sensitive material containing a resin (A) having a glass transition temperature of 155 ° C. or higher, a compound (B) having a glass transition temperature of 150 ° C. or lower, and a solvent (C).
- It is a radiation sensitive resin composition, Comprising: Solid content in an actinic ray sensitive or radiation sensitive resin composition is 20 mass% or more, and it is formed with the said actinic ray sensitive or radiation sensitive resin composition.
- the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition having a softening point of a resist pattern of 130 ° C. or more and 170 ° C.
- the present invention preferably uses the actinic ray-sensitive or radiation-sensitive resin composition.
- Actinic ray-sensitive or radiation-sensitive comprising a resin (A) having a glass transition temperature of 155 ° C. or higher, a compound (B) having a glass transition temperature of 150 ° C. or lower, and a solvent (C).
- resin composition the solid content in the actinic ray-sensitive or radiation-sensitive resin composition is 20% by mass or more, and the content of the resin (A) is all of the actinic ray-sensitive or radiation-sensitive resin composition.
- the activity is 50 to 90% by mass with respect to the solid content, and the content of the compound (B) is 1 to 50% by mass with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. It also relates to a light-sensitive or radiation-sensitive resin composition.
- the composition of the present invention preferably contains an acid generator.
- the acid generator is not particularly limited as long as it is a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator”).
- the acid generator is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation.
- the acid generator may be in the form of a low molecular compound or may be in a form incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
- the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
- the acid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above or in a resin different from the resin (A). Specific examples of the case where the acid generator is in a form incorporated in a part of the polymer include, for example, paragraphs ⁇ 0191> to ⁇ 0209> of JP2013-54196A.
- the acid generator photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, irradiation of actinic ray or radiation used for micro resist, etc.
- the known compounds that generate an acid and mixtures thereof can be appropriately selected and used.
- examples of the acid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.
- an acid generator having a pKa of the generated acid of ⁇ 2 or more is preferable.
- pKa is preferably ⁇ 1.5 or more, more preferably ⁇ 1 or more, in that the variation in thickness between the formed patterns is smaller.
- the upper limit of pKa is not particularly limited, but is preferably 1 or less.
- pKa (acid strength) is one of the indexes for quantitatively expressing the strength of acid, and is synonymous with an acidity constant. Considering a dissociation reaction in which hydrogen ions are released from an acid, its equilibrium constant Ka is expressed by its negative common logarithm pKa. A smaller pKa indicates a stronger acid. In this invention, it calculates by the calculation using the analysis software by ACD (Advanced Chemistry Development), ACD / pKa DB V8.0.
- Preferred compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).
- R 201 , R 202 and R 203 each independently represents an organic group.
- the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
- Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
- Examples of the group formed by combining two members out of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
- Z ⁇ represents a non-nucleophilic anion.
- non-nucleophilic anion as Z ⁇ examples include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.
- a non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. Thereby, the temporal stability of the composition is improved.
- the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.
- Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.
- the aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms.
- Examples of the aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion include preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group. it can.
- the alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent.
- examples of other non-nucleophilic anions include fluorinated phosphorus (for example, PF 6 ⁇ ), fluorinated boron (for example, BF 4 ⁇ ), fluorinated antimony and the like (for example, SbF 6 ⁇ ).
- non-nucleophilic anion of Z ⁇ examples include an aliphatic sulfonate anion in which at least ⁇ position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, an alkyl group Is preferably a bis (alkylsulfonyl) imide anion substituted with a fluorine atom, or a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom.
- the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion having 4 to 8 carbon atoms, a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, Pentafluorobenzenesulfonate anion, 3,5-bis (trifluoromethyl) benzenesulfonate anion.
- the non-nucleophilic anion of Z ⁇ is preferably represented by the general formula (2).
- the volume of the generated acid is large and acid diffusion is suppressed.
- Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- R 7 and R 8 are each independently a hydrogen atom, a fluorine atom, an alkyl group, or represents at least one alkyl group substituted with a fluorine atom, R 7 and R 8 when there are a plurality of respectively identical But it can be different.
- L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
- A represents an organic group containing a cyclic structure.
- x represents an integer of 1 to 20, and y represents an integer of 0 to 10.
- z represents an integer of 0 to 10.
- Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom as described above, and the alkyl group in the alkyl group substituted with a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms, An alkyl group having 1 to 4 carbon atoms is more preferable.
- the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
- Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
- fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , C 7 F 15 , C 8 F 17 , CH 2 CF 3 , CH 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9, CH 2 CH 2 C 4 F 9 is mentioned, among which fluorine atom and CF 3 are preferable.
- both Xf are fluorine atoms.
- R 7 and R 8 represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and the alkyl group preferably has 1 to 4 carbon atoms. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms.
- Specific examples of the alkyl group substituted with at least one fluorine atom of R 7 and R 8 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , and C 6 F 13.
- C 7 F 15 , C 8 F 17 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 , and CH 2 CH 2 C 4 F 9 can be mentioned, among which CF 3 is preferable.
- L represents a divalent linking group, and represents —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, —N (Ri) — (wherein Ri represents a hydrogen atom or alkyl), an alkylene group (preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group or an ethyl group, most preferably a methyl group).
- a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), or a divalent linking group in which a plurality of these are combined.
- the alkylene group in —CON (Ri) -alkylene group—, —N (Ri) CO-alkylene group—, —COO-alkylene group—, —OCO-alkylene group— is preferably an alkylene group having 1 to 20 carbon atoms. An alkylene group having 1 to 10 carbon atoms is more preferable. When there are a plurality of L, they may be the same or different. Specific examples and preferred examples of the alkyl group for Ri include those similar to the specific examples and preferred examples described above as R 1 to R 4 in the general formula (1).
- the organic group containing the cyclic structure of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having an aromatic attribute but also aromaticity).
- a tetrahydropyran ring, a lactone ring structure, and a sultone ring structure are examples of a tetrahydropyran ring, a lactone ring structure, and a sultone ring structure.
- the alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a norbornene-yl group, or a tricyclodecanyl group (for example, tricyclo [ 5.2.1.0 (2,6) ] decanyl group), tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group and the like are preferable, and an adamantyl group is particularly preferable.
- a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a norbornene-yl group, or a tricyclodecanyl group
- nitrogen atom-containing alicyclic groups such as piperidine group, decahydroquinoline group, decahydroisoquinoline group.
- an alicyclic group having a bulky structure of 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, a decahydroquinoline group, and a decahydroisoquinoline group.
- PEB post-exposure heating
- PEB post-exposure heating
- an adamantyl group and a decahydroisoquinoline group are particularly preferable.
- the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
- naphthalene having low absorbance is preferred from the viewpoint of light absorbance at 193 nm.
- the heterocyclic group include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
- a furan ring, a thiophene ring, and a pyridine ring are preferable.
- Other preferred heterocyclic groups include the structures shown below (wherein X represents a methylene group or an oxygen atom, and R represents a monovalent organic group).
- the cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably 1 to 12 carbon atoms), an aryl group (Preferably having 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like.
- the carbon constituting the organic group containing a cyclic structure may be a carbonyl carbon.
- X is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1.
- y is preferably 0 to 4, more preferably 0 or 1, and still more preferably 1.
- z is preferably 0 to 8, more preferably 0 to 4, and still more preferably 1.
- Z - is a non-nucleophilic anion, and may be a di-imide anion.
- the disulfonylimidoanion is preferably a bis (alkylsulfonyl) imide anion.
- the alkyl group in the bis (alkylsulfonyl) imide anion is preferably an alkyl group having 1 to 5 carbon atoms.
- Two alkyl groups in the bis (alkylsulfonyl) imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms) and form a ring together with the imide group and the two sulfonyl groups.
- the ring structure that may be formed by the bis (alkylsulfonyl) imide anion is preferably a 5- to 7-membered ring, and more preferably a 6-membered ring.
- These alkyl groups and alkylene groups formed by connecting two alkyl groups to each other can have a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryl Examples thereof include an oxysulfonyl group and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
- the non-nucleophilic anion of Z ⁇ has a fluorine content represented by (total mass of all fluorine atoms contained in the anion) / (total mass of all atoms contained in the anion) of 0.25 or less. Is preferably 0.20 or less, and more preferably 0.15 or less.
- Examples of the organic group represented by R 201 , R 202 and R 203 include the corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later. Can be mentioned.
- the compound which has two or more structures represented by general formula (ZI) may be sufficient.
- at least one of R 201 to R 203 of the compound represented by the general formula (ZI) is a single bond or at least one of R 201 to R 203 of the other compound represented by the general formula (ZI). It may be a compound having a structure bonded through a linking group.
- More preferred (ZI) components include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.
- the compound (ZI-1) is an arylsulfonium compound in which at least one of R 201 to R 203 in the general formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.
- the arylsulfonium compound all of R 201 to R 203 may be an aryl group, or a part of R 201 to R 203 may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.
- arylsulfonium compound examples include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
- the aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and 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. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue.
- the two or more aryl groups may be the same or different.
- the alkyl group or cycloalkyl group optionally possessed by the arylsulfonium compound is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
- the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 are an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms).
- An alkoxy group for example, having 1 to 15 carbon atoms
- a halogen atom for example, a hydroxyl group, and a phenylthio group may be substituted.
- Compound (ZI-2) is a compound in which R 201 to R 203 in formula (ZI) each independently represents an organic group having no aromatic ring.
- the aromatic ring includes an aromatic ring containing a hetero atom.
- the organic group containing 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, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group.
- a carbonylmethyl group particularly preferably a linear or branched 2-oxoalkyl group.
- the alkyl group and cycloalkyl group represented by R 201 to R 203 are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group), a carbon Examples thereof include cycloalkyl groups having a number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
- R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
- the compound (ZI-3) is a compound represented by the following general formula (ZI-3), which is a compound having a phenacylsulfonium salt structure.
- R 1c to R 5c are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents a nitro group, an alkylthio group or an arylthio group.
- R 6c and R 7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
- R x and R y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
- 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 form a ring structure.
- this ring structure may contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
- the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by combining two or more of these rings.
- Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, more preferably 5- or 6-membered rings.
- Examples of the group formed by combining any two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include a butylene group and a pentylene group.
- 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, and examples of the alkylene group include a methylene group and an ethylene group.
- Zc ⁇ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ⁇ in formula (ZI).
- alkoxy group in the alkoxycarbonyl group as R 1c ⁇ R 5c are the same as specific examples of the alkoxy group as the R 1c ⁇ R 5c.
- Specific examples of the alkyl group in the alkylcarbonyloxy group and alkylthio group as R 1c ⁇ R 5c are the same as specific examples of the alkyl group of the R 1c ⁇ R 5c.
- Specific examples of the cycloalkyl group in the cycloalkyl carbonyl group as R 1c ⁇ R 5c are the same as specific examples of the cycloalkyl group of the R 1c ⁇ R 5c.
- Specific examples of the aryl group in the aryloxy group and arylthio group as R 1c ⁇ R 5c are the same as specific examples of the aryl group of the R 1c ⁇ R 5c.
- Examples of the cation in the compound (ZI-2) or (ZI-3) in the present invention include cations described in paragraph ⁇ 0036> and thereafter of US Patent Application Publication No. 2012/0076996.
- the compound (ZI-4) is represented by the following general formula (ZI-4).
- R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
- R 14 is independently a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group, when a plurality of R 14 are present.
- R 15 each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent.
- Two R 15 may be bonded to each other to form a ring.
- the ring skeleton may contain a hetero atom such as an oxygen atom or a nitrogen atom.
- it is preferred that two R 15 are alkylene groups and are bonded to each other to form a ring structure.
- l represents an integer of 0-2.
- r represents an integer of 0 to 8.
- Z ⁇ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ⁇ in formula (ZI).
- the alkyl group of R 13 , R 14 and R 15 is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -Butyl group, t-butyl group and the like are preferable.
- Examples of the cation of the compound represented by the general formula (ZI-4) in the present invention include paragraphs ⁇ 0121>, ⁇ 0123>, ⁇ 0124> of JP 2010-256842 A, and JP 2011-76056 A. The cations described in paragraphs ⁇ 0127>, ⁇ 0129>, ⁇ 0130>, etc.
- R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
- the aryl group of R 204 to R 207 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- the aryl group of R 204 to R 207 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
- Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
- the alkyl group and cycloalkyl group in R 204 to R 207 are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups having a number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
- the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent.
- substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 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 (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups, and the like.
- Z ⁇ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ⁇ in formula (ZI).
- Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).
- Ar 3 and Ar 4 each independently represents an aryl group.
- R 208 , R 209 and R 210 each independently represents an alkyl group, a cycloalkyl group or an aryl group.
- A represents an alkylene group, an alkenylene group or an arylene group.
- Specific examples of the aryl group of Ar 3 , Ar 4 , R 208 , R 209 and R 210 are the same as the specific examples of the aryl group as R 201 , R 202 and R 203 in the above compound (ZI-1). Can be mentioned.
- Specific examples of the alkyl group and cycloalkyl group of R 208 , R 209 and R 210 are specific examples of the alkyl group and cycloalkyl group as R 201 , R 202 and R 203 in the compound (ZI-2), respectively. The same thing can be mentioned.
- the alkylene group of A is alkylene having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 to 2 carbon atoms.
- 12 alkenylene groups for example, ethenylene group, propenylene group, butenylene group, etc.
- the arylene groups for A are arylene groups having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) Can be mentioned.
- an acid generator a compound that generates an acid represented by the following general formula (III) or (IV) by irradiation with actinic rays or radiation can be mentioned.
- Rb 3 to Rb 5 each independently represents an alkyl group, a cycloalkyl group or an aryl group.
- Rb 3 and Rb 4 may combine to form a ring structure.
- Rb 3 to Rb 5 are more preferably substituted at the 1-position with an alkyl group substituted with a fluorine atom or a fluoroalkyl group, a fluorine atom or a fluoroalkyl group.
- An aryl group preferably a phenyl group.
- Rb 3 to Rb 5 have 5 or more carbon atoms, it is preferable that at least one carbon atom does not have all hydrogen atoms substituted with fluorine atoms, and the number of hydrogen atoms is more than fluorine atoms. preferable. By not having a perfluoroalkyl group having 5 or more carbon atoms, ecotoxicity is reduced.
- Rb 3 to Rb 5 are preferably a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a perfluoroalkyl group having 1 to 3 carbon atoms. Examples of the group formed by combining Rb 3 and Rb 4 include an alkylene group and an arylene group.
- the group formed by combining Rb 3 and Rb 4 is preferably a perfluoroalkylene group having 2 to 4 carbon atoms, and more preferably a perfluoropropylene group.
- Rc 6 represents a perfluoroalkylene group, and more preferably a perfluoroalkylene group having 2 to 4 carbon atoms.
- Ax represents a single bond or a divalent linking group (preferably —O—, —CO 2 —, —S—, —SO 3 —, —SO 2 N (Rd 1 ) —).
- Rd 1 represents a hydrogen atom or an alkyl group, and may combine with Rc 7 to form a ring structure.
- Rc 7 represents a hydrogen atom, a fluorine atom, an alkyl group, a cycloalkyl group or an aryl group. The alkyl group, cycloalkyl group and aryl group of Rc 7 preferably have no fluorine atom as a substituent.
- Examples of the compound that generates an acid represented by the general formula (III) or (IV) upon irradiation with actinic rays or radiation include, for example, diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, imidosulfonate, oxime sulfonate, o Mention may be made of nitrobenzyl sulfonate.
- a group that generates an acid represented by the general formula (III) or (IV) by irradiation with actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of a polymer for example, US Pat. , 849,137, German Patent No. 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63- No. 163452, JP-A-62-153853, JP-A-63-146029, and the like can be used.
- R 201 , R 202 and R 203 each independently represents an organic group.
- Xd ⁇ represents an anion of an acid represented by the general formula (III) or (IV).
- R 201 , R 202 and R 203 in the general formula (ZIa) correspond to the corresponding compounds (ZI-1a), (ZI-2a) and (ZI-3a) described later.
- the group can be mentioned.
- Two members out of R 201 to R 203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
- Examples of the group formed by combining two members out of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
- the compound which has two or more structures represented by general formula (ZIa) may be sufficient.
- the general formula R 201 ⁇ R 203 of a compound represented by (ZIa) at least one is, the structures attached to at least one of the general formula (ZIa) in another compound represented by R 201 ⁇ R 203 It may be a compound.
- More preferred (ZIa) components include compounds (ZI-1a), (ZI-2a), and (ZI-3a) described below.
- Compound (ZI-1a) is an arylsulfonium compound in which at least one of R 201 to R 203 in formula (ZIa) is an aryl group, that is, a compound having arylsulfonium as a cation.
- all of R 201 to R 203 may be an aryl group, or a part of R 201 to R 203 may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.
- arylsulfonium compound examples include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.
- the aryl group of the arylsulfonium compound is preferably an aryl group such as a phenyl group or a naphthyl group, or a heteroaryl group such as an indole residue or a pyrrole residue, more preferably a phenyl group or an indole residue.
- the two or more aryl groups may be the same or different.
- the alkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, sec- Examples thereof include a butyl group and a t-butyl group.
- the cycloalkyl group optionally contained in the arylsulfonium compound is preferably a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.
- the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 are an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms).
- An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group may be substituted.
- Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, and most preferably An alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms.
- the substituent may be substituted with any one of the three R 201 to R 203 or may be substituted with all three.
- R 201 to R 203 are an aryl group
- the substituent is preferably substituted at the p-position of the aryl group.
- the arylsulfonium cation is preferably a triphenylsulfonium cation which may be substituted, a naphthyltetrahydrothiophenium cation which may be substituted, or a phenyltetrahydrothiophenium cation which may be substituted.
- the compound (ZI-2a) is a compound in the case where R 201 to R 203 in the general formula (ZIa) each independently represents an organic group not containing an aromatic ring.
- the aromatic ring includes an aromatic ring having a hetero atom.
- the organic group containing 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, more preferably a linear, branched, cyclic 2-oxoalkyl group, or an alkoxycarbonylmethyl group, particularly preferably Is a linear, branched 2-oxoalkyl group.
- the alkyl group as R 201 to R 203 may be linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group). Butyl group, pentyl group).
- the alkyl group as R 201 to R 203 is more preferably a linear, branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.
- Preferred examples of the cycloalkyl group as R 201 to R 203 include a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).
- the cycloalkyl group as R 201 to R 203 is more preferably a cyclic 2-oxoalkyl group.
- the linear, branched, or cyclic 2-oxoalkyl group in R 201 to R 203 is preferably a group having> C ⁇ O at the 2-position of the above alkyl group or cycloalkyl group.
- the alkoxy group in the alkoxycarbonylmethyl group as R 201 to R 203 is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
- R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.
- the compound (ZI-3a) is a compound represented by the following general formula (ZI-3a), and is a compound having a phenacylsulfonium salt structure.
- R 1c to R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
- R 6c and R 7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
- Rx and Ry each independently represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group. Any two or more of R 1c to R 5c , and R x and R y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom, a sulfur atom, an ester bond, and an amide bond.
- Examples of the group formed by combining any two or more of R 1c to R 5c and R x and R y include a butylene group and a pentylene group.
- Xd ⁇ represents an anion of an acid represented by the general formula (III) or (IV), and is the same as Xd ⁇ in the general formula (ZIa).
- the alkyl group as R 1c to R 7c may be linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms. Examples thereof include a group (for example, methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group).
- Examples of the cycloalkyl group as R 1c to R 7c include a cycloalkyl group having 3 to 20 carbon atoms, preferably a cycloalkyl group having 3 to 8 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group). Can do.
- the alkoxy group as R 1c to R 5c may be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms.
- any one of R 1c to R 5c is a linear, branched alkyl group, cycloalkyl group, or a linear, branched, or cyclic alkoxy group, and more preferably the sum of the carbon number of R 1c to R 5c is 2 ⁇ 15.
- solvent solubility improves more and generation
- Examples of the alkyl group as R x and R y include the same alkyl groups as R 1c to R 7c .
- the alkyl group as R x and R y is more preferably a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.
- Examples of the cycloalkyl group as R x and R y include the same cycloalkyl groups as R 1c to R 7c .
- the cycloalkyl group as R x and R y is more preferably a cyclic 2-oxoalkyl group.
- Examples of the linear, branched and cyclic 2-oxoalkyl group include a group having> C ⁇ O at the 2-position of the alkyl group or cycloalkyl group as R 1c to R 7c .
- Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as R 1c to R 5c .
- R x, R y is preferably a number of 4 or more alkyl groups atoms, more preferably 6 or more, still more preferably 8 or more alkyl groups.
- R 204 to R 205 each independently represents an aryl group, an alkyl group or a cycloalkyl group.
- the aryl group for R 204 to R 205 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
- the alkyl group as R 204 to R 205 may be linear or branched, and is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group). Butyl group, pentyl group).
- Preferred examples of the cycloalkyl group as R 204 to R 205 include cycloalkyl groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group).
- substituent that R 204 to R 207 may have include, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 6 carbon atoms). 15), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like.
- an anion of the acid represented by the general formula (III) or (IV) is used.
- a sulfonium salt compound or an iodonium salt compound more preferably a compound represented by the general formula (ZIa), and particularly preferably a compound represented by (ZI-1a) to (ZI-3a).
- acid generators particularly preferable examples include compounds exemplified in US2012 / 0207978A1 ⁇ 0143>.
- the acid generator can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707.
- An acid generator can be used individually by 1 type or in combination of 2 or more types.
- the content of the acid generator in the composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 25%, based on the total solid content of the composition. % By mass, more preferably 0.5 to 20% by mass, particularly preferably 0.5 to 15% by mass.
- the acid generator is represented by the above general formula (ZI-3) or (ZI-4) (when there are a plurality of types)
- the content is the total solid content of the composition.
- 0.1 to 35% by mass is preferable, 0.5 to 30% by mass is more preferable, and 0.5 to 25% by mass is particularly preferable. Specific examples of the acid generator are shown below, but the present invention is not limited thereto.
- the composition of the present invention may contain a hydrophobic resin.
- the hydrophobic resin is preferably different from the resin (A).
- the hydrophobic resin is preferably designed to be unevenly distributed at the interface as described above.
- unlike the surfactant it is not always necessary to have a hydrophilic group in the molecule, and the polar / nonpolar substance is mixed uniformly. You don't have to contribute to As an effect of adding the hydrophobic resin, outgas suppression can be exemplified.
- Hydrophobic resin is a "fluorine atom", “silicon atom”, and It preferably has one or more of “CH 3 partial structures contained in the side chain portion of the resin”, and more preferably has two or more.
- the hydrophobic resin contains a fluorine atom and / or a silicon atom
- the fluorine atom and / or silicon atom in the hydrophobic resin may be contained in the main chain of the resin or in the side chain. It may be.
- the hydrophobic resin when it contains a fluorine atom, it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
- the alkyl group having a fluorine atom preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms
- the cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
- the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
- alkyl group having a fluorine atom examples include groups represented by the following general formulas (F2) to (F4).
- the invention is not limited to this.
- R 57 to R 68 each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched).
- R 57 to R 61 , at least one of R 62 to R 64 , and at least one of R 65 to R 68 are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms). All of R 57 to R 61 and R 65 to R 67 are preferably fluorine atoms.
- R 62 , R 63 and R 68 are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R 62 and R 63 may be connected to each other to form a ring.
- Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
- Specific examples of the group represented by the general formula (F3) include those exemplified in US2012 / 0251948A1 [0500].
- Specific examples of the group represented by the general formula (F4) include, for example, —C (CF 3 ) 2 OH, —C (C 2 F 5 ) 2 OH, —C (CF 3 ) (CH 3 ) OH, —CH (CF 3 ) OH and the like can be mentioned, and —C (CF 3 ) 2 OH is preferable.
- the partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple
- the hydrophobic resin may contain a silicon atom.
- the partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
- alkylsilyl structure or the cyclic siloxane structure include partial structures described in paragraphs ⁇ 0304> to ⁇ 0307> of JP2013-178370A.
- Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in US2012 / 0251948A1 [0519].
- the hydrophobic resin preferably includes a CH 3 partial structure in the side chain portion.
- CH 3 partial structure contained in the side chain portion in the hydrophobic resin is intended to encompass CH 3 partial structure an ethyl group, and a propyl group having.
- methyl groups directly bonded to the main chain of the hydrophobic resin (for example, ⁇ -methyl groups of repeating units having a methacrylic acid structure) contribute to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. Since it is small, it is not included in the CH 3 partial structure.
- the hydrophobic resin includes a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M)
- R 11 to R 14 are CH 3 “as is”
- the CH 3 is not included in the CH 3 partial structure of the side chain moiety in the present invention.
- CH 3 partial structure exists through some atoms from C-C backbone, and those falling under CH 3 partial structures in the present invention.
- R 11 is an ethyl group (CH 2 CH 3 )
- R 11 to R 14 each independently represents a side chain portion.
- R 11 to R 14 in the side chain portion include a hydrogen atom and a monovalent organic group.
- the monovalent organic group for R 11 to R 14 include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl.
- Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.
- the hydrophobic resin is preferably a resin having a repeating unit having a CH 3 partial structure in the side chain portion.
- the repeating unit represented by the following general formula (II) and the following general unit It is more preferable to have at least one repeating unit (x) among the repeating units represented by the formula (III).
- X b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom
- R 2 has one or more CH 3 partial structure represents a stable organic radical to acid.
- the organic group that is stable to acid is more preferably an organic group that does not have the “acid-decomposable group” described in the resin (A).
- the alkyl group of Xb1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
- X b1 is preferably a hydrogen atom or a methyl group.
- R 2 include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH 3 partial structures.
- R 2 is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH 3 partial structures.
- the acid-stable organic group having one or more CH 3 partial structures as R 2 preferably has 2 or more and 10 or less CH 3 partial structures, and more preferably 2 or more and 8 or less.
- Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.
- the repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.
- the repeating unit represented by formula (III) will be described in detail.
- X b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom
- R 3 represents an acid-stable organic group having one or more CH 3 partial structures
- n represents an integer of 1 to 5.
- the alkyl group of Xb2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.
- X b2 is preferably a hydrogen atom. Since R 3 is an organic group that is stable against acid, more specifically, R 3 is preferably an organic group that does not have the “acid-decomposable group” described in the resin (A).
- R 3 includes an alkyl group having one or more CH 3 partial structures.
- the acid-stable organic group having one or more CH 3 partial structures as R 3 preferably has 1 or more and 10 or less CH 3 partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.
- n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.
- the repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit. Specifically, “a group that decomposes by the action of an acid to generate a polar group” It is preferable that it is a repeating unit which does not have ".”
- the repeating unit represented by the general formula (II) and the general formula (S) is preferably 90 mol% or more, more preferably 95 mol% or more, based on all repeating units of the hydrophobic resin. It is more preferable. Content is 100 mol% or less normally with respect to all the repeating units of hydrophobic resin.
- the hydrophobic resin contains at least one repeating unit (x) among the repeating units represented by the general formula (II) and the repeating unit represented by the general formula (III) as all repeating units of the hydrophobic resin.
- the surface free energy of hydrophobic resin increases by containing 90 mol% or more. As a result, the hydrophobic resin is less likely to be unevenly distributed on the surface of the resist film, so that the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved.
- the hydrophobic resin includes the following groups (x) to (z) regardless of whether (i) it contains a fluorine atom and / or a silicon atom, or (ii) contains a CH 3 partial structure in the side chain portion. It may have at least one group selected from (X) an acid group, (Y) a group having a lactone structure, an acid anhydride group, or an acid imide group, (Z) a group decomposable by the action of an acid
- Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
- Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and
- the repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable.
- the repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
- the content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the hydrophobic resin. It is. Specific examples of the repeating unit having an acid group (x) are shown below, but the present invention is not limited thereto.
- Rx represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
- the group having a lactone structure As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.
- the repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester.
- this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group.
- this repeating unit may be introduce
- Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the resin (A).
- the content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin. It is more preferably mol%, and further preferably 5 to 95 mol%.
- Examples of the repeating unit having a group (z) capable of decomposing by the action of an acid in the hydrophobic resin include the same repeating units having an acid-decomposable group as mentioned for the resin (A).
- the repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom.
- the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 10%, based on all repeating units in the hydrophobic resin. 80 mol%, more preferably 20 to 60 mol%.
- the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin.
- the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol% in all repeating units contained in the hydrophobic resin.
- the content of silicon atom is preferably 2 to 50% by mass, more preferably 2 to 30% by mass with respect to the weight average molecular weight of the hydrophobic resin.
- the repeating unit containing a silicon atom is preferably 10 to 100 mol%, and more preferably 20 to 100 mol% in all repeating units contained in the hydrophobic resin.
- the hydrophobic resin does not substantially contain a fluorine atom and a silicon atom.
- the content of the repeating unit having a fluorine atom or a silicon atom is preferably 5 mol% or less with respect to all repeating units in the hydrophobic resin, and is preferably 3 mol% or less. Is more preferably 1 mol% or less, and ideally 0 mol%, that is, it does not contain a fluorine atom and a silicon atom.
- hydrophobic resin is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, it is preferable that the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is 95 mol% or more in the total repeating units of the hydrophobic resin. 97 mol% or more is more preferable, 99 mol% or more is further preferable, and ideally 100 mol%.
- the standard polystyrene equivalent weight average molecular weight of the hydrophobic resin is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. Moreover, the hydrophobic resin may be used alone or in combination.
- the content of the hydrophobic resin in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and more preferably 0.1 to 10% by mass with respect to the total solid content in the composition of the present invention. 7 mass% is still more preferable.
- the hydrophobic resin has a small amount of impurities such as metals, and the residual monomer or oligomer component is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass, 0.05 to 1% by mass is even more preferred.
- the molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is in the range of 1-2.
- hydrophobic resin various commercially available products can be used, and can be synthesized according to a conventional method (for example, radical polymerization).
- a conventional method for example, radical polymerization
- a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and the polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours.
- the dropping polymerization method is added, and the dropping polymerization method is preferable.
- reaction solvent the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as described in the resin (A), but in the synthesis of the hydrophobic resin, the reaction concentration Is preferably 30 to 50% by mass.
- the composition of the present invention preferably contains an acid diffusion controller (D).
- the acid diffusion controller (D) acts as a quencher that traps the acid generated from the acid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
- Examples of the acid diffusion controller (D) include a basic compound, a low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid, and a basic compound whose basicity is reduced or eliminated by irradiation with actinic rays or radiation.
- an onium salt that is a weak acid relative to the acid generator can be used.
- Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).
- R 200 , R 201 and R 202 may be the same or different and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number). 6-20), wherein R 201 and R 202 may combine with each other to form a ring.
- R 203 , R 204 , R 205 and R 206 may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
- the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
- the alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
- Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond. Specific examples of preferred compounds include those exemplified in US2012 / 0219913A1 ⁇ 0379>.
- Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.
- amine compound a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
- the amine compound is more preferably a tertiary amine compound.
- the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms).
- 6 to 12 carbon atoms may be bonded to the nitrogen atom.
- the amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
- the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
- an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
- ammonium salt compound a primary, secondary, tertiary or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
- the ammonium salt compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group, provided that at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.
- the ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
- the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
- an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
- anion of the ammonium salt compound examples include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable. The following compounds are also preferable as the basic compound.
- JP2011-22560A [0180] to [0225], JP2012-137735A [0218] to [0219], International Publication Pamphlet WO2011 / 158687A1 [ [0416] to [0438] can also be used.
- These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.
- the composition of the present invention may or may not contain a basic compound.
- the content of the basic compound is usually 0.001 to 10 mass based on the solid content of the composition. %, Preferably 0.01 to 5% by mass.
- the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment.
- the acid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.
- a low molecular weight compound having a nitrogen atom and a group capable of leaving by the action of an acid is an amine having a group on the nitrogen atom that is released by the action of an acid.
- a derivative is preferred.
- the group capable of leaving by the action of an acid an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, and a hemiaminal ether group are preferable, and a carbamate group and a hemiaminal ether group are particularly preferable. .
- the molecular weight of the compound (D-1) is preferably 100 to 1,000, more preferably 100 to 700, and particularly preferably 100 to 500.
- Compound (D-1) may have a carbamate group having a protecting group on the nitrogen atom.
- the protecting group constituting the carbamate group can be represented by the following general formula (d-1).
- Rb each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group ( Preferably, it represents 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms).
- Rb may be connected to each other to form a ring.
- the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are substituted with a functional group such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group, alkoxy group, or halogen atom. It may be. The same applies to the alkoxyalkyl group represented by Rb.
- Rb is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
- Examples of the ring formed by connecting two Rb to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
- Specific examples of the group represented by the general formula (d-1) include structures disclosed in US2012 / 0135348 A1 ⁇ 0466>, but are not limited thereto.
- the compound (D-1) particularly preferably has a structure represented by the following general formula (6).
- Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
- l 2
- two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula.
- the heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.
- Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.
- l represents an integer of 0 to 2
- the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are described above as the groups in which the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb may be substituted. It may be substituted with a group similar to the group.
- Ra alkyl group, cycloalkyl group, aryl group, and aralkyl group examples include: The same group as the specific example mentioned above about Rb is mentioned.
- Specific examples of the particularly preferable compound (D-1) in the present invention include compounds disclosed in US2012 / 0135348 A1 ⁇ 0475>, but are not limited thereto.
- the compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
- the compound (D-1) can be used singly or in combination of two or more.
- the content of the compound (D-1) in the composition of the present invention is preferably 0.001 to 20% by mass, more preferably 0.001 to 10% by mass, based on the total solid content of the composition. More preferably, the content is 0.01 to 5% by mass.
- a basic compound whose basicity decreases or disappears upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (PA)”) has a proton acceptor functional group and is irradiated with actinic rays or radiation. Is a compound whose proton acceptor properties are degraded, disappeared, or changed from proton acceptor properties to acidic properties.
- the proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron.
- a functional group having a macrocyclic structure such as a cyclic polyether or a ⁇ -conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute.
- the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
- Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.
- the compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity.
- the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group.
- the acid dissociation constant pKa of the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation preferably satisfies pKa ⁇ 1, more preferably ⁇ 13 ⁇ pKa ⁇ 1. More preferably, ⁇ 13 ⁇ pKa ⁇ 3.
- the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution.
- Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.) It shows that acid strength is so large that this value is low.
- the acid dissociation constant pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the following software package 1, Hammett
- the values based on the substituent constants and the database of known literature values can also be obtained by calculation.
- the values of pKa described in this specification all indicate values obtained by calculation using this software package.
- the compound (PA) generates, for example, a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition upon irradiation with actinic rays or radiation. Since the compound represented by the general formula (PA-1) has an acidic group together with the proton acceptor functional group, the proton acceptor property is reduced or disappeared compared to the compound (PA), or the proton acceptor property is reduced. It is a compound that has changed to acidic.
- PA-1 a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition upon irradiation with actinic rays or radiation. Since the compound represented by the general formula (PA-1) has an acidic group together with the proton acceptor functional group, the proton acceptor property is reduced or disappeared compared to the compound (PA), or the proton acceptor property is reduced. It is a compound that has changed to acidic.
- Q represents —SO 3 H, —CO 2 H, or —W 1 NHW 2 R f .
- R f represents an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and W 1 and W 2 each independently represents —SO 2 — or —CO—.
- A represents a single bond or a divalent linking group.
- X represents —SO 2 — or —CO—.
- n represents 0 or 1.
- B represents a single bond, an oxygen atom, or —N (R x ) R y —.
- R x represents a hydrogen atom or a monovalent organic group
- R y represents a single bond or a divalent organic group.
- R x may be bonded to R y to form a ring, or R x may be bonded to R to form a ring.
- R represents a monovalent organic group having a proton acceptor functional group.
- the divalent linking group in A is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. More preferred is an alkylene group having at least one fluorine atom, and the preferred carbon number is 2 to 6, more preferably 2 to 4.
- the alkylene chain may have a linking group such as an oxygen atom or a sulfur atom.
- the alkylene group is particularly preferably an alkylene group in which 30 to 100% of the hydrogen atoms are substituted with fluorine atoms, and more preferably, the carbon atom bonded to the Q site has a fluorine atom.
- a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.
- the monovalent organic group in Rx is preferably an organic group having 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may further have a substituent.
- the alkyl group in Rx may have a substituent, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. May be.
- the cycloalkyl group in Rx may have a substituent, and is preferably a monocyclic cycloalkyl group or a polycyclic cycloalkyl group having 3 to 20 carbon atoms, and an oxygen atom, a sulfur atom, a nitrogen atom in the ring You may have an atom.
- the aryl group in Rx may have a substituent, and preferably has 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
- the aralkyl group in Rx may have a substituent, and preferably has 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.
- the alkenyl group in Rx may have a substituent and may be linear or branched.
- the alkenyl group preferably has 3 to 20 carbon atoms. Examples of such alkenyl groups include vinyl groups, allyl groups, and styryl groups.
- Rx further has a substituent
- substituents include, for example, a halogen atom, a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl Group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, nitro group, hydrazino group, heterocyclic group and the like.
- Preferred examples of the divalent organic group for Ry include an alkylene group.
- Examples of the ring structure which Rx and Ry may be bonded to each other include a 5- to 10-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring.
- the proton acceptor functional group in R is as described above, and examples thereof include azacrown ether, primary to tertiary amines, and groups having a heterocyclic aromatic structure containing nitrogen such as pyridine and imidazole.
- the organic group having such a structure is preferably an organic group having 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.
- the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkyl group in the alkenyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group in R include a proton acceptor functional group or an ammonium group.
- a proton acceptor functional group or an ammonium group are the same as the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group mentioned above.
- R and Rx are preferably bonded to each other to form a ring.
- the number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.
- Examples of the monocyclic structure include a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring containing a nitrogen atom.
- Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures.
- R f in -W 1 NHW 2 R f represented by Q preferred is an alkyl group which may have a fluorine atom of 1 to 6 carbon atoms, more preferably perfluoroalkyl of 1 to 6 carbon atoms It is a group.
- W 1 and W 2 at least one is preferably —SO 2 —, and more preferably, both W 1 and W 2 are —SO 2 —.
- Q is particularly preferably —SO 3 H or —CO 2 H from the viewpoint of the hydrophilicity of the acid group.
- PA-1 a compound in which the Q site is a sulfonic acid can be synthesized by using a general sulfonamidation reaction.
- a method in which one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine compound to form a sulfonamide bond, and then the other sulfonyl halide part is hydrolyzed, or a cyclic sulfonic acid anhydride is used. It can be obtained by a method of ring-opening by reacting with an amine compound.
- the compound (PA) is preferably an ionic compound.
- the proton acceptor functional group may be contained in either the anion portion or the cation portion, but is preferably contained in the anion portion.
- Preferred examples of the compound (PA) include compounds represented by the following general formulas (4) to (6).
- C + represents a counter cation.
- the counter cation is preferably an onium cation. More specifically, in the acid generator, a sulfonium cation described as S + (R 201 ) (R 202 ) (R 203 ) in general formula (ZI), I + (R 204 ) in general formula (ZII) ( A preferred example is the iodonium cation described as R 205 ).
- Specific examples of the compound (PA) include compounds exemplified in US2011 / 0269072A1 ⁇ 0280>.
- a compound (PA) other than the compound that generates the compound represented by the general formula (PA-1) can be appropriately selected.
- an ionic compound that has a proton acceptor moiety in the cation moiety may be used.
- a compound represented by the following general formula (7) is exemplified.
- A represents a sulfur atom or an iodine atom.
- m represents 1 or 2
- n represents 1 or 2.
- R represents an aryl group.
- R N represents an aryl group substituted with a proton acceptor functional group.
- X ⁇ represents a counter anion. Specific examples of X ⁇ include the same as the above-mentioned anion of the acid generator. Specific examples of the aryl group of R and R N is a phenyl group are preferably exemplified.
- proton acceptor functional group R N are the same as those of the proton acceptor functional group described in the foregoing formula (PA-1).
- Specific examples of the ionic compound having a proton acceptor site in the cation moiety include compounds exemplified in US2011 / 0269072A1 ⁇ 0291>. Such a compound can be synthesized with reference to methods described in, for example, JP-A-2007-230913 and JP-A-2009-122623.
- a compound (PA) may be used individually by 1 type, and may be used in combination of 2 or more type.
- the content of the compound (PA) is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, based on the total solid content of the composition.
- an onium salt that is a weak acid relative to the acid generator can be used as the acid diffusion controller (D).
- an acid generator and an onium salt that generates an acid that is a weak acid preferably a weak acid having a pKa of more than ⁇ 1 relative to the acid generated from the acid generator are used in combination
- an onium salt having an unreacted weak acid anion a weak acid is released by salt exchange to produce an onium salt having a strong acid anion.
- the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.
- the onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).
- R 51 represents a hydrocarbon group which may have a substituent
- Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S).
- R 52 is an organic group
- Y 3 is a linear, branched or cyclic alkylene group or an arylene group
- Rf is a fluorine atom.
- Each of the M + is independently a sulfonium or iodonium cation.
- Preferable examples of the sulfonium cation or iodonium cation represented by M + include the sulfonium cation exemplified for the acid generator (ZI) and the iodonium cation exemplified for (ZII).
- Preferable examples of the anion moiety of the compound represented by the general formula (d1-1) include the structures exemplified in paragraph [0198] of JP2012-242799A.
- Preferable examples of the anion moiety of the compound represented by the general formula (d1-2) include the structures exemplified in paragraph [0201] of JP2012-242799A.
- Preferable examples of the anion moiety of the compound represented by the general formula (d1-3) include the structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.
- An onium salt that is a weak acid relative to the acid generator is a compound having a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety are linked by a covalent bond (hereinafter, “ Also referred to as “compound (D-2)”.
- the compound (D-2) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).
- R 1 , R 2 and R 3 represent a substituent having 1 or more carbon atoms.
- L 1 represents a divalent linking group or a single bond linking the cation moiety and the anion moiety.
- -X - it is, -COO -, -SO 3 - represents an anion portion selected from -R 4 -, -SO 2 -, -N.
- R 4 is a group having a carbonyl group: —C ( ⁇ O) —, a sulfonyl group: —S ( ⁇ O) 2 —, and a sulfinyl group: —S ( ⁇ O) — at the site of connection with the adjacent N atom.
- R 1 , R 2 , R 3 , R 4 and L 1 may be bonded to each other to form a ring structure.
- R 1 to R 3 may be combined to form a double bond with the N atom.
- Examples of the substituent having 1 or more carbon atoms in R 1 to R 3 include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.
- L 1 as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L 1 is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.
- Preferable examples of the compound represented by the general formula (C-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [0029] of JP2013-8020A. ] Can be mentioned.
- Preferable examples of the compound represented by the general formula (C-2) include compounds exemplified in paragraphs [0012] to [0013] of JP2012-189977A.
- Preferable examples of the compound represented by the general formula (C-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP 2012-252124 A.
- the content of the onium salt that is a weak acid relative to the acid generator is preferably 0.5 to 10.0% by mass, and preferably 0.5 to 8.0% by mass based on the solid content of the composition. % Is more preferable, and 1.0 to 8.0% by mass is even more preferable.
- the composition of the present invention usually contains a solvent.
- Solvents that can be used in preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 4 carbon atoms). 10), an organic solvent such as a monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate and the like. Specific examples of these solvents include those described in US Patent Application Publication No.
- the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group the above-mentioned exemplary compounds can be selected as appropriate.
- the solvent containing a hydroxyl group alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether ( PGME, also known as 1-methoxy-2-propanol), ethyl lactate is more preferred.
- alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, butyl acetate are particularly preferred, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2 -Heptanone is most preferred.
- PGMEA propylene glycol monomethyl ether Acetate
- ethyl ethoxypropionate 2-heptanone
- ⁇ -butyrolactone cyclohexanone
- the mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. .
- a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
- the solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.
- the composition of the present invention may or may not contain a carboxylic acid onium salt.
- carboxylic acid onium salts include those described in US Patent Application Publication No. 2008/0187860 ⁇ 0605> to ⁇ 0606>.
- These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.
- the content thereof is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total solid content of the composition. More preferably, it is 1 to 7% by mass.
- the composition of the present invention may further have solubility in a surfactant, an acid proliferation agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a developer.
- a compound to be promoted for example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound
- a compound to be promoted for example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound
- Such a phenol compound having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized by those skilled in the art.
- alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.
- the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably a composition for forming an actinic ray-sensitive or radiation-sensitive film having a thickness of 1 ⁇ m or more.
- the film thickness of the conductive film is more preferably 2 ⁇ m or more, and further preferably 3 ⁇ m or more.
- the film thickness of the actinic ray-sensitive or radiation-sensitive film is usually 12 ⁇ m or less.
- the present invention also relates to an actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention.
- the main use of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a use for forming a thick film (for example, having a thickness of 1 ⁇ m or more).
- the viscosity of the actinic ray-sensitive or radiation-sensitive resin composition is preferably 100 to 500 mPa ⁇ s, and preferably 120 to 480 mPa ⁇ s. More preferably, it is more preferably 150 to 450 mPa ⁇ s.
- the solid content concentration of the composition of the present invention is preferably 20 to 60% by mass, more preferably 20 to 55% by mass, and further preferably 20 to 50% by mass. Thereby, the composition which has the viscosity of the said range can be prepared suitably.
- the solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.
- the above components are dissolved in a predetermined organic solvent, preferably the above mixed solvent, filtered, and then applied onto a predetermined substrate.
- the pore size of the filter used for filter filtration is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and still more preferably 0.03 ⁇ m or less made of polytetrafluoroethylene, polyethylene, or nylon.
- filter filtration for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel.
- the composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.
- the pattern forming method of the present invention comprises: (I) a step of forming (forming a film) an actinic ray-sensitive or radiation-sensitive film (hereinafter also simply referred to as a film) having a film thickness of 1 ⁇ m or more on the substrate by the actinic ray-sensitive or radiation-sensitive resin composition; (Ii) irradiating the actinic ray-sensitive or radiation-sensitive film with an actinic ray or radiation (exposure step); and (Iii) A pattern forming method including a step of developing the actinic ray-sensitive or radiation-sensitive film irradiated with the actinic ray or radiation with a developer (development step).
- the pattern forming method of the present invention preferably includes (ii) a heating step after the (ii) exposure step.
- the pattern forming method of the present invention may include (ii) an exposure step a plurality of times.
- the pattern forming method of the present invention may include (iv) a heating step a plurality of times.
- the step of forming a film on the substrate using the composition of the present invention, the step of exposing the film, and the developing step can be performed by generally known methods.
- the step of forming the film on the substrate includes a method of coating the composition on the substrate, and the coating method is a general conventional coating sequence (for example, after dropping the resist composition, the number of rotations of the substrate). And a method of maintaining the number of revolutions at which the film thickness is determined) can be used.
- unevenness in the thickness of the resist film may occur if it is a normal method. Can be improved.
- a resist composition is dropped onto a substrate, and then the number of rotations of the substrate is maintained at a first medium speed, and then maintained at a second low speed. Is applied at a rotational speed that determines the film thickness.
- the first medium-speed rotation step and the second low-speed rotation step are alternately repeated a plurality of times.
- the first medium speed is preferably 300 rpm to 1000 rpm
- the second low speed is preferably 50 rpm to 200 rpm.
- the substrate on which the film is formed is not particularly limited, and silicon, SiN, inorganic substrates such as SiO 2 and SiN, coated inorganic substrates such as SOG, semiconductor manufacturing processes such as IC, liquid crystal, and thermal head
- silicon, SiN, inorganic substrates such as SiO 2 and SiN coated inorganic substrates such as SOG
- semiconductor manufacturing processes such as IC, liquid crystal, and thermal head
- a substrate generally used in a circuit board manufacturing process or other photofabrication lithography process can be used.
- an antireflection film may be formed between the resist film and the substrate.
- the antireflection film a known organic or inorganic antireflection film can be appropriately used.
- the thickness of the film formed from the actinic ray-sensitive or radiation-sensitive resin composition in the pattern forming method of the present invention is 1 ⁇ m or more, more preferably 2 ⁇ m or more, and 3 ⁇ m or more. Is more preferable.
- the film thickness is usually 12 ⁇ m or less.
- PB preheating step
- PEB post-exposure heating step
- the heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB.
- the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like. The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.
- gray scale exposure As the exposure, it is preferable to carry out gray scale exposure (gray scale exposure).
- gray scale exposure the resist film is exposed through a mask in which predetermined halftone dots are formed so as to have a predetermined light transmittance so as to obtain a desired shape. That is, it is an exposure process that can give gradation to the height of a pattern (resist pattern) obtained by irradiating light to a mask having a minute opening.
- the immersion exposure method can be applied in the step of performing exposure according to the present invention.
- the immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method.
- a super-resolution technique such as a phase shift method or a modified illumination method.
- a step of washing the surface of the membrane with an aqueous chemical solution may be performed.
- the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the film.
- an additive liquid that reduces the surface tension of water and increases the surface activity may be added in a small proportion.
- This additive is preferably one that does not dissolve the resist film on the wafer and can ignore the influence on the optical coating on the lower surface of the lens element.
- an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like.
- the optical image projected on the resist film is distorted.
- pure water filtered through an ion exchange filter or the like may be used.
- the electrical resistance of the water used as the immersion liquid is preferably 18.3 M ⁇ cm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.
- the receding contact angle of the resist film is preferably 70 ° or more at a temperature of 23 ⁇ 3 ° C. and a humidity of 45 ⁇ 5%. In such a case, it is suitable for exposure through an immersion medium. Further, it is more preferably 75 ° or more, and further preferably 75 to 85 °.
- the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited.
- a hydrophobic resin described later in the composition it is preferable to include a hydrophobic resin described later in the composition.
- an immersion liquid hardly soluble film (hereinafter also referred to as “top coat”) formed of a hydrophobic resin may be provided on the upper layer of the resist film.
- a top coat may be provided on the upper layer of the resist film containing the hydrophobic resin. The necessary functions for the top coat are appropriate application to the upper layer of the resist film and poor immersion liquid solubility.
- the top coat is not mixed with the resist film and can be uniformly applied to the upper layer of the resist film.
- the topcoat include hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, fluorine-containing polymers, and the like. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.
- the top coat may contain a basic compound.
- a developer may be used, or a separate release agent may be used.
- the release agent a solvent having low penetration into the film is preferable.
- the peeling step can be performed simultaneously with the film development step, it is preferable that the peeling can be performed with a developer containing an organic solvent.
- the resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid.
- the topcoat is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.
- the topcoat is preferably not mixed with the membrane and further not mixed with the immersion liquid.
- the solvent used for the topcoat is a poorly water-soluble and water-insoluble medium in the solvent used for the composition of the present invention.
- the topcoat may be water-soluble or water-insoluble.
- the formation of the top coat is not limited to immersion exposure, and may be performed in the case of dry exposure (exposure not involving an immersion liquid). By forming the top coat, for example, generation of outgas can be suppressed.
- the topcoat composition used for forming the topcoat will be described.
- the solvent is preferably an organic solvent. More preferred is an alcohol solvent.
- the solvent is an organic solvent, it is preferably a solvent that does not dissolve the resist film.
- an alcohol solvent, a fluorine solvent, or a hydrocarbon solvent is preferably used, and a non-fluorine alcohol solvent is more preferably used.
- a primary alcohol is preferable from the viewpoint of applicability, and a primary alcohol having 4 to 8 carbon atoms is more preferable.
- the primary alcohol having 4 to 8 carbon atoms a linear, branched, or cyclic alcohol can be used, and for example, 1-butanol, 1-hexanol, 1-pentanol, 3-methyl is preferable. Examples include 1-butanol, 2-ethylbutanol, and perfluorobutyltetrahydrofuran.
- resins having an acidic group described in JP-A-2009-134177 and JP-A-2009-91798 can also be preferably used.
- the weight average molecular weight of the resin is not particularly limited, but is preferably 2,000 to 1,000,000, more preferably 5,000 to 500,000, still more preferably 10,000 to 100,000.
- the weight average molecular weight of the resin indicates a polystyrene-equivalent molecular weight measured by GPC (Gel permeation chromatography) (carrier: tetrahydrofuran (THF) or N-methyl-2-pyrrolidone (NMP)).
- the pH of the top coat composition is not particularly limited, but is preferably 0 to 10, more preferably 0 to 8, and still more preferably 1 to 7.
- the topcoat composition may contain additives such as a photoacid generator and a nitrogen-containing basic compound.
- a nitrogen-containing basic compound US Published Patent Publication US2013 / 0244438A can be mentioned.
- the concentration of the resin in the top coat composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.3 to 3% by mass.
- the topcoat material may contain components other than the resin, but the ratio of the resin to the solid content of the topcoat composition is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and still more preferably Is from 95 to 100% by weight.
- the solid content concentration of the topcoat composition in the present invention is preferably 0.1 to 10% by mass, more preferably 0.2 to 6% by mass, and 0.3 to 5% by mass. Is more preferable. By setting the solid content concentration within the above range, the topcoat composition can be uniformly applied onto the resist film.
- a resist film can be formed on the substrate using the above composition, and a top coat can be formed on the resist film using the top coat composition.
- the thickness of the resist film is preferably 10 to 100 nm, and the thickness of the top coat is preferably 10 to 200 nm, more preferably 20 to 100 nm, and further preferably 40 to 80 nm.
- the method for forming the top coat is not particularly limited, but the top coat composition can be applied and dried by the same means as the resist film forming method to form the top coat.
- the resist film having a top coat as an upper layer is usually irradiated with actinic rays or radiation through a mask, preferably baked (heated) and developed. Thereby, a good pattern can be obtained.
- the immersion head In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern.
- the contact angle of the immersion liquid with respect to the resist film is important. For this reason, the resist is required to have the capability of following the high-speed scanning of the exposure head without any remaining droplets.
- the developer used in the step of developing the film formed using the composition of the present invention is not particularly limited.
- a developer containing an alkali developer or an organic solvent (hereinafter also referred to as an organic developer).
- an organic developer can be used.
- alkali developer examples include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium Hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyl Tetraalkylammonium hydroxide such as methylammonium hydrox
- Alkaline aqueous solutions such as quaternary ammonium salts, cyclic amines such as pyrrole and pihelidine can be used. Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
- the alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
- the pH of the alkali developer is usually from 10.0 to 15.0.
- the alkali concentration and pH of the alkali developer can be appropriately adjusted and used.
- the alkali developer may be used after adding a surfactant or an organic solvent.
- pure water can be used, and an appropriate amount of a surfactant can be added.
- a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent
- the solvent described in paragraph ⁇ 0507> of JP-A-218223 isoamyl acetate, butyl butanoate, butyl butyrate, methyl 2-hydroxyisobutyrate, and the like.
- a plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water.
- the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture. That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
- the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .
- the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
- the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
- the surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.
- fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in US Pat. Nos.
- the amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.
- the organic developer may contain a basic compound.
- Specific examples and preferred examples of the basic compound that can be contained in the organic developer used in the present invention are the same as those in the basic compound that can be contained in the composition described above as the acid diffusion controller (D).
- a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
- dip method a method in which a substrate is immersed in a tank filled with a developer for a certain period of time
- paddle a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time
- spray method a method of spraying the developer on the substrate surface
- the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is Preferably it is 2 mL / sec / mm 2 or less, More preferably, it is 1.5 mL / sec / mm 2 or less, More preferably, it is 1 mL / sec / mm 2 or less.
- There is no particular lower limit on the flow rate but 0.2 mL / sec / mm 2 or more is preferable in consideration of throughput.
- the details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied to the resist film by the developer is reduced, and the resist film and the resist pattern are carelessly cut or collapsed. This is considered to be suppressed.
- the developer discharge pressure (mL / sec / mm 2 ) is a value at the developing nozzle outlet in the developing device.
- Examples of the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank. Moreover, you may implement the process of stopping image development, substituting with another solvent after the process developed using the developing solution containing an organic solvent.
- a step of developing using a developer containing an organic solvent (organic solvent developing step) and a step of developing using an alkaline aqueous solution (alkali developing step) are used in combination. Also good. Thereby, a finer pattern can be formed.
- organic solvent developing step organic solvent developing step
- alkali developing step a step of developing using an alkaline aqueous solution
- a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by further performing the alkali development step.
- a pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 ⁇ 0077).
- the order of the alkali development step and the organic solvent development step is not particularly limited, but it is more preferable to perform the alkali development before the organic solvent development step.
- the rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used.
- a rinsing liquid a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents should be used. Is preferred. Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.
- the step of developing using a developer containing an organic solvent at least one selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and hydrocarbon solvents.
- the step of washing with a rinsing liquid containing an organic solvent is performed, more preferably the step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent, particularly preferably a monohydric alcohol.
- a cleaning step is performed using the rinsing liquid contained, and most preferably, a cleaning step is performed using a rinsing liquid containing a monohydric alcohol having 5 or more carbon atoms.
- examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms are 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc.
- the hydrocarbon solvent used in the rinsing step is preferably a hydrocarbon compound having 6 to 30 carbon atoms, more preferably a hydrocarbon compound having 8 to 30 carbon atoms, still more preferably a hydrocarbon compound having 7 to 30 carbon atoms, A hydrocarbon compound having 10 to 30 carbon atoms is particularly preferred. Especially, pattern collapse is suppressed by using the rinse liquid containing a decane and / or undecane.
- a plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.
- the water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
- the vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable.
- the wafer that has been developed using the developer containing the organic solvent is cleaned using the rinse solution containing the organic solvent.
- the cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied. Among these, a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm.
- the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking.
- the heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
- Various materials used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and the pattern forming method of the present invention preferably does not contain impurities such as metals.
- the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 10 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less.
- Examples of a method for removing impurities such as metals from the various materials include filtration using a filter.
- the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
- a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
- the filter may be a composite material obtained by combining these materials and ion exchange media.
- a filter that has been washed in advance with an organic solvent may be used.
- a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different hole diameters and / or materials may be used in combination.
- various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
- a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials.
- the inside of the apparatus may be lined with Teflon (registered trademark), and distillation may be performed under a condition in which contamination is suppressed as much as possible.
- the preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
- impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used.
- adsorbent known adsorbents can be used.
- inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
- metal impurities such as metals contained in the various materials
- it is necessary to prevent metal impurities from being mixed in the manufacturing process. Whether or not the metal impurities have been sufficiently removed from the manufacturing apparatus can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing apparatus.
- the content of the metal component contained in the cleaning liquid after use is more preferably 100 ppt (parts per trigger) or less, further preferably 10 ppt or less, and particularly preferably 1 ppt or less.
- a method for improving the surface roughness of the pattern may be applied to the pattern formed by the method of the present invention.
- Examples of the method for improving the surface roughness of the pattern include a method of treating a resist pattern with a plasma of a hydrogen-containing gas disclosed in International Publication Pamphlet 2014/002808.
- JP 2004-235468, US Published Patent Application 2010/0020297, JP 2009-19969, Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.
- the pattern forming method of the present invention can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823).
- the resist pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.
- the present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.
- the electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).
- Table 1 shows resist compositions used for evaluation.
- the addition amount (mass%) of each component other than the solvent means mass% relative to the solid content excluding the solvent.
- the ratio of each component in the column of resin (A) and compound (B) is a weight ratio when the sum of resin (A) and compound (B) is 100.
- the numerical value in parentheses in an example using two types of acid generator and acid diffusion controller indicates the content (% by mass) based on the total solid content of the composition of the compound.
- the numerical values in the solvent column and the mass ratio of the main solvent and the auxiliary solvent are shown.
- Resin structure is as follows.
- Table 2 shows the composition ratio (molar ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) of the above-described resin.
- Mw weight average molecular weight
- Mn dispersity
- composition ratio of each repeating unit of the following resin is shown in molar ratio.
- the glass transition temperatures of the resins A-1 to A-3, B-1 to B-3, D-1 to D-3, Compound C, and Compounds C-1 to C-6 are as follows. It was measured by a thermal analysis device DSC Q1000 manufactured by Instrument Corporation.
- the structure of the acid generator is as follows.
- the structure of the acid diffusion controller is as follows.
- the structure of the additive is as follows.
- the solvent is as follows.
- PGMEA Propylene glycol monomethyl ether acetate
- PGME Propylene glycol monomethyl ether
- MAK 2-Heptanone
- the resist composition prepared above was formed on a Si substrate (manufactured by Advanced Materials Technology), which had been subjected to hexamethyldisilazane treatment, without providing an antireflection layer. Dropped in a stationary state. After dropping, the substrate is rotated, and the number of rotations is maintained at 500 rpm for 3 seconds, then maintained at 100 rpm for 2 seconds, further maintained at 500 rpm for 3 seconds, and again maintained at 100 rpm for 2 seconds, and then the film thickness setting rotation is performed. The number was increased to 1200 rpm and maintained for 60 seconds.
- TMAH tetramethylammonium hydroxide
- the interface between the resist film portion and the space portion in the chip section is observed with a scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation), and the thickness of the resist film portion (corresponding to the depth of the space portion). ) Is 100%, the space width of the space portion at a depth of 20% from the surface (that is, the upper surface) of the resist film portion is a space portion at a height of 50% from the surface of the resist film portion.
- the minimum value of the temperature at which the shape of the resist film portion changed to a state where it was 1.2 times or more than the space width was defined as the softening point (° C.). The results are shown in Table 3.
- the resist composition prepared above was formed on a Si substrate (manufactured by Advanced Materials Technology), which had been subjected to hexamethyldisilazane treatment, without providing an antireflection layer. Dropped in a stationary state. After dropping, the substrate is rotated, and the number of rotations is maintained at 500 rpm for 3 seconds, then maintained at 100 rpm for 2 seconds, further maintained at 500 rpm for 3 seconds, and again maintained at 100 rpm for 2 seconds, and then the film thickness setting rotation is performed. The number was increased to 1200 rpm and maintained for 60 seconds.
- TMAH tetramethylammonium hydroxide
- the space width was 3 ⁇ m.
- An isolated space pattern having a pitch width of 33 ⁇ m was formed.
- the pattern exposure is exposure through a mask having a line-and-space pattern such that the space width after reduced projection exposure is 3 ⁇ m and the pitch width is 33 ⁇ m.
- the exposure amount is 3 ⁇ m for the space width and 33 ⁇ m for the pitch width.
- the optimum exposure amount (sensitivity) for forming an isolated space pattern (mJ / cm 2 ) was used. In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation).
- the minimum line width of the space width in the isolated space pattern formed when exposure is performed through the mask used in the pattern formation and the exposure amount is changed is defined as the resolution, and the smaller the minimum line width, the higher the resolution. Judged high.
- the space width was measured using a scanning electron microscope (SEM) (9380II manufactured by Hitachi High-Technologies Corporation).
- the Si substrate (8-inch silicon wafer) was dry-etched using the isolated space pattern formed with the above sensitivity as a processing mask.
- etching using a fluorine-based gas was performed to process the Si substrate.
- 1 inch corresponds to 25.4 mm.
- a gas in which Ar: C 4 F 6 : O 2 is mixed at a flow rate ratio of 25: 1: 2 is used, processing pressure is 4 Pa, source power is 500 W, wafer bias is 700 W, antenna bias is 600 W, and processing is performed.
- a condition of time 60 seconds was applied.
- etching using oxygen gas was performed to process the resist mask pattern.
- etching conditions a gas in which CF 4 : O 2 was mixed at a flow rate ratio of 1:24 was used, and conditions of a processing pressure of 0.5 Pa, a source power of 700 W, an antenna bias of 100 W, and a processing time of 60 seconds were applied. .
- the wafer is cleaved, and the sidewall roughness of the resist is observed with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- A is the one in which the roughness is hardly seen
- B is the one in which the roughness is slightly seen
- Those with large roughness were classified as C.
- the dry etching apparatus used was U-621 manufactured by Hitachi High-Technologies Corporation.
- Table 3 shows the results of the above evaluations.
- Comparative Example 1 in which the softening point of the isolated space pattern exceeds 170 ° C. does not suppress roughness on the side wall of the pattern, and Comparative Examples 2 to 7 in which the softening point of the isolated space pattern is less than 130 ° C. are resolved. It was found to be inferior to both the property and the exposure latitude. On the other hand, in each of Examples 1 to 18 that satisfy the requirements of the present invention, both excellent resolution and excellent exposure latitude are achieved at a high level, and the roughness on the side wall of the resist pattern that can occur during etching is reduced. It turned out that it can suppress. Further, it was found that Examples 19 to 24 using the polyether-based compound having the group represented by the general formula (a) described above are superior in crack performance as the compound (B).
- a pattern from a thick resist film for example, having a thickness of 1 ⁇ m or more
- excellent resolution and excellent exposure latitude are compatible at a high level and etching is performed.
- Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film capable of suppressing roughness on the side wall of a resist pattern that can sometimes be generated, a pattern forming method, and an electronic device using these can be provided.
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Abstract
Description
このようななか、本発明者らは、従来の厚膜レジスト膜形成用のレジスト組成物について検討したところ、解像性、露光ラチチュード等のリソグラフィー性能を損なうことなく、エッチング時に発生し得るレジストパターンの側壁におけるラフネスを抑制することが非常に難しいことが明らかになった。
ガラス転移温度が155℃以上の樹脂(A)、
ガラス転移温度が150℃以下の化合物(B)、及び
溶剤(C)を含有する、
感活性光線性又は感放射線性樹脂組成物であって、
上記感活性光線性又は感放射線性樹脂組成物中の固形分含有量が20質量%以上であり、
上記感活性光線性又は感放射線性樹脂組成物によって形成されるレジストパターンの軟化点が130℃以上170℃以下である、感活性光線性又は感放射線性樹脂組成物。
〔2〕
上記化合物(B)が樹脂である、〔1〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔3〕
上記化合物(B)としての樹脂の重量平均分子量が1000~18000である、〔2〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔4〕
上記樹脂(B)がヒドロキシスチレンに由来する繰り返し単位を有する、〔2〕又は〔3〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔5〕
化合物(B)がポリエーテル系化合物である、〔1〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔6〕
上記ポリエーテル系化合物の分子量が100~5000である、〔5〕に記載の感活性光線性又は感放射線性樹脂組成物。
〔7〕
上記感活性光線性又は感放射線性樹脂組成物の粘度が100~500mPa・sである、〔1〕~〔6〕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。
〔8〕
上記樹脂(A)のガラス転移温度が170℃以上である、〔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。
〔9〕
上記樹脂(A)の重量平均分子量が18000以上である、〔1〕~〔8〕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。
〔10〕
上記樹脂(A)がヒドロキシスチレンに由来する繰り返し単位を有する、〔1〕~〔9〕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。
〔11〕
〔1〕~〔10〕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より形成された感活性光線性又は感放射線性膜。
〔12〕
(i)〔1〕~〔10〕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によって基板上に膜厚が1μm以上の感活性光線性又は感放射線性膜を形成する工程、
(ii)上記感活性光線性又は感放射線性膜に活性光線又は放射線を照射する工程、及び、
(iii)上記活性光線又は放射線が照射された感活性光線性又は感放射線性膜を、現像液を用いて現像する工程、を有するパターン形成方法。
〔13〕
〔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。
本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。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)をも包含するものである。
本明細書における「活性光線」又は「放射線」とは、例えば、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(EUV光)、X線、電子線(EB)等を意味する。また、本発明において光とは、活性光線又は放射線を意味する。
また、本明細書における「露光」とは、特に断らない限り、水銀灯、エキシマレーザーに代表される遠紫外線、極紫外線、X線、EUV光などによる露光のみならず、電子線、イオンビーム等の粒子線による描画も露光に含める。
また、本明細書において、(メタ)アクリレートはアクリレート及びメタクリレートを表し、(メタ)アクリルはアクリル及びメタクリルを表す。
本明細書において、樹脂の重量平均分子量(Mw)、数平均分子量(Mn)、及び分散度(Mw/Mn)は、GPC(Gel Permeation Chromatography)装置(東ソー製HLC-8120GPC)によるGPC測定(溶媒:テトラヒドロフラン、流量(サンプル注入量):10μl、カラム:東ソー社製TSK gel Multipore HXL-M(×4本)、カラム温度:40℃、流速:1.0mL/分、検出器:示差屈折率(RI)検出器)によるポリスチレン換算値として定義される。
また、本明細書において、ガラス転移温度は、ティー・エイ・インスツルメント社製熱分析装置DSC Q1000により測定されるものである。
また、本明細書において、粘度は、25.0℃における粘度であり、TOKI SANGYO製RE-85Lにより測定されるものである。
本発明の感活性光線性又は感放射線性樹脂組成物(以下、単に本発明の組成物とも言う)は、ガラス転移温度が155℃以上の樹脂(A)、ガラス転移温度が150℃以下の化合物(B)、及び溶剤(C)を含有する、感活性光線性又は感放射線性樹脂組成物であって、上記感活性光線性又は感放射線性樹脂組成物中の固形分含有量が20質量%以上であり、上記感活性光線性又は感放射線性樹脂組成物によって形成されるレジストパターンの軟化点が130℃以上170℃以下である。
本発明において、レジストパターンの軟化点とは、具体的には、スペース幅が10μm、ピッチ幅が100μm、レジスト膜部の厚さが7.5μmの孤立スペースパターンの軟化点を言う。
本発明は上記構成をとるため、厚膜の(例えば1μm以上の厚さを有する)レジスト膜からパターンを形成する場合において、優れた解像性と、優れた露光ラチチュードとを高次元で両立するとともに、エッチング時に発生し得るレジストパターンの側壁におけるラフネスを抑制できるものである。
その理由は明らかではないが、以下の通りと推測される。
また、上記感活性光線性又は感放射線性樹脂組成物は、ガラス転移温度が155℃以上の樹脂(A)を含有している。これにより、レジスト膜の膜質が柔らかすぎないため、露光部において、酸発生剤より発生した酸が、未露光部に拡散し難く、その結果、優れた解像性が得られるものと推測される。
また、上記レジスト膜は、感活性光線性又は感放射線性樹脂組成物がガラス転移温度が155℃以上の樹脂(A)を含有している等の理由により、レジストパターン(スペース幅が10μm、ピッチ幅が100μm、レジスト膜部の厚さが7.5μmの孤立スペースパターン)の軟化点が130℃以上となっている。これにより、得られる孤立スペースパターンの膜質は、ある程度以上の固さを有しているため、例えば、上記孤立スペースパターンよりも、より微細度が高い(スペース幅が短い)孤立スペースパターン等を形成する場合においても、優れた露光ラチチュードが得られたものと推察される。
また、上記感活性光線性又は感放射線性樹脂組成物は、ガラス転移温度が150℃以下の化合物(B)を含有しており、これを主な理由として、レジストパターン(スペース幅が10μm、ピッチ幅が100μm、レジスト膜部の厚さが7.5μmの孤立スペースパターン)の軟化点が170℃以下となっている。これにより、得られるパターンの膜質が、固すぎない(ある程度以上の柔軟性を有している)。その結果、例えば、上記パターンよりも、より微細度が高い(スペース幅が短い)孤立スペースパターン等を基板上に形成し、この基板をエッチングする場合においても、レジストパターンの側壁にラフネスが生じることを抑制できたものと推察される。ここで、上記軟化点を170℃以下とするためには、単純に、樹脂(A)のガラス転移温度を下げる手法も考えられるが、この場合は、樹脂(A)によってもたらされる優れた解像性や露光ラチチュードが失われる傾向となる。
しかしながら、本発明における感活性光線性又は感放射線性樹脂組成物は、ガラス転移温度が155℃以上の樹脂(A)を含有した上で、ガラス転移温度が150℃以下の化合物(B)を含有する等により、上記軟化点を170℃以下とするものであるため、優れた解像性と、優れた露光ラチチュードとを高次元で両立しながらも、エッチング時に発生し得るレジストパターンの側壁におけるラフネスを抑制できたものと考えられる。
(1)感活性光線性又は感放射線性樹脂組成物から形成された厚さが7.5μmのレジスト膜に対して、パターン露光及び現像により、スペース幅が10μm、ピッチ幅が100μm、レジスト膜部の厚さが7.5μmの孤立スペースパターンを形成する。
(2)上記において形成した孤立スペースパターンを有するチップを複数用意し、ホットプレート上で100℃~200℃の範囲で5℃刻みに各々60秒間加熱処理した後(すなわち、例えば、サンプルAとしてのチップに対しては150℃、60秒間の加熱処理を行い、サンプルBとしてのチップに対しては155℃、60秒間の加熱処理を行い、サンプルCとしてのチップに対しては150℃、60秒間の加熱処理を行った後)、各チップを割断した。
(3)チップの割断面における、レジスト膜部とスペース部の界面を走査型電子顕微鏡(SEM)(株式会社日立ハイテクノロジーズ製9380II)にて観察し、レジスト膜部の厚さ(スペース部の深さに相当)を100%とした場合に、レジスト膜部の表面(すなわち上面)から深さ20%の高さにおけるスペース部のスペース幅が、レジスト膜部の表面から深さ50%の高さにおけるスペース部のスペース幅に対して1.2倍以上となる状態までレジスト膜部の形状が変化した温度の最小値を軟化点(℃)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、アルカリ現像用のポジ型レジスト組成物であっても、有機溶剤現像用のネガ型レジスト組成物であってもよいが、アルカリ現像用のポジ型レジスト組成物であることが好ましい。また本発明に係る組成物は、典型的には化学増幅型のレジスト組成物である。
本発明の組成物は、ガラス転移温度が155℃以上の樹脂(A)を含有する。
樹脂(A)は、典型的には、酸の作用によって分解し、現像液に対する溶解性が変化する樹脂であり、酸の作用によりアルカリ現像液に対する溶解性が増大し、又は、酸の作用により有機溶剤を主成分とする現像液に対する溶解性が減少する樹脂であることが好ましく、樹脂の主鎖又は側鎖、又は、主鎖及び側鎖の両方に、酸の作用により分解し、極性基を生じる基(以下、「酸分解性基」ともいう)を有することが好ましい。
極性基としては、フェノール性水酸基、カルボキシル基、フッ素化アルコール基、スルホン酸基、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、トリス(アルキルスルホニル)メチレン基等の酸性基(従来レジストの現像液として用いられている、2.38質量%テトラメチルアンモニウムヒドロキシド水溶液中で解離する基)、又はアルコール性水酸基等が挙げられる。
好ましい極性基としては、カルボキシル基、フッ素化アルコール基(好ましくはヘキサフルオロイソプロパノール基)、スルホン酸基が挙げられる。
酸の作用により脱離する基としては、例えば、-C(R36)(R37)(R38)、-C(R36)(R37)(OR39)、-C(R01)(R02)(OR39)、-C(R01)(R02)-C(=O)-O-C(R36)(R37)(R38)又は-CH(R36)(Ar)等を挙げることができる。
式中、R36~R39は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。R36とR37とは、互いに結合して環を形成してもよい。
R01及びR02は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
Arは、アリール基を表す。
R36~R39、R01、又はR02としてのシクロアルキル基は、単環のシクロアルキル基であってもよく、多環のシクロアルキル基であってもよい。単環のシクロアルキル基としては、炭素数3~8のシクロアルキル基が好ましく、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、シクロへキシル基及びシクロオクチルが挙げられる。多環のシクロアルキル基としては、炭素数6~20のシクロアルキル基が好ましく、例えば、アダマンチル基、ノルボルニル基、イソボロニル基、カンファニル基、ジシクロペンチル基、α-ピナニル基、トリシクロデカニル基、テトラシクロドデシル基及びアンドロスタニル基が挙げられる。なお、シクロアルキル基中の炭素原子の一部は、酸素原子等のヘテロ原子によって置換されていてもよい。
R36~R39、R01、R02、又はArとしてのアリール基は、炭素数6~10のアリール基であることが好ましく、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。
R36~R39、R01、又はR02としてのアラルキル基は、炭素数7~12のアラルキル基であることが好ましく、例えば、ベンジル基、フェネチル基及びナフチルメチル基が好ましい。
R36~R39、R01、又はR02としてのアルケニル基は、炭素数2~8のアルケニル基であることが好ましく、例えば、ビニル基、アリル基、ブテニル基及びシクロへキセニル基が挙げられる。
上記各基は、置換基を有していてもよい。この置換基としては、例えば、アルキル基、シクロアルキル基、アリール基、アミノ基、アミド基、ウレイド基、ウレタン基、ヒドロキシル基、カルボキシル基、ハロゲン原子、アルコキシ基、チオエーテル基、アシル基、アシロキシ基、アルコキシカルボニル基、シアノ基及びニトロ基が挙げられる。これら置換基は、炭素数が8以下であることが好ましい。
Xa1は、水素原子、又は、アルキル基を表す。
Tは、単結合又は2価の連結基を表す。
Rx1~Rx3は、各々独立に、アルキル基(直鎖若しくは分岐)又はシクロアルキル基(単環若しくは多環)を表す。
Rx1~Rx3の2つが結合して、シクロアルキル基(単環若しくは多環)を形成してもよい。
Tの2価の連結基としては、アルキレン基、-COO-Rt-基、-O-Rt-基等が挙げられる。式中、Rtは、アルキレン基又はシクロアルキレン基を表す。
Tは、単結合又は-COO-Rt-基が好ましい。Rtは、炭素数1~5のアルキレン基が好ましく、-CH2-基、-(CH2)2-基、-(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、シクロヘキシル基などの単環のシクロアルキル基、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、アダマンチル基などの多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としては、シクロペンチル基、シクロヘキシル基などの単環のシクロアルキル基、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、アダマンチル基などの多環のシクロアルキル基が好ましい。炭素数5~6の単環のシクロアルキル基が特に好ましい。
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、又は、カルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
一般式(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。
具体例中、Rx、Xa1は、水素原子、CH3、CF3、又はCH2OHを表す。Rxa、Rxbは各々炭素数1~4のアルキル基を表す。Zは、極性基を含む置換基を表し、複数存在する場合は各々独立である。pは0又は正の整数を表す。Zにより表される極性基を含む置換基としては、例えば、水酸基、シアノ基、アミノ基、アルキルアミド基又はスルホンアミド基を有する、直鎖又は分岐のアルキル基、シクロアルキル基が挙げられ、好ましくは、水酸基を有するアルキル基である。分岐状アルキル基としてはイソプロピル基が特に好ましい。
R31は、水素原子又はアルキル基を表す。
R32は、アルキル基又はシクロアルキル基を表し、その具体例としては、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、sec-ブチル基、tert-ブチル基、シクロヘキシル基などが挙げられる。
R33は、R32が結合している炭素原子とともに単環の脂環炭化水素構造を形成するのに必要な原子団を表す。脂環炭化水素構造は、環を構成する炭素原子の一部が、ヘテロ原子、又は、ヘテロ原子を有する基で置換されていてもよい。
R32は、メチル基、エチル基、n-プロピル基、イソプロピル基、tert-ブチル基又はシクロヘキシル基であることが好ましく、メチル基、エチル基、イソプロピル基又はtert-ブチル基であることがより好ましい。
R33が炭素原子とともに形成する単環の脂環炭化水素構造は、3~8員環であることが好ましく、5又は6員環であることがより好ましい。
R33が炭素原子とともに形成する単環の脂環炭化水素構造において、環を構成し得るヘテロ原子としては、酸素原子、硫黄原子等が挙げられ、ヘテロ原子を有する基としては、カルボニル基等が挙げられる。ただし、ヘテロ原子を有する基は、エステル基(エステル結合)ではないことが好ましい。
R33が炭素原子とともに形成する単環の脂環炭化水素構造は、炭素原子と水素原子とのみから形成されることが好ましい。
一般式(3)で表される構造を有する繰り返し単位の具体例を以下に挙げるが、これらに限定されるものではない。
n個のYは、各々独立に、水素原子又は酸の作用により脱離する基を表す。但し、Yの少なくとも1つは、酸の作用により脱離する基を表す。
nは、1~4の整数を表し、1~2が好ましく、1がより好ましい。
アルコキシカルボニル基に含まれるアルキル基としては、上記R01~R03におけるアルキル基と同様のものが好ましい。
シクロアルキル基は、単環のシクロアルキル基であってもよく、多環のシクロアルキル基であってもよい。好ましくは、シクロプロピル基、シクロペンチル基及びシクロヘキシル基等の炭素数3~8の単環のシクロアルキル基が挙げられる。なお、これらシクロアルキル基は、置換基を有していてもよい。
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、フッ素原子がより好ましい。
Ar1としての芳香環基は、炭素数6~14のものが好ましく、例えば、ベンゼン環、トルエン環又はナフタレン環が挙げられる。なお、これら芳香環基は、置換基を有していてもよい。
上記Yの少なくとも1つとしての酸の作用により脱離する基は、上述したものを好適に挙げることできる。
Mは、単結合又は2価の連結基を表す。
Qは、アルキル基、シクロアルキル基、環状脂肪族基、芳香環基、アミノ基、アンモニウム基、メルカプト基、シアノ基又はアルデヒド基を表す。環状脂肪族基及び芳香環基は、ヘテロ原子を含んでいてもよい。
Q、M、L1の少なくとも2つが互いに結合して、5員又は6員環を形成していてもよい。
L1及びL2としてのシクロアルキル基は、例えば炭素数3~15のシクロアルキル基であり、具体的には、シクロペンチル基、シクロヘキシル基、ノルボルニル基及びアダマンチル基が挙げられる。
L1及びL2としてのアリール基は、例えば炭素数6~15のアリール基であり、具体的には、フェニル基、トリル基、ナフチル基及びアントリル基が挙げられる。
L1及びL2としてのアラルキル基は、例えば炭素数6~20のアラルキル基であり、具体的には、ベンジル基及びフェネチル基が挙げられる。
Qとしての環状脂肪族基又は芳香環基としては、例えば、上述したL1及びL2としてのシクロアルキル基及びアリール基が挙げられる。これらシクロアルキル基及びアリール基は、好ましくは、炭素数3~15の基である。
Qとしてのヘテロ原子を含んだ環状脂肪族基又は芳香環基としては、例えば、チイラン、シクロチオラン、チオフェン、フラン、ピロール、ベンゾチオフェン、ベンゾフラン、ベンゾピロール、トリアジン、イミダゾール、ベンゾイミダゾール、トリアゾール、チアジアゾール、チアゾール及びピロリドン等の複素環構造を有した基が挙げられる。但し、炭素とヘテロ原子とで形成される環、又は、ヘテロ原子のみによって形成される環であれば、これらに限定されない。
Q、M及びL1の少なくとも2つが互いに結合して形成し得る環構造としては、例えば、これらがプロピレン基又はブチレン基を形成してなる5員又は6員環構造が挙げられる。なお、この5員又は6員環構造は、酸素原子を含有している。
-(M-Q)で表される基としては、炭素数1~20の基が好ましく、炭素数1~10の基がより好ましく、炭素数1~8が更に好ましい。
R1は、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルキルオキシカルボニル基を表す。
ARがナフチル基、アントリル基又はフルオレン基である場合、Rnが結合している炭素原子とARとの結合位置には、特に制限はない。例えば、ARがナフチル基である場合、この炭素原子は、ナフチル基のα位に結合していてもよく、β位に結合していてもよい。或いは、ARがアントリル基である場合、この炭素原子は、アントリル基の1位に結合していてもよく、2位に結合していてもよく、9位に結合していてもよい。
ARとしてのアリール基は、それぞれ、1以上の置換基を有していてもよい。このような置換基の具体例としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基、ペンチル基、ヘキシル基、オクチル基及びドデシル基等の炭素数が1~20の直鎖又は分岐鎖アルキル基、これらアルキル基部分を含んだアルコキシ基、シクロペンチル基及びシクロヘキシル基等のシクロアルキル基、これらシクロアルキル基部分を含んだシクロアルコキシ基、水酸基、ハロゲン原子、アリール基、シアノ基、ニトロ基、アシル基、アシルオキシ基、アシルアミノ基、スルホニルアミノ基、アルキルチオ基、アリールチオ基、アラルキルチオ基、チオフェンカルボニルオキシ基、チオフェンメチルカルボニルオキシ基、及びピロリドン残基等のヘテロ環残基が挙げられる。この置換基としては、炭素数1~5の直鎖若しくは分岐鎖アルキル基、これらアルキル基部分を含んだアルコキシ基が好ましく、パラメチル基又はパラメトキシ基がより好ましい。
更に、この環は、置換基を有していてもよい。この置換基としては、Rnが有していてもよい更なる置換基について後述するものと同様のものが挙げられる。
また、一般式(BZ)により表される繰り返し単位は、ラフネス性能の観点から、2個以上の芳香環を含有ことが好ましい。この繰り返し単位が有する芳香環の個数は、通常、5個以下であることが好ましく、3個以下であることがより好ましい。
また、一般式(BZ)により表される繰り返し単位において、ラフネス性能の観点から、ARは2個以上の芳香環を含有することがより好ましく、ARがナフチル基又はビフェニル基であることが更に好ましい。ARが有する芳香環の個数は、通常、5個以下であることが好ましく、3個以下であることがより好ましい。
Rnのアルキル基は、直鎖アルキル基であってもよく、分岐鎖アルキル基であってもよい。このアルキル基としては、好ましくは、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基、オクチル基及びドデシル基等の炭素数が1~20のものが挙げられる。Rnのアルキル基は、炭素数1~5のものが好ましく、炭素数1~3のものがより好ましい。
Rnのシクロアルキル基としては、例えば、シクロペンチル基及びシクロヘキシル基等の炭素数が3~15のものが挙げられる。
Rnのアリール基としては、例えば、フェニル基、キシリル基、トルイル基、クメニル基、ナフチル基及びアントリル基等の炭素数が6~14のものが好ましい。
R1は、上述したように、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルキルオキシカルボニル基を表す。
R1のアルキル基及びシクロアルキル基としては、例えば、先にRnについて説明したのと同様のものが挙げられる。これらアルキル基及びシクロアルキル基の各々は、置換基を有していてもよい。この置換基としては、例えば、先にRnについて説明したのと同様のものが挙げられる。
R1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。中でも、フッ素原子が特に好ましい。
R1のアルキルオキシカルボニル基に含まれるアルキル基部分としては、例えば、先にR1のアルキル基として挙げた構成を採用することができる。
RnとARとが互いに結合して非芳香族環を形成することが好ましく、これにより、特に、ラフネス性能をより向上させることができる。
非芳香族環は、脂肪族環であっても、環員として酸素原子、窒素原子、硫黄原子等のヘテロ原子を含むヘテロ環であってもよい。
非芳香族環は、置換基を有していてもよい。この置換基としては、例えば、Rnが有していてもよい更なる置換基について先に説明したのと同様のものが挙げられる。
ラクトン基又はスルトン基としては、ラクトン構造又はスルトン構造を有していればいずれでも用いることができるが、好ましくは5~7員環のラクトン構造又はスルトン構造であり、5~7員環のラクトン構造又はスルトン構造にビシクロ構造、スピロ構造を形成する形で他の環構造が縮環しているものが好ましい。下記一般式(LC1-1)~(LC1-17)、(SL1-1)及び(SL1-2)のいずれかで表されるラクトン構造又はスルトン構造を有する繰り返し単位を有することがより好ましい。また、ラクトン構造又はスルトン構造が主鎖に直接結合していてもよい。好ましいラクトン構造又はスルトン構造としては(LC1-1)、(LC1-4)、(LC1-5)、(LC1-8)であり、(LC1-4)であることがより好ましい。特定のラクトン構造又はスルトン構造を用いることでラインウィズスラフネス(LWR)、現像欠陥が良好になる。
水酸基又はシアノ基を有する繰り返し単位の具体例としては、米国公開特許2012/0135348号公報の段落0340に開示された繰り返し単位を挙げることができるが、本発明はこれらに限定されない。
アルカリ可溶性基を有する繰り返し単位の含有量は、樹脂(A)中の全繰り返し単位に対し、0~20mol%が好ましく、より好ましくは3~15mol%、更に好ましくは5~10mol%である。
アルカリ可溶性基を有する繰り返し単位の具体例としては、米国公開特許2012/0135348号公報の段落0344に開示された繰り返し単位を挙げることができるが、本発明は、これに限定されるものではない。
フェノール性水酸基とは、芳香環基の水素原子を水酸基で置換してなる基である。芳香環は単環又は多環の芳香環であり、例えば、ベンゼン環、ナフタレン環、アントラセン環、フルオレン環、フェナントレン環などの炭素数6~18の置換基を有していてもよい芳香族炭化水素環、又は、例えば、チオフェン環、フラン環、ピロール環、ベンゾチオフェン環、ベンゾフラン環、ベンゾピロール環、トリアジン環、イミダゾール環、ベンゾイミダゾール環、トリアゾール環、チアジアゾール環、チアゾール環等のヘテロ環を含む芳香環ヘテロ環を挙げることができる。なかでも、ベンゼン環、ナフタレン環が解像性の観点で好ましく、ベンゼン環が最も好ましい。
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。Raは、水素原子、メチル基、ヒドロキシメチル基、トリフルオロメチル基が好ましく、水素原子、メチル基が特に好ましい。
R5が有する環状構造には、単環式炭化水素基及び多環式炭化水素基が含まれる。単環式炭化水素基としては、たとえば、シクロペンチル基、シクロヘキシル基、シクロへプチル基、シクロオクチル基などの炭素数3~12のシクロアルキル基、シクロへキセニル基など炭素数3~12のシクロアルケニル基が挙げられる。好ましい単環式炭化水素基としては、炭素数3~7の単環式炭化水素基であり、より好ましくは、シクロペンチル基、シクロヘキシル基が挙げられる。
多環式炭化水素基には環集合炭化水素基、架橋環式炭化水素基が含まれ、環集合炭化水素基の例としては、ビシクロヘキシル基、パーヒドロナフタレニル基などが含まれる。架橋環式炭化水素環として、例えば、ピナン、ボルナン、ノルピナン、ノルボルナン、ビシクロオクタン環(ビシクロ[2.2.2]オクタン環、ビシクロ[3.2.1]オクタン環等)などの2環式炭化水素環及び、ホモブレダン、アダマンタン、トリシクロ[5.2.1.02,6]デカン、トリシクロ[4.3.1.12,5]ウンデカン環などの3環式炭化水素環、テトラシクロ[4.4.0.12,5.17,10]ドデカン、パーヒドロ-1,4-メタノ-5,8-メタノナフタレン環などの4環式炭化水素環などが挙げられる。また、架橋環式炭化水素環には、縮合環式炭化水素環、例えば、パーヒドロナフタレン(デカリン)、パーヒドロアントラセン、パーヒドロフェナントレン、パーヒドロアセナフテン、パーヒドロフルオレン、パーヒドロインデン、パーヒドロフェナレン環などの5~8員シクロアルカン環が複数個縮合した縮合環も含まれる。
好ましい架橋環式炭化水素環として、ノルボルニル基、アダマンチル基、ビシクロオクタニル基、トリシクロ[5、2、1、02,6]デカニル基、などが挙げられる。より好ましい架橋環式炭化水素環としてノルボニル基、アダマンチル基が挙げられる。
これらの脂環式炭化水素基は置換基を有していても良く、好ましい置換基としてはハロゲン原子、アルキル基、水素原子が置換されたヒドロキシル基、水素原子が置換されたアミノ基などが挙げられる。好ましいハロゲン原子としては臭素、塩素、フッ素原子、好ましいアルキル基としてはメチル、エチル、ブチル、t-ブチル基が挙げられる。上記のアルキル基は更に置換基を有していても良く、更に有していてもよい置換基としては、ハロゲン原子、アルキル基、水素原子が置換されたヒドロキシル基、水素原子が置換されたアミノ基を挙げることができる。
上記水素原子が置換された基としては、たとえばアルキル基、シクロアルキル基、アラルキル基、置換メチル基、置換エチル基、アルコキシカルボニル基、アラルキルオキシカルボニル基が挙げられる。好ましいアルキル基としては、炭素数1~4のアルキル基、好ましい置換メチル基としてはメトキシメチル、メトキシチオメチル、ベンジルオキシメチル、t-ブトキシメチル、2-メトキシエトキシメチル基、好ましい置換エチル基としては、1-エトキシエチル、1-メチル-1-メトキシエチル、好ましいアシル基としては、ホルミル、アセチル、プロピオニル、ブチリル、イソブチリル、バレリル、ピバロイル基などの炭素数1~6の脂肪族アシル基、アルコキシカルボニル基としては炭素数1~4のアルコキシカルボニル基などが挙げられる。
樹脂(A)は、極性基を持たない脂環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含有していても含有していなくてもよいが、含有する場合、この繰り返し単位の含有量は、樹脂(A)中の全繰り返し単位に対し、1~40モル%が好ましく、より好ましくは2~20モル%である。
極性基を持たない脂環炭化水素構造を有し、酸分解性を示さない繰り返し単位の具体例としては、米国公開特許2012/0135348号公報の段落0354に開示された繰り返し単位を挙げることができるが、本発明はこれらに限定されない。
これにより、本発明の組成物に用いられる樹脂に要求される性能、特に、(1)塗布溶剤に対する溶解性、(2)製膜性(ガラス転移点)、(3)アルカリ現像性、(4)膜べり(親疎水性、酸基選択)、(5)未露光部の基板への密着性、(6)ドライエッチング耐性、等の微調整が可能となる。
その他にも、上記種々の繰り返し構造単位に相当する単量体と共重合可能である付加重合性の不飽和化合物であれば、共重合されていてもよい。
本発明の組成物に用いられる樹脂(A)において、各繰り返し構造単位の含有モル比はレジストのドライエッチング耐性や標準現像液適性、基板密着性、レジストプロファイル、更にはレジストの一般的な必要性能である解像力、耐熱性、感度等を調節するために適宜設定される。
重合反応は窒素やアルゴンなど不活性ガス雰囲気下で行われることが好ましい。重合開始剤として市販のラジカル開始剤(アゾ系開始剤、パーオキサイドなど)を用いて、重合を開始させる。ラジカル開始剤としてはアゾ系開始剤が好ましく、エステル基、シアノ基、カルボキシル基を有するアゾ系開始剤が好ましい。好ましい開始剤としては、アゾビスイソブチロニトリル、アゾビスジメチルバレロニトリル、ジメチル2,2'-アゾビス(2-メチルプロピオネート)などが挙げられる。所望により開始剤を追加、あるいは分割で添加し、反応終了後、溶剤に投入して粉体あるいは固形回収等の方法で所望のポリマーを回収する。反応の濃度は5~50質量%であり、好ましくは10~30質量%である。反応温度は、通常10~150℃であり、好ましくは30~120℃、更に好ましくは60~100℃である。
樹脂(A)の重量平均分子量が上記範囲内であることにより、樹脂(A)のガラス転移温度を、より確実に、155℃以上としやすく、また、レジストパターン(スペース幅が10μm、ピッチ幅が100μm、レジスト膜部の厚さが7.5μmの孤立スペースパターン)の軟化点を、より確実に、130℃以上としやすくなる。
分散度(分子量分布)は、通常1.0~3.0であり、好ましくは1.0~2.6、更に好ましくは1.0~2.0、特に好ましくは1.1~2.0の範囲のものが使用される。分子量分布の小さいものほど、解像度、レジスト形状が優れ、且つレジストパターンの側壁がスムーズであり、ラフネス性に優れる。
また、樹脂(A)のガラス転移温度は、200℃以下であることが好ましく、195℃以下であることがより好ましく、190℃以下であることが更に好ましい。
ガラス転移温度の測定方法は、上述の通りである。
樹脂(A)は、ガラス転移温度が155℃以上であれば特に限定されず、このような樹脂は、上記の通り、樹脂(A)が有していても良い繰り返し単位(特にフェノール性水酸基を有する繰り返し単位)の含有量や、重量平均分子量などを上記した好適な範囲内とすることにより、好適に得ることができる。
樹脂(A)の組成物全体中の含有量は、組成物の全固形分に対して50~90質量%が好ましく、より好ましくは50~80質量%である。
樹脂(A)の含有量を上記範囲とすることにより、レジストパターン(スペース幅が10μm、ピッチ幅が100μm、レジスト膜部の厚さが7.5μmの孤立スペースパターン)の軟化点を、より確実に、130℃以上とすることができる。
本発明の組成物は、ガラス転移温度が150℃以下の化合物(B)を含有する。
化合物(B)としての樹脂(単に、以下、「樹脂(B)」ともいう)は、樹脂(A)で挙げた繰り返し単位を有する樹脂を挙げることができる。
樹脂(B)は、ガラス転移温度が150℃以下であれば、特に限定されないが、フェノール性水酸基を有する繰り返し単位の含有量が、樹脂(B)の全繰り返し単位に対して、53mol%以下であることが好ましく、50mol%以下であることがより好ましい。これにより、樹脂(B)のガラス転移温度を、好適に、150℃以下とすることができる。
樹脂(B)がフェノール性水酸基を有する繰り返し単位を有する場合、その含有量は、樹脂(B)の全繰り返し単位に対して、10mol%以上であることが好ましく、20mol%以上であることがより好ましい。
樹脂(B)は、フェノール性水酸基を有する繰り返し単位としては、ヒドロキシスチレンに由来する繰り返し単位を有することが好ましい。
本発明の化合物(B)としての樹脂の分散度(分子量分布)の好ましい範囲は、樹脂(A)において記載したものと同様である。
ポリエーテル系化合物は、2個以上のエーテル結合を有する化合物である。ポリエーテル系化合物によれば、ガラス転移温度が150℃以下という要件を好適に達成できる。
ポリエーテル系化合物としては、下記一般式(1)で表される部分構造を有する化合物が挙げられる。
上記一般式(1)中、nは、2以上の整数を表す。なかでも、2~20の整数であることが好ましい。複数あるR11は同一であっても異なってもよい。nの平均値は、2~25であることが好ましく、2~10であることがより好ましく、4~8であることがさらに好ましい。
上記一般式(1)中、*は、結合手を表す。
上記一般式(1-1)中、R12およびR13は、それぞれ独立に、水素原子又はアルキル基を表す。アルキル基の炭素数は特に制限されないが、1~15であることが好ましい。
上記一般式(1-1)中、mは、2以上の整数を表す。mは、2~20の整数であることが好ましく、そのなかでも、DOF(Depth of focus)がより大きくなる理由から、10以下であることがより好ましい。複数あるR11は同一であっても異なってもよい。mの平均値は、DOFがより大きくなる理由から、上限は25以下であることが好ましく、20以下であることがより好ましく、10以下であることがさらに好ましく、8以下であることが特に好ましく、6以下であることが最も好ましい。下限は、2以上であることが好ましく、4以上であることがより好ましい。より具体的には、mの平均値は、2~25であることが好ましく、2~15であることがより好ましく、2~8であることがさらに好ましく、4~8であることが特に好ましく、4~6であることが最も好ましい。
上記一般式(1-2)中のmの定義および好適な態様は、上述した一般式(1-1)中のmと同じである。
上記一般式(1-2)で表される化合物としては、例えば、クラウンエーテルが挙げられる。
これにより、厚膜の(例えば1μm以上の厚さを有する)レジスト膜から得られたレジストパターンが、測長SEMの真空チャンバー内にて測定される際に、クラックが発生しにくくなる。その結果、レジストパターンの性能評価をより正確に実施できる。
上記効果が得られる理由は定かではないが、以下の通りと推測される。
Rは、水素原子又は水酸基を表す。
一般式(a)で表される基を有するポリエーテル系化合物の沸点は、典型的には、550℃以下である。
ここで、ClogP値とは、繰り返し単位に対応するモノマー(不飽和二重結合基を有する化合物)のClogP値であり、Chem DrawUltra ver. 12.0.2.1076 (Cambridge corporation社)による算出値である。
化合物(B)が樹脂である場合、そのガラス転移温度は、100℃以上であることが好ましく、120℃以上であることがより好ましく、130℃以上であることが更に好ましい。
化合物(B)が樹脂(重合体)でない場合、そのガラス転移温度は、-20℃以上であることが好ましく、-15℃以上であることが好ましい。この場合、化合物(B)のガラス転移温度は、通常、0℃以下である。
ガラス転移温度の測定方法は、上述の通りである。
化合物(B)は、ガラス転移温度が150℃以下であれば特に限定されず、このような化合物が樹脂である場合は、上記の通り、樹脂(B)が有していても良い繰り返し単位(特にフェノール性水酸基を有する繰り返し単位)の含有量や、重量平均分子量などを上記した好適な範囲内とすることにより、また、化合物(B)が樹脂でない場合は、化合物の種類を適宜選択することにより(例えば、上記のように、ポリエーテル系化合物を選択することなどにより)、好適に得ることができる。
化合物(B)の含有量を上記範囲とすることにより、レジストパターン(スペース幅が10μm、ピッチ幅が100μm、レジスト膜部の厚さが7.5μmの孤立スペースパターン)の軟化点を、より確実に、170℃以下とすることができる。
本発明の組成物は、酸発生剤を含有することが好ましい。酸発生剤は、活性光線又は放射線の照射により酸を発生する化合物(以下、「酸発生剤」とも言う)であれば特に制限されない。
酸発生剤は、活性光線又は放射線の照射により有機酸を発生する化合物であることが好ましい。
酸発生剤が、低分子化合物の形態である場合、分子量が3000以下であることが好ましく、2000以下であることがより好ましく、1000以下であることが更に好ましい。
酸発生剤が、重合体の一部に組み込まれた形態である場合、前述した樹脂(A)の一部に組み込まれてもよく、樹脂(A)とは異なる樹脂に組み込まれてもよい。酸発生剤が、重合体の一部に組み込まれた形態である場合の具体例としては、例えば、特開2013-54196の段落<0191>~<0209>を挙げることができる。
例えば、酸発生剤としては、ジアゾニウム塩、ホスホニウム塩、スルホニウム塩、ヨードニウム塩、イミドスルホネート、オキシムスルホネート、ジアゾジスルホン、ジスルホン、o-ニトロベンジルスルホネートを挙げることができる。
pKa(酸強度)とは、酸の強さを定量的に表すための指標のひとつであり、酸性度定数と同義である。酸から水素イオンが放出される解離反応を考え、その平衡定数Kaをその負の常用対数pKaによって表したものである。pKaが小さいほど強い酸であることを示す。本発明では、ACD(Advanced Chemistry Development)社製解析ソフト、ACD/pKa DB V8.0を用いた計算によりに算出される。
R201、R202及びR203は、各々独立に、有機基を表す。
R201、R202及びR203としての有機基の炭素数は、一般的に1~30、好ましくは1~20である。
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、エステル結合、アミド結合、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、アルキレン基(例えば、ブチレン基、ペンチレン基)を挙げることができる。
Z-は、非求核性アニオンを表す。
Z-としての非求核性アニオンとしては、例えば、スルホン酸アニオン、カルボン酸アニオン、スルホニルイミドアニオン、ビス(アルキルスルホニル)イミドアニオン、トリス(アルキルスルホニル)メチルアニオン等を挙げることができる。
スルホン酸アニオンとしては、例えば、脂肪族スルホン酸アニオン、芳香族スルホン酸アニオン、カンファースルホン酸アニオンなどが挙げられる。
カルボン酸アニオンとしては、例えば、脂肪族カルボン酸アニオン、芳香族カルボン酸アニオン、アラルキルカルボン酸アニオンなどが挙げられる。
脂肪族スルホン酸アニオン及び芳香族スルホン酸アニオンにおけるアルキル基、シクロアルキル基及びアリール基は、置換基を有していてもよい。
その他の非求核性アニオンとしては、例えば、フッ素化燐(例えば、PF6 -)、フッ素化硼素(例えば、BF4 -)、フッ素化アンチモン等(例えば、SbF6 -)を挙げることができる。
Xfは、各々独立に、フッ素原子、又は少なくとも一つのフッ素原子で置換されたアルキル基を表す。
R7及びR8は、各々独立に、水素原子、フッ素原子、アルキル基、又は、少なくとも一つのフッ素原子で置換されたアルキル基を表し、複数存在する場合のR7及びR8は、それぞれ同一でも異なっていてもよい。
Lは、2価の連結基を表し、複数存在する場合のLは同一でも異なっていてもよい。
Aは、環状構造を含む有機基を表す。
xは、1~20の整数を表し、yは、0~10の整数を表す。zは、0~10の整数を表す。
Xfとして、好ましくは、フッ素原子又は炭素数1~4のパーフルオロアルキル基である。具体的には、フッ素原子、CF3、C2F5、C3F7、C4F9、C5F11、C6F13、C7F15、C8F17、CH2CF3、CH2CH2CF3、CH2C2F5、CH2CH2C2F5、CH2C3F7、CH2CH2C3F7、CH2C4F9、CH2CH2C4F9が挙げられ、中でもフッ素原子、CF3が好ましい。特に、双方のXfがフッ素原子であることが好ましい。
Riについてのアルキル基の具体例及び好ましい例としては、一般式(1)におけるR1~R4として前述した具体例及び好ましい例と同様のものが挙げられる。
脂環基としては、単環でも多環でもよく、シクロペンチル基、シクロヘキシル基、シクロオクチル基などの単環のシクロアルキル基、ノルボルニル基、ノルボルネン-イル基、トリシクロデカニル基(例えば、トリシクロ[5.2.1.0(2,6)]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、アダマンチル基などの多環のシクロアルキル基が好ましく、アダマンチル基が特に好ましい。また、ピペリジン基、デカヒドロキノリン基、デカヒドロイソキノリン基等の窒素原子含有脂環基も好ましい。中でも、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、アダマンチル基、デカヒドロキノリン基、デカヒドロイソキノリン基といった炭素数7以上のかさ高い構造を有する脂環基が、PEB(露光後加熱)工程での膜中拡散性を抑制できる点から好ましい。中でも、アダマンチル基、デカヒドロイソキノリン基が特に好ましい。
アリール基としては、ベンゼン環、ナフタレン環、フェナンスレン環、アントラセン環が挙げられる。中でも193nmにおける光吸光度の観点から低吸光度のナフタレンが好ましい。
複素環基としては、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、ピリジン環が挙げられる。中でもフラン環、チオフェン環、ピリジン環が好ましい。その他の好ましい複素環基として、下記に示す構造を挙げることができる(式中、Xはメチレン基又は酸素原子を表し、Rは1価の有機基を表す)。
なお、環状構造を含む有機基を構成する炭素(環形成に寄与する炭素)はカルボニル炭素であっても良い。
ジスルホニルイミド酸アニオンとしては、ビス(アルキルスルホニル)イミドアニオンであることが好ましい。
ビス(アルキルスルホニル)イミドアニオンにおけるアルキル基は、炭素数1~5のアルキル基が好ましい。
ビス(アルキルスルホニル)イミドアニオンにおける2つのアルキル基が互いに連結してアルキレン基(好ましくは炭素数2~4)を成し、イミド基及び2つのスルホニル基とともに環を形成していてもよい。ビス(アルキルスルホニル)イミドアニオンが形成していてもよい上記の環構造としては、5~7員環であることが好ましく、6員環であることがより好ましい。
これらのアルキル基、及び2つのアルキル基が互いに連結して成すアルキレン基が有し得る置換基としてはハロゲン原子、ハロゲン原子で置換されたアルキル基、アルコキシ基、アルキルチオ基、アルキルオキシスルホニル基、アリールオキシスルホニル基、シクロアルキルアリールオキシスルホニル基等を挙げることができ、フッ素原子又はフッ素原子で置換されたアルキル基が好ましい。
なお、一般式(ZI)で表される構造を複数有する化合物であってもよい。例えば、一般式(ZI)で表される化合物のR201~R203の少なくとも1つが、一般式(ZI)で表されるもうひとつの化合物のR201~R203の少なくとも一つと、単結合又は連結基を介して結合した構造を有する化合物であってもよい。
化合物(ZI-1)は、上記一般式(ZI)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化合物、即ち、アリールスルホニウムをカチオンとする化合物である。
アリールスルホニウム化合物は、R201~R203の全てがアリール基でもよいし、R201~R203の一部がアリール基で、残りがアルキル基又はシクロアルキル基でもよい。
アリールスルホニウム化合物としては、例えば、トリアリールスルホニウム化合物、ジアリールアルキルスルホニウム化合物、アリールジアルキルスルホニウム化合物、ジアリールシクロアルキルスルホニウム化合物、アリールジシクロアルキルスルホニウム化合物を挙げることができる。
アリールスルホニウム化合物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の直鎖又は分岐アルキル基及び炭素数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、シクロヘキシル基等を挙げることができる。
化合物(ZI-2)は、式(ZI)におけるR201~R203が、各々独立に、芳香環を有さない有機基を表す化合物である。ここで芳香環とは、ヘテロ原子を含有する芳香族環も包含するものである。
R201~R203としての芳香環を含有しない有機基は、一般的に炭素数1~30、好ましくは炭素数1~20である。
R201~R203は、各々独立に、好ましくはアルキル基、シクロアルキル基、アリル基、ビニル基であり、更に好ましくは直鎖又は分岐の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メチル基、特に好ましくは直鎖又は分岐2-オキソアルキル基である。
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、ニトロ基によって更に置換されていてもよい。
化合物(ZI-3)とは、以下の一般式(ZI-3)で表される化合物であり、フェナシルスルフォニウム塩構造を有する化合物である。
R1c~R5cは、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アルキルカルボニルオキシ基、シクロアルキルカルボニルオキシ基、ハロゲン原子、水酸基、ニトロ基、アルキルチオ基又はアリールチオ基を表す。
R6c及びR7cは、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアリール基を表す。
Rx及びRyは、各々独立に、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。
上記環構造としては、芳香族若しくは非芳香族の炭化水素環、芳香族若しくは非芳香族の複素環、又は、これらの環が2つ以上組み合わされてなる多環縮合環を挙げることができる。環構造としては、3~10員環を挙げることができ、4~8員環であることが好ましく、5又は6員環であることがより好ましい。
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であることが好ましく、アルキレン基としては、メチレン基、エチレン基等を挙げることができる。
Zc-は、非求核性アニオンを表し、一般式(ZI)に於けるZ-と同様の非求核性アニオンを挙げることができる。
R1c~R5cとしてのアルキルカルボニルオキシ基及びアルキルチオ基におけるアルキル基の具体例は、上記R1c~R5cとしてのアルキル基の具体例と同様である。
R1c~R5cとしてのシクロアルキルカルボニルオキシ基におけるシクロアルキル基の具体例は、上記R1c~R5cとしてのシクロアルキル基の具体例と同様である。
R1c~R5cとしてのアリールオキシ基及びアリールチオ基におけるアリール基の具体例は、上記R1c~R5cとしてのアリール基の具体例と同様である。
化合物(ZI-4)は、下記一般式(ZI-4)で表される。
R13は水素原子、フッ素原子、水酸基、アルキル基、シクロアルキル基、アルコキシ基、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、複数存在する場合は各々独立して、水酸基、アルキル基、シクロアルキル基、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を表す。これらの基は置換基を有してもよい。
R15は各々独立して、アルキル基、シクロアルキル基又はナフチル基を表す。これらの基は置換基を有してもよい。2個のR15が互いに結合して環を形成してもよい。2個の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、窒素原子などのヘテロ原子を含んでもよい。一態様において、2個の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。
lは0~2の整数を表す。
rは0~8の整数を表す。
Z-は、非求核性アニオンを表し、一般式(ZI)に於けるZ-と同様の非求核性アニオンを挙げることができる。
本発明における一般式(ZI-4)で表される化合物のカチオンとしては、特開2010-256842号公報の段落<0121>、<0123>、<0124>、及び、特開2011-76056号公報の段落<0127>、<0129>、<0130>等に記載のカチオンを挙げることができる。
一般式(ZII)、(ZIII)中、R204~R207は、各々独立に、アリール基、アルキル基又はシクロアルキル基を表す。
R204~R207のアリール基としてはフェニル基、ナフチル基が好ましく、更に好ましくはフェニル基である。R204~R207のアリール基は、酸素原子、窒素原子、硫黄原子等を有する複素環構造を有するアリール基であってもよい。複素環構造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、ベンゾチオフェン等を挙げることができる。
R204~R207におけるアルキル基及びシクロアルキル基としては、好ましくは、炭素数1~10の直鎖又は分岐アルキル基(例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基)、炭素数3~10のシクロアルキル基(シクロペンチル基、シクロヘキシル基、ノルボニル基)を挙げることができる。
酸発生剤として、更に、下記一般式(ZIV)、(ZV)、(ZVI)で表される化合物も挙げられる。
Ar3及びAr4は、各々独立に、アリール基を表す。
R208、R209及びR210は、各々独立に、アルキル基、シクロアルキル基又はアリール基を表す。
Aは、アルキレン基、アルケニレン基又はアリーレン基を表す。
R208、R209及びR210のアルキル基及びシクロアルキル基の具体例としては、各々、上記化合物(ZI-2)におけるR201、R202及びR203としてのアルキル基及びシクロアルキル基の具体例と同様のものを挙げることができる。
Rb3~Rb5は、各々独立に、アルキル基、シクロアルキル基又はアリール基を表す。Rb3とRb4が結合して環構造を形成してもよい。
Rb3~Rb5として、好ましくは、炭素数1~4のパーフロロアルキル基であり、より好ましくは、炭素数1~3のパーフロロアルキル基である。
Rb3とRb4が結合して形成される基としては、アルキレン基、アリーレン基が挙げられる。
Rb3とRb4が結合して形成される基として、好ましくは、炭素数2~4のパーフロロアルキレン基であり、更に好ましくは、パーフロロプロピレン基である。Rb3とRb4が結合して環構造を形成することで環構造を形成しないものと比べて酸性度が向上し、組成物の感度が向上する。
Rc6は、パーフロロアルキレン基を表し、より好ましくは、炭素数2~4のパーフロロアルキレン基である。
Axは、単結合又は2価の連結基(好ましくは、-O-、-CO2-、-S-、-SO3-、-SO2N(Rd1)-)を表す。Rd1は、水素原子又はアルキル基を表し、Rc7と結合して環構造を形成してもよい。
Rc7は、水素原子、フッ素原子、アルキル基、シクロアルキル基又はアリール基を表す。Rc7のアルキル基、シクロアルキル基、アリール基は、置換基としてフッ素原子を有さないことが好ましい。
R201、R202及びR203は、各々独立に有機基を表す。
Xd-は、一般式(III)又は(IV)で表される酸のアニオンを表す。
アリールスルホニウム化合物は、R201~R203の全てがアリール基でもよいし、R201~R203の一部がアリール基で、残りがアルキル基、シクロアルキル基でもよい。
アリールスルホニウム化合物としては、例えば、トリアリールスルホニウム化合物、ジアリールアルキルスルホニウム化合物、アリールジアルキルスルホニウム化合物、ジアリールシクロアルキルスルホニウム化合物、アリールジシクロアルキルスルホニウム化合物を挙げることができる。
アリールスルホニウム化合物のアリール基としてはフェニル基、ナフチル基などのアリール基、インドール残基、ピロール残基、などのヘテロアリール基が好ましく、更に好ましくはフェニル基、インドール残基である。アリールスルホニム化合物が2つ以上のアリール基を有する場合に、2つ以上あるアリール基は同一であっても異なっていてもよい。
アリールスルホニウム化合物が必要に応じて有しているアルキル基は、炭素数1~15の直鎖、分岐状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-ブチル基等を挙げることができる。
アリールスルホニウム化合物が必要に応じて有しているシクロアルキル基は、炭素数3~15のシクロアルキル基が好ましく、例えば、シクロプロピル基、シクロブチル基、シクロヘキシル基等を挙げることができる。
R201~R203のアリール基、アルキル基、シクロアルキル基は、アルキル基(例えば炭素数1~15)、シクロアルキル基(例えば炭素数3~15)、アリール基(例えば炭素数6~14)、アルコキシ基(例えば炭素数1~15)、ハロゲン原子、水酸基、フェニルチオ基を置換基として有してもよい。好ましい置換基としては炭素数1~12の直鎖、分岐状アルキル基、炭素数3~12のシクロアルキル基、炭素数1~12の直鎖、分岐又は環状のアルコキシ基であり、最も好ましくは炭素数1~4のアルキル基、炭素数1~4のアルコキシ基である。置換基は、3つのR201~R203のうちのいずれか1つに置換していてもよいし、3つ全てに置換していてもよい。また、R201~R203がアリール基の場合に、置換基はアリール基のp-位に置換していることが好ましい。
アリールスルホニウムカチオンとして、好ましくは、置換していてもよいトリフェニルスルホニウムカチオン、置換していてもよいナフチルテトラヒドロチオフェニウムカチオン、置換していてもよいフェニルテトラヒドロチオフェニウムカチオンである。
化合物(ZI-2a)は、一般式(ZIa)におけるR201~R203が、各々独立に、芳香環を含有しない有機基を表す場合の化合物である。ここで芳香環とは、ヘテロ原子を有する芳香族環も包含するものである。
R201~R203としての芳香環を含有しない有機基は、一般的に炭素数1~30、好ましくは炭素数1~20である。
R201~R203は、各々独立に、好ましくはアルキル基、シクロアルキル基、アリル基、ビニル基であり、更に好ましくは直鎖、分岐、環状2-オキソアルキル基、アルコキシカルボニルメチル基、特に好ましくは直鎖、分岐2-オキソアルキル基である。
R201~R203としてのシクロアルキル基は、好ましくは、炭素数3~10のシクロアルキル基(シクロペンチル基、シクロヘキシル基、ノルボニル基)を挙げることができる。R201~R203としてのシクロアルキル基は、環状2-オキソアルキル基であることがより好ましい。
R201~R203における直鎖、分岐、環状の2-オキソアルキル基は、好ましくは、上記のアルキル基、シクロアルキル基の2位に>C=Oを有する基を挙げることができる。
R201~R203としてのアルコキシカルボニルメチル基におけるアルコキシ基としては、好ましくは炭素数1~5のアルコキシ基(メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペントキシ基)を挙げることができる。
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、ニトロ基によって更に置換されていてもよい。
R1c~R5cは、各々独立に、水素原子、アルキル基、シクロアルキル基、アルコキシ基、又はハロゲン原子を表す。
R6c及びR7cは、各々独立に、水素原子、アルキル基又はシクロアルキル基を表す。
Rx及びRyは、各々独立に、アルキル基、シクロアルキル基、アリル基、又はビニル基を表す。
R1c~R5c中のいずれか2つ以上、及びRxとRyは、それぞれ結合して環構造を形成しても良く、この環構造は、酸素原子、硫黄原子、エステル結合、アミド結合を含んでいてもよい。R1c~R5c中のいずれか2つ以上、及びRxとRyが結合して形成する基としては、ブチレン基、ペンチレン基等を挙げることができる。
Xd-は、一般式(III)又は(IV)で表される酸のアニオンを表し、一般式(ZIa)に於ける、Xd-と同様のものである。
R1c~R7cとしてのシクロアルキル基は、例えば、炭素数3~20個のシクロアルキル基、好ましくは、炭素数3~8個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)を挙げることができる。
R1c~R5cとしてのアルコキシ基は、直鎖、分岐、環状のいずれであってもよく、例えば炭素数1~10のアルコキシ基、好ましくは、炭素数1~5の直鎖及び分岐アルコキシ基(例えば、メトキシ基、エトキシ基、直鎖又は分岐プロポキシ基、直鎖又は分岐ブトキシ基、直鎖又は分岐ペントキシ基)、炭素数3~8の環状アルコキシ基(例えば、シクロペンチルオキシ基、シクロヘキシルオキシ基)を挙げることができる。
好ましくはR1c~R5cのうちいずれかが直鎖、分岐状アルキル基、シクロアルキル基又は直鎖、分岐、環状アルコキシ基であり、更に好ましくはR1cからR5cの炭素数の和が2~15である。これにより、より溶剤溶解性が向上し、保存時にパーティクルの発生が抑制される。
Rx及びRyとしてのシクロアルキル基は、R1c~R7cとしてのシクロアルキル基と同様のものを挙げることができる。Rx及びRyとしてのシクロアルキル基は、環状2-オキソアルキル基であることがより好ましい。
直鎖、分岐、環状2-オキソアルキル基は、R1c~R7cとしてのアルキル基、シクロアルキル基の2位に>C=Oを有する基を挙げることができる。
アルコキシカルボニルメチル基におけるアルコキシ基については、R1c~R5cとしてのアルコキシ基と同様のものを挙げることができる。
Rx、Ryは、好ましくは炭素数4個以上のアルキル基であり、より好ましくは6個以上、更に好ましくは8個以上のアルキル基である。
R204~R205は、各々独立に、アリール基、アルキル基又はシクロアルキル基を表す。
R204~R205のアリール基としては、フェニル基、ナフチル基が好ましく、更に好ましくはフェニル基である。
R204~R205としてのアルキル基は、直鎖、分岐状のいずれであってもよく、好ましくは、炭素数1~10の直鎖又は分岐アルキル基(例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基)を挙げることができる。
R204~R205としてのシクロアルキル基は、好ましくは、炭素数3~10のシクロアルキル基(シクロペンチル基、シクロヘキシル基、ノルボニル基)を挙げることができる。
R204~R207が有していてもよい置換基としては、例えば、アルキル基(例えば炭素数1~15)、シクロアルキル基(例えば炭素数3~15)、アリール基(例えば炭素数6~15)、アルコキシ基(例えば炭素数1~15)、ハロゲン原子、水酸基、フェニルチオ基等を挙げることができる。
酸発生剤は、公知の方法で合成することができ、例えば、特開2007-161707号公報に記載の方法に準じて合成することができる。
酸発生剤は、1種類単独又は2種類以上を組み合わせて使用することができる。
また、酸発生剤が上記一般式(ZI-3)又は(ZI-4)により表される場合(複数種存在する場合はその合計)には、その含有量は、組成物の全固形分を基準として、0.1~35質量%が好ましく、0.5~30質量%がより好ましく、0.5~25質量%が特に好ましい。
酸発生剤の具体例を以下に示すが、本発明はこれに限定されるものではない。
本発明の組成物は、疎水性樹脂を含有してもよい。なお、疎水性樹脂は樹脂(A)とは異なることが好ましい。
疎水性樹脂は前述のように界面に偏在するように設計されることが好ましいが、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/非極性物質を均一に混合することに寄与しなくてもよい。
疎水性樹脂を添加することの効果として、アウトガスの抑制などを挙げることができる。
“樹脂の側鎖部分に含有されたCH3部分構造”のいずれか1種以上を有することが好ましく、2種以上を有することがさらに好ましい。
疎水性樹脂が、フッ素原子及び/又は珪素原子を含む場合、疎水性樹脂に於ける上記フッ素原子及び/又は珪素原子は、樹脂の主鎖中に含まれていてもよく、側鎖中に含まれていてもよい。
フッ素原子を有するアルキル基(好ましくは炭素数1~10、より好ましくは炭素数1~4)は、少なくとも1つの水素原子がフッ素原子で置換された直鎖又は分岐アルキル基であり、更にフッ素原子以外の置換基を有していてもよい。
フッ素原子を有するシクロアルキル基は、少なくとも1つの水素原子がフッ素原子で置換された単環又は多環のシクロアルキル基であり、更にフッ素原子以外の置換基を有していてもよい。
フッ素原子を有するアリール基としては、フェニル基、ナフチル基などのアリール基の少なくとも1つの水素原子がフッ素原子で置換されたものが挙げられ、更にフッ素原子以外の置換基を有していてもよい。
R57~R68は、各々独立に、水素原子、フッ素原子又はアルキル基(直鎖若しくは分岐)を表す。但し、R57~R61の少なくとも1つ、R62~R64の少なくとも1つ、及びR65~R68の少なくとも1つは、各々独立に、フッ素原子又は少なくとも1つの水素原子がフッ素原子で置換されたアルキル基(好ましくは炭素数1~4)を表す。
R57~R61及びR65~R67は、全てがフッ素原子であることが好ましい。R62、R63及びR68は、少なくとも1つの水素原子がフッ素原子で置換されたアルキル基(好ましくは炭素数1~4)が好ましく、炭素数1~4のパーフルオロアルキル基であることが更に好ましい。R62とR63は、互いに連結して環を形成してもよい。
一般式(F3)で表される基の具体例としては、US2012/0251948A1〔0500〕に例示されたものを挙げることが出来る。
一般式(F4)で表される基の具体例としては、例えば、-C(CF3)2OH、-C(C2F5)2OH、-C(CF3)(CH3)OH、-CH(CF3)OH等が挙げられ、-C(CF3)2OHが好ましい。
フッ素原子を含む部分構造は、主鎖に直接結合してもよく、更に、アルキレン基、フェニレン基、エーテル結合、チオエーテル結合、カルボニル基、エステル結合、アミド結合、ウレタン結合及びウレイレン結合よりなる群から選択される基、或いはこれらの2つ以上を組み合わせた基を介して主鎖に結合してもよい。
アルキルシリル構造、又は環状シロキサン構造としては、特開2013-178370号公報の段落<0304>~<0307>に記載された部分構造などを挙げることができる。
フッ素原子又は珪素原子を有する繰り返し単位の例としては、US2012/0251948A1〔0519〕に例示されたものを挙げることが出来る。
ここで、疎水性樹脂中の側鎖部分が有するCH3部分構造は、エチル基、プロピル基等が有するCH3部分構造を包含するものである。
一方、疎水性樹脂の主鎖に直接結合しているメチル基(例えば、メタクリル酸構造を有する繰り返し単位のα-メチル基)は、主鎖の影響により疎水性樹脂の表面偏在化への寄与が小さいため、CH3部分構造に包含されないものとする。
一方、C-C主鎖から何らかの原子を介して存在するCH3部分構造は、本発明におけるCH3部分構造に該当するものとする。例えば、R11がエチル基(CH2CH3)である場合、本発明におけるCH3部分構造を「1つ」有するものとする。
R11~R14は、各々独立に、側鎖部分を表す。
側鎖部分のR11~R14としては、水素原子、1価の有機基などが挙げられる。
R11~R14についての1価の有機基としては、アルキル基、シクロアルキル基、アリール基、アルキルオキシカルボニル基、シクロアルキルオキシカルボニル基、アリールオキシカルボニル基、アルキルアミノカルボニル基、シクロ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などが挙げられ、これらの基は、更に置換基を有していてもよい。
Xb1は、水素原子又はメチル基であることが好ましい。
R2としては、1つ以上のCH3部分構造を有する、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アリール基、及び、アラルキル基が挙げられる。上記のシクロアルキル基、アルケニル基、シクロアルケニル基、アリール基、及び、アラルキル基は、更に、置換基としてアルキル基を有していてもよい。
R2は、1つ以上のCH3部分構造を有する、アルキル基又はアルキル置換シクロアルキル基が好ましい。
R2としての1つ以上のCH3部分構造を有する酸に安定な有機基は、CH3部分構造を2個以上10個以下有することが好ましく、2個以上8個以下有することがより好ましい。
一般式(II)で表される繰り返し単位の好ましい具体例を以下に挙げる。なお、本発明はこれに限定されるものではない。
以下、一般式(III)で表される繰り返し単位について詳細に説明する。
Xb2のアルキル基は、炭素数1~4のものが好ましく、メチル基、エチル基、プロピル基、ヒドロキシメチル基又はトリフルオロメチル基等が挙げられるが、水素原子である事が好ましい。
Xb2は、水素原子であることが好ましい。
R3は、酸に対して安定な有機基であるため、より具体的には、上記樹脂(A)において説明した“酸分解性基”を有さない有機基であることが好ましい。
R3としての1つ以上のCH3部分構造を有する酸に安定な有機基は、CH3部分構造を1個以上10個以下有することが好ましく、1個以上8個以下有することがより好ましく、1個以上4個以下有することが更に好ましい。
nは1から5の整数を表し、1~3の整数を表すことがより好ましく、1又は2を表すことが更に好ましい。
(x)酸基、
(y)ラクトン構造を有する基、酸無水物基、又は酸イミド基、
(z)酸の作用により分解する基
好ましい酸基としては、フッ素化アルコール基(好ましくはヘキサフルオロイソプロパノール)、スルホンイミド基、ビス(アルキルカルボニル)メチレン基が挙げられる。
酸基(x)を有する繰り返し単位の含有量は、疎水性樹脂中の全繰り返し単位に対し、1~50モル%が好ましく、より好ましくは3~35モル%、更に好ましくは5~20モル%である。
酸基(x)を有する繰り返し単位の具体例を以下に示すが、本発明は、これに限定されるものではない。式中、Rxは水素原子、CH3、CF3、又は、CH2OHを表す。
これらの基を含んだ繰り返し単位は、例えば、アクリル酸エステル及びメタクリル酸エステルによる繰り返し単位等の、樹脂の主鎖に直接この基が結合している繰り返し単位である。或いは、この繰り返し単位は、この基が連結基を介して樹脂の主鎖に結合している繰り返し単位であってもよい。或いは、この繰り返し単位は、この基を有する重合開始剤又は連鎖移動剤を重合時に用いて、樹脂の末端に導入されていてもよい。
ラクトン構造を有する基を有する繰り返し単位としては、例えば、先に樹脂(A)の項で説明したラクトン構造を有する繰り返し単位と同様のものが挙げられる。
疎水性樹脂が珪素原子を有する場合、珪素原子の含有量は、疎水性樹脂の重量平均分子量に対し、2~50質量%であることが好ましく、2~30質量%であることがより好ましい。また、珪素原子を含む繰り返し単位は、疎水性樹脂に含まれる全繰り返し単位中、10~100モル%であることが好ましく、20~100モル%であることがより好ましい。
また、疎水性樹脂は、1種で使用してもよいし、複数併用してもよい。
疎水性樹脂の組成物中の含有量は、本発明の組成物中の全固形分に対し、0.01~10質量%が好ましく、0.05~8質量%がより好ましく、0.1~7質量%が更に好ましい。
反応溶媒、重合開始剤、反応条件(温度、濃度等)、及び、反応後の精製方法は、樹脂(A)で説明した内容と同様であるが、疎水性樹脂の合成においては、反応の濃度が30~50質量%であることが好ましい。
本発明の組成物は、酸拡散制御剤(D)を含有することが好ましい。酸拡散制御剤(D)は、露光時に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(D)としては、塩基性化合物、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、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、又は、酸発生剤に対して相対的に弱酸となるオニウム塩を使用することができる。
R200、R201及びR202は、同一でも異なってもよく、水素原子、アルキル基(好ましくは炭素数1~20)、シクロアルキル基(好ましくは炭素数3~20)又はアリール基(炭素数6~20)を表し、ここで、R201とR202は、互いに結合して環を形成してもよい。
R203、R204、R205及びR206は、同一でも異なってもよく、炭素数1~20個のアルキル基を表す。
これら一般式(A)及び(E)中のアルキル基は、無置換であることがより好ましい。
好ましい化合物の具体例としては、US2012/0219913A1 <0379>に例示された化合物を挙げることができる。
好ましい塩基性化合物として、更に、フェノキシ基を有するアミン化合物、フェノキシ基を有するアンモニウム塩化合物、スルホン酸エステル基を有するアミン化合物及びスルホン酸エステル基を有するアンモニウム塩化合物を挙げることができる。
また、下記化合物も塩基性化合物として好ましい。
これらの塩基性化合物は、1種類を単独で用いてもよく、2種類以上を組み合わせて用いてもよい。
酸発生剤(複数種類有する場合はその合計)と塩基性化合物の組成物中の使用割合は、酸発生剤/塩基性化合物(モル比)=2.5~300であることが好ましい。即ち、感度、解像度の点からモル比は2.5以上が好ましく、露光後加熱処理までの経時によるレジストパターンの太りによる解像度の低下抑制の点から300以下が好ましい。酸発生剤/塩基性化合物(モル比)は、より好ましくは5.0~200、更に好ましくは7.0~150である。
酸の作用により脱離する基として、アセタール基、カルボネート基、カルバメート基、3級エステル基、3級水酸基、ヘミアミナールエーテル基が好ましく、カルバメート基、ヘミアミナールエーテル基であることが特に好ましい。
化合物(D-1)の分子量は、100~1000が好ましく、100~700がより好ましく、100~500が特に好ましい。
化合物(D-1)は、窒素原子上に保護基を有するカルバメート基を有してもよい。カルバメート基を構成する保護基としては、下記一般式(d-1)で表すことができる。
Rbは、各々独立に、水素原子、アルキル基(好ましくは炭素数1~10)、シクロアルキル基(好ましくは炭素数3~30)、アリール基(好ましくは炭素数3~30)、アラルキル基(好ましくは炭素数1~10)、又はアルコキシアルキル基(好ましくは炭素数1~10)を表す。Rbは相互に連結して環を形成していてもよい。
Rbが示すアルキル基、シクロアルキル基、アリール基、アラルキル基は、ヒドロキシル基、シアノ基、アミノ基、ピロリジノ基、ピペリジノ基、モルホリノ基、オキソ基等の官能基、アルコキシ基、ハロゲン原子で置換されていてもよい。Rbが示すアルコキシアルキル基についても同様である。
2つのRbが相互に連結して形成する環としては、脂環式炭化水素基、芳香族炭化水素基、複素環式炭化水素基若しくはその誘導体等が挙げられる。
一般式(d-1)で表される基の具体的な構造としては、US2012/0135348 A1 <0466>に開示された構造を挙げることができるが、これに限定されるものではない。
Rbは、上記一般式(d-1)におけるRbと同義であり、好ましい例も同様である。
lは0~2の整数を表し、mは1~3の整数を表し、l+m=3を満たす。
一般式(6)において、Raとしてのアルキル基、シクロアルキル基、アリール基、アラルキル基は、Rbとしてのアルキル基、シクロアルキル基、アリール基、アラルキル基が置換されていてもよい基として前述した基と同様な基で置換されていてもよい。
本発明における特に好ましい化合物(D-1)の具体的としては、US2012/0135348 A1 <0475>に開示された化合物を挙げることができるが、これに限定されるものではない。
本発明において、化合物(D-1)は、一種単独でも又は2種以上を混合しても使用することができる。
本発明の組成物における化合物(D-1)の含有量は、組成物の全固形分を基準として、0.001~20質量%であることが好ましく、より好ましくは0.001~10質量%、更に好ましくは0.01~5質量%である。
プロトンアクセプター性は、pH測定を行うことによって確認することができる。
Qは、-SO3H、-CO2H、又は-W1NHW2Rfを表す。ここで、Rfは、アルキル基(好ましくは炭素数1~20)、シクロアルキル基(好ましくは炭素数3~20)又はアリール基(好ましくは炭素数6~30)を表し、W1及びW2は、各々独立に、-SO2-又は-CO-を表す。
Aは、単結合又は2価の連結基を表す。
Xは、-SO2-又は-CO-を表す。
nは、0又は1を表す。
Bは、単結合、酸素原子、又は-N(Rx)Ry-を表す。ここで、Rxは水素原子又は1価の有機基を表し、Ryは単結合又は2価の有機基を表す。Rxは、Ryと結合して環を形成していてもよく、Rと結合して環を形成していてもよい。
Rは、プロトンアクセプター性官能基を有する1価の有機基を表す。
Aにおける2価の連結基としては、好ましくは炭素数2~12の2価の連結基であり、例えば、アルキレン基、フェニレン基等が挙げられる。より好ましくは少なくとも1つのフッ素原子を有するアルキレン基であり、好ましい炭素数は2~6、より好ましくは炭素数2~4である。アルキレン鎖中に酸素原子、硫黄原子などの連結基を有していてもよい。アルキレン基は、特に水素原子数の30~100%がフッ素原子で置換されたアルキレン基が好ましく、Q部位と結合した炭素原子がフッ素原子を有することがより好ましい。更にはパーフルオロアルキレン基が好ましく、パーフロロエチレン基、パーフロロプロピレン基、パーフロロブチレン基がより好ましい。
Rxにおけるアルキル基としては、置換基を有していてもよく、好ましくは炭素数1~20の直鎖及び分岐アルキル基であり、アルキル鎖中に酸素原子、硫黄原子、窒素原子を有していてもよい。
Rxにおけるシクロアルキル基としては、置換基を有していてもよく、好ましくは炭素数3~20の単環シクロアルキル基又は多環シクロアルキル基であり、環内に酸素原子、硫黄原子、窒素原子を有していてもよい。
Rxにおけるアリール基としては、置換基を有してもよく、好ましくは炭素数6~14のものが挙げられ、例えば、フェニル基及びナフチル基等が挙げられる。
Rxにおけるアラルキル基としては、置換基を有してもよく、好ましくは炭素数7~20のものが挙げられ、例えば、ベンジル基及びフェネチル基等が挙げられる。
Rxにおけるアルケニル基は、置換基を有してもよく、直鎖状であってもよく、分岐鎖状であってもよい。このアルケニル基の炭素数は、3~20であることが好ましい。このようなアルケニル基としては、例えば、ビニル基、アリル基及びスチリル基等が挙げられる。
RxとRyが互いに結合して形成してもよい環構造としては、窒素原子を含む5~10員の環、特に好ましくは6員の環が挙げられる。
このような構造を有する有機基として、好ましい炭素数は4~30の有機基であり、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルケニル基などを挙げることができる。
単環式構造としては、窒素原子を含む4員環、5員環、6員環、7員環、8員環等を挙げることができる。多環式構造としては、2又は3以上の単環式構造の組み合わせから成る構造を挙げることができる。
Qは、酸基の親水性の観点から、-SO3H又は-CO2Hであることが特に好ましい。
一般式(PA-1)で表される化合物の内、Q部位がスルホン酸である化合物は、一般的なスルホンアミド化反応を用いることで合成できる。例えば、ビススルホニルハライド化合物の一方のスルホニルハライド部を選択的にアミン化合物と反応させて、スルホンアミド結合を形成した後、もう一方のスルホニルハライド部分を加水分解する方法、あるいは環状スルホン酸無水物をアミン化合物と反応させ開環させる方法により得ることができる。
化合物(PA)として、好ましくは下記一般式(4)~(6)で表される化合物が挙げられる。
C+はカウンターカチオンを示す。
カウンターカチオンとしては、オニウムカチオンが好ましい。より詳しくは、酸発生剤において、一般式(ZI)におけるS+(R201)(R202)(R203)として説明されているスルホニウムカチオン、一般式(ZII)におけるI+(R204)(R205)として説明されているヨードニウムカチオンが好ましい例として挙げられる。
化合物(PA)の具体例としては、US2011/0269072A1 <0280>に例示された化合物を挙げることが出来る。
mは1又は2を表し、nは1又は2を表す。但し、Aが硫黄原子の時、m+n=3、Aがヨウ素原子の時、m+n=2である。
Rは、アリール基を表す。
RNは、プロトンアクセプター性官能基で置換されたアリール基を表す。X-は、対アニオンを表す。
X-の具体例としては、前述した酸発生剤のアニオンと同様のものを挙げることができる。
R及びRNのアリール基の具体例としては、フェニル基が好ましく挙げられる。
以下に、カチオン部にプロトンアクセプター部位を有するイオン性化合物の具体例としては、US2011/0269072A1 <0291>に例示された化合物を挙げることが出来る。
なお、このような化合物は、例えば、特開2007―230913号公報及び特開2009―122623号公報などに記載の方法を参考にして合成できる。
化合物(PA)の含有量は、組成物の全固形分を基準として、0.1~10質量%が好ましく、1~8質量%がより好ましい。
酸発生剤と、酸発生剤から生じた酸に対して相対的に弱酸(好ましくはpKaが-1超の弱酸)である酸を発生するオニウム塩を混合して用いた場合、活性光線性又は放射線の照射により酸発生剤から生じた酸が未反応の弱酸アニオンを有するオニウム塩と衝突すると、塩交換により弱酸を放出して強酸アニオンを有するオニウム塩を生じる。この過程で強酸がより触媒能の低い弱酸に交換されるため、見かけ上、酸が失活して酸拡散の制御を行うことができる。
一般式(d1‐2)で表される化合物のアニオン部の好ましい例としては、特開2012-242799号公報の段落〔0201〕に例示された構造を挙げることが出来る。
一般式(d1‐3)で表される化合物のアニオン部の好ましい例としては、特開2012-242799号公報の段落〔0209〕及び〔0210〕に例示された構造を挙げることが出来る。
化合物(D-2)としては、下記一般式(C-1)~(C-3)のいずれかで表される化合物であることが好ましい。
R1、R2、R3は、炭素数1以上の置換基を表す。
L1は、カチオン部位とアニオン部位を連結する2価の連結基又は単結合を表す。
-X-は、-COO-、-SO3 -、-SO2 -、-N--R4から選択されるアニオン部位を表す。R4は、隣接するN原子との連結部位に、カルボニル基:-C(=O)-、スルホニル基:-S(=O)2-、スルフィニル基:-S(=O)-を有する1価の置換基を表す。
R1、R2、R3、R4、L1は互いに結合して環構造を形成してもよい。また、(C-3)において、R1~R3のうち2つを合わせて、N原子と2重結合を形成してもよい。
一般式(C-1)で表される化合物の好ましい例としては、特開2013-6827号公報の段落〔0037〕~〔0039〕及び特開2013-8020号公報の段落〔0027〕~〔0029〕に例示された化合物を挙げることが出来る。
一般式(C-2)で表される化合物の好ましい例としては、特開2012-189977号公報の段落〔0012〕~〔0013〕に例示された化合物を挙げることが出来る。
一般式(C-3)で表される化合物の好ましい例としては、特開2012-252124号公報の段落〔0029〕~〔0031〕に例示された化合物を挙げることが出来る。
本発明の組成物は、通常、溶剤を含有する。
組成物を調製する際に使用することができる溶剤としては、例えば、アルキ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、アルキレングリコールモノアルキルエーテル、乳酸アルキルエステル、アルコキシプロピオン酸アルキル、環状ラクトン(好ましくは炭素数4~10)、環を有してもよいモノケトン化合物(好ましくは炭素数4~10)、アルキレンカーボネート、アルコキシ酢酸アルキル、ピルビン酸アルキル等の有機溶剤を挙げることができる。
これらの溶剤の具体例は、米国特許出願公開2008/0187860号明細書[0441]~<0455>に記載のもの、及び、酢酸イソアミル、ブタン酸ブチル、2-ヒドロキシイソ酪酸メチル、イソ酪酸イソブチル、プロピオン酸ブチル等を挙げることができる。
水酸基を含有する溶剤、水酸基を含有しない溶剤としては前述の例示化合物が適宜選択可能であるが、水酸基を含有する溶剤としては、アルキレングリコールモノアルキルエーテル、乳酸アルキル等が好ましく、プロピレングリコールモノメチルエーテル(PGME、別名1-メトキシ-2-プロパノール)、乳酸エチルがより好ましい。また、水酸基を含有しない溶剤としては、アルキレングリコールモノアルキルエーテルアセテート、アルキルアルコキシプロピオネート、環を含有してもよいモノケトン化合物、環状ラクトン、酢酸アルキルなどが好ましく、これらの内でも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、別名1-メトキシ-2-アセトキシプロパン)、エチルエトキシプロピオネート、2-ヘプタノン、γ-ブチロラクトン、シクロヘキサノン、酢酸ブチルが特に好ましく、プロピレングリコールモノメチルエーテルアセテート、エチルエトキシプロピオネート、2-ヘプタノンが最も好ましい。
水酸基を含有する溶剤と水酸基を含有しない溶剤との混合比(質量)は、1/99~99/1、好ましくは10/90~90/10、更に好ましくは20/80~60/40である。水酸基を含有しない溶剤を50質量%以上含有する混合溶剤が塗布均一性の点で特に好ましい。
溶剤は、プロピレングリコールモノメチルエーテルアセテートを含むことが好ましく、プロピレングリコールモノメチルエーテルアセテート単独溶剤、又は、プロピレングリコールモノメチルエーテルアセテートを含有する2種類以上の混合溶剤であることが好ましい。
本発明の組成物は、カルボン酸オニウム塩を含有してもしなくてもよい。このようなカルボン酸オニウム塩は、米国特許出願公開2008/0187860号明細書<0605>~<0606>に記載のものを挙げることができる。
これらのカルボン酸オニウム塩は、スルホニウムヒドロキシド、ヨードニウムヒドロキシド、アンモニウムヒドロキシドとカルボン酸とを、適当な溶剤中酸化銀と反応させることによって合成できる。
本発明の組成物には、必要に応じて更に、界面活性剤、酸増殖剤、染料、可塑剤、光増感剤、光吸収剤、アルカリ可溶性樹脂、溶解阻止剤及び現像液に対する溶解性を促進させる化合物(例えば、分子量1000以下のフェノール化合物、カルボキシル基を有する脂環族、又は脂肪族化合物)等を含有させることができる。
カルボキシル基を有する脂環族、又は脂肪族化合物の具体例としてはコール酸、デオキシコール酸、リトコール酸などのステロイド構造を有するカルボン酸誘導体、アダマンタンカルボン酸誘導体、アダマンタンジカルボン酸、シクロヘキサンカルボン酸、シクロヘキサンジカルボン酸などが挙げられるが、これらに限定されるものではない。
また、感活性光線性又は感放射線性膜の膜厚は、通常、12μm以下である。
なお、本発明は、上記本発明の感活性光線性又は感放射線性樹脂組成物により形成された感活性光線性又は感放射線性膜にも関する。
厚膜のレジスト膜を形成する際の塗工性等の観点から、感活性光線性又は感放射線性樹脂組成物の粘度は、100~500mPa・sであることが好ましく、120~480mPa・sであることがより好ましく、150~450mPa・sであることが更に好ましい。
固形分濃度とは、組成物の総質量に対する、溶剤を除く他のレジスト成分の質量の質量百分率である。
次に、本発明のパターン形成方法について説明する。
本発明のパターン形成方法は、
(i)感活性光線性又は感放射線性樹脂組成物によって基板上に膜厚が1μm以上の感活性光線性又は感放射線性膜(以下、単に膜とも言う)を形成(製膜)する工程、
(ii)前記感活性光線性又は感放射線性膜に活性光線又は放射線を照射する工程(露光工程)、及び、
(iii)前記活性光線又は放射線が照射された感活性光線性又は感放射線性膜を、現像液を用いて現像する工程(現像工程)、を有するパターン形成方法である。
本発明のパターン形成方法は、(ii)露光工程を、複数回含んでいてもよい。
本発明のパターン形成方法は、(iv)加熱工程を、複数回含んでいてもよい。
特に、膜を基板上に形成する工程としては、組成物を基板上に塗布する方法が挙げられ、塗布方法は一般的な従来の塗布シーケンス(例えば、レジスト組成物を滴下後、基板の回転数を増加させ、膜厚を決定する回転数で維持する方法)を用いることができる。また、厚膜レジスト膜を形成すべく、基板に高粘度を有する組成物を塗布する場合においては、通常の方法であると、レジスト膜の厚みのムラが生じる場合があり、以下の塗布方法によって改善することができる。その方法は、先ず、基板上にレジスト組成物を滴下した後、基板の回転数を第一の中速の回転数で維持し、その後、第二の低速の回転数で維持してレジスト組成物を段階的に塗り広げた後、膜厚を決定する回転数で維持する方法である。好ましくは、塗り広げのステップにおいて、第一の中速の回転のステップと、第二の低速の回転のステップとを交互に複数回繰り返すことがよい。また第一の中速の回転数は好ましくは300rpm~1000rpmであり、第二の低速の回転数は好ましくは、50rpm~200rpmである。
また、露光工程の後かつ現像工程の前に、露光後加熱工程(PEB;Post Exposure Bake)を含むことも好ましい。
加熱温度はPB、PEB共に70~130℃で行うことが好ましく、80~120℃で行うことがより好ましい。
加熱時間は30~300秒が好ましく、30~180秒がより好ましく、30~90秒が更に好ましい。
加熱は通常の露光・現像機に備わっている手段で行うことができ、ホットプレート等を用いて行ってもよい。
ベークにより露光部の反応が促進され、感度やパターンプロファイルが改善する。
グレースケール露光とは、所望の形状が得られるように、所定の光透過率を有するように所定の網点が形成されたマスクを介してレジスト膜に露光処理を施すものである。つまり、微小な開口をもつマスクに光を照射することにより、得られるパターン(レジストパターン)の高さに階調をもたせることができる露光処理である。
液浸露光を行う場合には、(1)基板上に膜を形成した後、露光する工程の前に、及び/又は、(2)液浸液を介して膜に露光する工程の後、膜を加熱する工程の前に、膜の表面を水系の薬液で洗浄する工程を実施してもよい。
液浸液は、露光波長に対して透明であり、かつ膜上に投影される光学像の歪みを最小限に留めるよう、屈折率の温度係数ができる限り小さい液体が好ましいが、特に露光光源がArFエキシマレーザー(波長;193nm)である場合には、上述の観点に加えて、入手の容易さ、取り扱いのし易さといった点から水を用いるのが好ましい。
水を用いる場合、水の表面張力を減少させるとともに、界面活性力を増大させる添加剤(液体)を僅かな割合で添加してもよい。この添加剤はウエハ上のレジスト膜を溶解させず、かつレンズ素子の下面の光学コートに対する影響が無視できるものが好ましい。
このような添加剤としては、例えば、水とほぼ等しい屈折率を有する脂肪族系のアルコールが好ましく、具体的にはメチルアルコール、エチルアルコール、イソプロピルアルコール等が挙げられる。水とほぼ等しい屈折率を有するアルコールを添加することにより、水中のアルコール成分が蒸発して含有濃度が変化しても、液体全体としての屈折率変化を極めて小さくできるといった利点が得られる。
液浸液として用いる水の電気抵抗は、18.3MΩcm以上であることが望ましく、TOC(有機物濃度)は20ppb以下であることが望ましく、脱気処理をしていることが望ましい。
レジスト膜の後退接触角は温度23±3℃、湿度45±5%において70°以上であることが好ましく、このような場合、液浸媒体を介して露光する場合に好適である。また、75°以上であることがより好ましく、75~85°であることが更に好ましい。
トップコートは、具体的には、炭化水素ポリマー、アクリル酸エステルポリマー、ポリメタクリル酸、ポリアクリル酸、ポリビニルエーテル、シリコン含有ポリマー、フッ素含有ポリマーなどが挙げられる。トップコートから液浸液へ不純物が溶出すると光学レンズを汚染するという観点からは、トップコートに含まれるポリマーの残留モノマー成分は少ない方が好ましい。トップコートは、塩基性化合物を含んでいてもよい。
トップコートと液浸液との間には屈折率の差がない方が、解像力が向上する。液浸液として水を用いる場合には、トップコートは液浸液の屈折率に近いことが好ましい。屈折率を液浸液に近くするという観点からは、トップコート中にフッ素原子を有することが好ましい。また、透明性・屈折率の観点から薄膜の方が好ましい。
トップコートは、膜と混合せず、更に液浸液とも混合しないことが好ましい。この観点から、液浸液が水の場合には、トップコートに使用される溶剤は、本発明の組成物に使用される溶剤に難溶で、かつ非水溶性の媒体であることが好ましい。更に、液浸液が有機溶剤である場合には、トップコートは水溶性であっても非水溶性であってもよい。
トップコートの形成は、液浸露光の場合に限定されず、ドライ露光(液浸液を介さない露光)の場合に行ってもよい。トップコートを形成することにより、例えば、アウトガスの発生を抑制できる。
以下、トップコートの形成に用いられるトップコート組成物について説明する。
溶剤が有機溶剤である場合、レジスト膜を溶解しない溶剤であることが好ましい。使用しうる溶剤としては、アルコール系溶剤、フッ素系溶剤、炭化水素系溶剤を用いることが好ましく、非フッ素系のアルコール系溶剤を用いることがより好ましい。アルコール系溶剤としては、塗布性の観点からは1級のアルコールが好ましく、更に好ましくは炭素数4~8の1級アルコールである。炭素数4~8の1級アルコールとしては、直鎖状、分岐状、環状のアルコールを用いることができるが、好ましくは、例えば、1-ブタノール、1-ヘキサノール、1-ペンタノール、3-メチル-1-ブタノール、2-エチルブタノール及びパーフルオロブチルテトラヒドロフラン等が挙げられる。
また、トップコート組成物用の樹脂としては、特開2009-134177号、特開2009-91798号に記載の酸性基を有する樹脂も、好ましく用いることができる。
樹脂の重量平均分子量は特に制限はないが、2000から100万が好ましく、より好ましくは5000から50万、更に好ましくは1万から10万である。ここで、樹脂の重量平均分子量は、GPC(Gel permeation chromatography)(キャリア:テトラヒドロフラン(THF)あるいはN-メチル-2-ピロリドン(NMP))によって測定したポリスチレン換算分子量を示す。
トップコート組成物のpHは、特に制限はないが、好ましくは0~10、より好ましくは0~8、更に好ましくは1~7である。
トップコート組成物は、光酸発生剤及び含窒素塩基性化合物などの添加剤を含有してもよい。含窒素塩基性化合物を含有するトップコート組成物の例としては、米国公開特許公報US2013/0244438A号を挙げることができる。
本発明におけるトップコート組成物の固形分濃度は、0.1~10質量%であることが好ましく、0.2~6質量%であることがより好ましく、0.3~5質量%であることが更に好ましい。固形分濃度を上記範囲とすることで、トップコート組成物をレジスト膜上に均一に塗布することができる。
トップコートを形成する方法は特に制限されないが、上記レジスト膜の形成方法と同様の手段によりトップコート組成物を塗布、乾燥し、トップコートを形成することができる。
トップコートを上層に有するレジスト膜に、通常はマスクを通して、活性光線又は放射線を照射し、好ましくはベーク(加熱)を行い、現像する。これにより良好なパターンを得ることができる。
アルカリ現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、n-プロピルアミン等の第一アミン類、ジエチルアミン、ジ-n-ブチルアミン等の第二アミン類、トリエチルアミン、メチルジエチルアミン等の第三アミン類、ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン類、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドドキシド、テトラブチルアンモニウムヒドロキシド、テトラペンチルアンモニウムヒドロキシド、テトラヘキシルアンモニウムヒドロキシド、テトラオクチルアンモニウムヒドロキシド、エチルトリメチルアンモニウムヒドロキシド、ブチルトリメチルアンモニウムヒドロキシド、メチルトリアミルアンモニウムヒドロキシド、ジブチルジペンチルアンモニウムヒドロキシド等のテトラアルキルアンモニウムヒドロキシド、トリメチルフェニルアンモニウムヒドロキシド、トリメチルベンジルアンモニウムヒドロキシド、トリエチルベンジルアンモニウムヒドロキシド等の第四級アンモニウム塩、ピロール、ピヘリジン等の環状アミン類等のアルカリ性水溶液を使用することができる。更に、上記アルカリ性水溶液にアルコール類、界面活性剤を適当量添加して使用することもできる。アルカリ現像液のアルカリ濃度は、通常0.1~20質量%である。アルカリ現像液のpHは、通常10.0~15.0である。アルカリ現像液のアルカリ濃度及びpHは、適宜調製して用いることができる。アルカリ現像液は、界面活性剤や有機溶剤を添加して用いてもよい。
アルカリ現像の後に行うリンス処理におけるリンス液としては、純水を使用し、界面活性剤を適当量添加して使用することもできる。
上記の溶剤は、複数混合してもよいし、上記以外の溶剤や水と混合し使用してもよい。但し、本発明の効果を十二分に奏するためには、現像液全体としての含水率が10質量%未満であることが好ましく、実質的に水分を含有しないことがより好ましい。
すなわち、有機系現像液に対する有機溶剤の使用量は、現像液の全量に対して、90質量%以上100質量%以下であることが好ましく、95質量%以上100質量%以下であることが好ましい。
界面活性剤としては特に限定されないが、例えば、イオン性や非イオン性のフッ素系及び/又はシリコン系界面活性剤等を用いることができる。これらのフッ素及び/又はシリコン系界面活性剤として、例えば特開昭62-36663号公報、特開昭61-226746号公報、特開昭61-226745号公報、特開昭62-170950号公報、特開昭63-34540号公報、特開平7-230165号公報、特開平8-62834号公報、特開平9-54432号公報、特開平9-5988号公報、米国特許第5405720号明細書、同5360692号明細書、同5529881号明細書、同5296330号明細書、同5436098号明細書、同5576143号明細書、同5294511号明細書、同5824451号明細書記載の界面活性剤を挙げることができ、好ましくは、非イオン性の界面活性剤である。非イオン性の界面活性剤としては特に限定されないが、フッ素系界面活性剤又はシリコン系界面活性剤を用いることが更に好ましい。
吐出される現像液の吐出圧を上記の範囲とすることにより、現像後のレジスト残渣に由来するパターンの欠陥を著しく低減することができる。
このメカニズムの詳細は定かではないが、恐らくは、吐出圧を上記範囲とすることで、現像液がレジスト膜に与える圧力が小さくなり、レジスト膜及びレジストパターンが不用意に削られたり崩れたりすることが抑制されるためと考えられる。
なお、現像液の吐出圧(mL/sec/mm2)は、現像装置中の現像ノズル出口における値である。
また、有機溶剤を含む現像液を用いて現像する工程の後に、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。
本発明において、有機溶剤現像工程によって露光強度の弱い部分が除去されるが、更にアルカリ現像工程を行うことによって露光強度の強い部分も除去される。このように現像を複数回行う多重現像プロセスにより、中間的な露光強度の領域のみを溶解させずにパターン形成が行えるので、通常より微細なパターンを形成できる(特開2008-292975号公報 <0077>と同様のメカニズム)。
本発明のパターン形成方法においては、アルカリ現像工程及び有機溶剤現像工程の順序は特に限定されないが、アルカリ現像を、有機溶剤現像工程の前に行うことがより好ましい。
有機溶剤を含む現像液を用いて現像する工程の後のリンス工程に用いるリンス液としては、レジストパターンを溶解しなければ特に制限はなく、一般的な有機溶剤を含む溶液を使用することができる。リンス液としては、炭化水素系溶剤、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤及びエーテル系溶剤からなる群より選択される少なくとも1種類の有機溶剤を含有するリンス液を用いることが好ましい。
炭化水素系溶剤、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤及びエーテル系溶剤の具体例としては、有機溶剤を含む現像液において説明したものと同様のものを挙げることができる。
リンス工程で用いられる炭化水素系溶剤としては、炭素数6~30の炭化水素化合物が好ましく、炭素数8~30の炭化水素化合物がより好ましく、炭素数7~30の炭化水素化合物が更に好ましく、炭素数10~30の炭化水素化合物が特に好ましい。中でも、デカン及び/又はウンデカンを含むリンス液を用いることにより、パターン倒れが抑制される。
リンス液中の含水率は、10質量%以下が好ましく、より好ましくは5質量%以下、特に好ましくは3質量%以下である。含水率を10質量%以下にすることで、良好な現像特性を得ることができる。
リンス工程においては、有機溶剤を含む現像液を用いる現像を行ったウエハを上記の有機溶剤を含むリンス液を用いて洗浄処理する。洗浄処理の方法は特に限定されないが、たとえば、一定速度で回転している基板上にリンス液を吐出しつづける方法(回転塗布法)、リンス液が満たされた槽中に基板を一定時間浸漬する方法(ディップ法)、基板表面にリンス液を噴霧する方法(スプレー法)、などを適用することができ、この中でも回転塗布方法で洗浄処理を行い、洗浄後に基板を2000rpm~4000rpmの回転数で回転させ、リンス液を基板上から除去することが好ましい。また、リンス工程の後に加熱工程(Post Bake)を含むことも好ましい。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。リンス工程の後の加熱工程は、通常40~160℃、好ましくは70~95℃で、通常10秒~3分、好ましくは30秒から90秒間行う。
前記各種材料から金属等の不純物を除去する方法としては、例えば、フィルターを用いた濾過を挙げることができる。フィルター孔径としては、ポアサイズ10nm以下が好ましく、5nm以下がより好ましく、3nm以下が更に好ましい。フィルターの材質としては、ポリテトラフロロエチレン製、ポリエチレン製、ナイロン製のフィルターが好ましい。フィルターは、これらの材質とイオン交換メディアを組み合わせた複合材料であってもよい。フィルターは、有機溶剤であらかじめ洗浄したものを用いてもよい。フィルター濾過工程では、複数種類のフィルターを直列又は並列に接続して用いてもよい。複数種類のフィルターを使用する場合は、孔径及び/又は材質が異なるフィルターを組み合わせて使用しても良い。また、各種材料を複数回濾過してもよく、複数回濾過する工程が循環濾過工程であっても良い。
また、前記各種材料に含まれる金属等の不純物を低減する方法としては、各種材料を構成する原料として金属含有量が少ない原料を選択する、各種材料を構成する原料に対してフィルター濾過を行う、装置内をテフロン(登録商標)でライニングする等してコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。各種材料を構成する原料に対して行うフィルター濾過における好ましい条件は、前記した条件と同様である。
フィルター濾過の他、吸着材による不純物の除去を行っても良く、フィルター濾過と吸着材を組み合わせて使用しても良い。吸着材としては、公知の吸着材を用いることができ、例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材を使用することができる。
上記各種材料に含まれる金属等の不純物を低減するためには、製造工程における金属不純物の混入を防止することが必要である。製造装置から金属不純物が十分に除去されたかどうかは、製造装置の洗浄に使用された洗浄液中に含まれる金属成分の含有量を測定することで確認することができる。使用後の洗浄液に含まれる金属成分の含有量は、100ppt(parts per trillion)以下がより好ましく、10ppt以下が更に好ましく、1ppt以下が特に好ましい。
本発明のパターン形成方法は、DSA(Directed Self-Assembly)におけるガイドパターン形成(例えば、ACS Nano Vol.4 No.8 Page4815-4823参照)にも用いることができる。
また、上記の方法によって形成されたレジストパターンは、例えば特開平3-270227及び特開2013-164509に開示されたスペーサープロセスの芯材(コア)として使用できる。
本発明の電子デバイスは、電気電子機器(家電、OA・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。
表1に示す成分を溶剤に溶解させて、それぞれについてのレジスト溶液を調製し、これを3μmのポアサイズを有するポリエチレンフィルターで濾過した。これにより、表1に記載の固形分濃度を有する感活性光線性又は感放射線性樹脂組成物(レジスト組成物)を調製した。
PGMEA:プロピレングリコールモノメチルエーテルアセテート
PGME:プロピレングリコールモノメチルエーテル
EL:乳酸エチル
EEP:3-エトキシプロピオン酸エチル
MAK:2-ヘプタノン
上記で調製したレジスト組成物の粘度を、25.0℃において、TOKI SANGYO製RE-85Lにより測定した。結果を表1に示す。
東京エレクトロン製スピンコーターACT-8を利用して、ヘキサメチルジシラザン処理を施したSi基板(Advanced Materials Technology社製)上に、反射防止層を設けることなく、上記で調製したレジスト組成物を基板が静止した状態で滴下した。滴下した後、基板を回転し、その回転数を、3秒間500rpmで維持し、その後2秒間100rpmで維持し、さらに3秒間500rpmで維持し、再び2秒間100rpmで維持した後、膜厚設定回転数(1200rpm)に上げて60秒間維持した。その後、ホットプレート上で130℃で60秒間加熱乾燥を行い、膜厚7.5μmのポジ型レジスト膜を形成した。このレジスト膜に対して、縮小投影露光及び現像後に形成されるパターンのスペース幅が10μm、ピッチ幅が100μmとなるような、ラインアンドスペースパターンを有するマスクを介して、KrFエキシマレーザースキャナー(ASML製、PAS5500/850C波長248nm)を用いて、NA=0.68、σ=0.60の露光条件でパターン露光した。照射後に130℃、60秒ベークし、2.38質量%テトラメチルアンモニウムハイドロオキサイド(TMAH)水溶液を用いて60秒間浸漬した後、30秒間、純水でリンスして乾燥し、スペース幅が10μm、ピッチ幅が100μm、レジスト膜部の厚さが7.5μmの孤立スペースパターンを形成した。
上記において形成した孤立スペースパターンを有するチップを複数用意し、各チップに対して、100℃~200℃の範囲で5℃刻みに各々60秒間加熱処理した後、各チップを割断した。チップの割断面における、レジスト膜部とスペース部の界面を走査型電子顕微鏡(SEM)(株式会社日立ハイテクノロジーズ製9380II)にて観察し、レジスト膜部の厚さ(スペース部の深さに相当)を100%とした場合に、レジスト膜部の表面(すなわち上面)から深さ20%の高さにおけるスペース部のスペース幅が、レジスト膜部の表面から深さ50%の高さにおけるスペース部のスペース幅に対して1.2倍以上となる状態までレジスト膜部の形状が変化した温度の最小値を軟化点(℃)とした。
結果を表3に示す。
東京エレクトロン製スピンコーターACT-8を利用して、ヘキサメチルジシラザン処理を施したSi基板(Advanced Materials Technology社製)上に、反射防止層を設けることなく、上記で調製したレジスト組成物を基板が静止した状態で滴下した。滴下した後、基板を回転し、その回転数を、3秒間500rpmで維持し、その後2秒間100rpmで維持し、さらに3秒間500rpmで維持し、再び2秒間100rpmで維持した後、膜厚設定回転数(1200rpm)に上げて60秒間維持した。その後、ホットプレート上で130℃で60秒間加熱乾燥を行い、膜厚7.5μmのポジ型レジスト膜を形成した。このレジスト膜に対し、縮小投影露光及び現像後に形成されるパターンのスペース幅が3μm、ピッチ幅が33μmとなるような、ラインアンドスペースパターンを有するマスクを介して、KrFエキシマレーザースキャナー(ASML製、PAS5500/850C波長248nm)を用いて、NA=0.68、σ=0.60の露光条件でパターン露光した。照射後に130℃、60秒ベークし、2.38質量%テトラメチルアンモニウムハイドロオキサイド(TMAH)水溶液を用いて60秒間浸漬した後、30秒間、純水でリンスして乾燥して、スペース幅が3μm、ピッチ幅が33μmの孤立スペースパターンを形成した。
上記パターン露光は、縮小投影露光後のスペース幅が3μm、ピッチ幅が33μmとなるような、ラインアンドスペースパターンを有するマスクを介する露光であり、露光量は、スペース幅が3μm、ピッチ幅が33μmの孤立スペースパターンを形成する最適露光量(感度)(mJ/cm2)とした。上記感度の決定において、パターンのスペース幅の測定は走査型電子顕微鏡(SEM)(株式会社日立ハイテクノロジーズ製9380II)を用いた。
上記パターン形成において使用したマスクを介して露光し、露光量を変化させた時に形成される孤立スペースパターンにおけるスペース幅の最小線幅を解像性とし、最小線幅が小さいほど、解像性が高いと判断した。スペース幅の測定は走査型電子顕微鏡(SEM)(株式会社日立ハイテクノロジーズ製9380II)を用いた。
上記感度において形成した孤立スペースパターンを有するウエハにおいて、スペース幅が10%変化する露光量を最適露光量で割った値(百分率)を露光ラチチュードとした。値が大きいほど露光量変化による性能変化が小さく、露光ラチチュードが良好である。
上記感度において形成した孤立スペースパターンを加工マスクとして、Si基板(8インチシリコンウエハ)をドライエッチング処理した。先ず、フッ素系ガスを使用したエッチングを行い、Si基板を加工した。ここで、1インチは25.4mmに相当する。エッチング条件としては、Ar:C4F6:O2を流量比にて25:1:2にて混合したガスを使用し、処理圧力4Pa、ソースパワー500W、ウェーハバイアス700W、アンテナバイアス600W、加工時間60秒の条件を適用した。続いて、酸素ガスを使用したエッチングを行い、レジストマスクパターンを加工した。エッチング条件としては、CF4:O2を流量比にて1:24にて混合したガスを使用し、処理圧力0.5Pa、ソースパワー700W、アンテナバイアス100W、加工時間60秒の条件を適用した。
上記ドライエッチング処理を行った後に、ウェハを割断し、レジストの側壁ラフネスを走査型電子顕微鏡(SEM)にて観察し、ラフネスが殆ど見られないものをA、ラフネスがやや見られるものをB、ラフネスが大きいものをCで分類した。なお、ドライエッチング装置は株式会社日立ハイテクノロジーズ製 U-621を用いた。
上記孤立スペースパターンを有するウエハを、SEM(KLA-Tencor社製eCD2)内のチャンバーにて0.002Pa圧力下において、60秒間真空処理を行った。真空引き後のウエハを光学顕微鏡(オリンパス株式会社社製MX61L)により観察し、ウエハ表面のひび割れ(クラック)を観察した。ひび割れが50個以上の多数の場合D、ひび割れが5個~49個の場合C、ひび割れが1~4個の場合B、ひび割れ0個の場合をAとして評価した。
一方、本発明の要件を満たす実施例1~18は、何れも、優れた解像性と、優れた露光ラチチュードとを高次元で両立するとともに、エッチング時に発生し得るレジストパターンの側壁におけるラフネスを抑制できることが分かった。
また、化合物(B)として、上述した一般式(a)で表される基を有するポリエーテル系化合物を使用した実施例19~24は、クラック性能により優れることが分かった。
本出願は、2015年12月25日出願の日本特許出願(特願2015-255192)、及び2016年9月14日出願の日本特許出願(特願2016-179803)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (13)
- ガラス転移温度が155℃以上の樹脂(A)、
ガラス転移温度が150℃以下の化合物(B)、及び
溶剤(C)を含有する、
感活性光線性又は感放射線性樹脂組成物であって、
前記感活性光線性又は感放射線性樹脂組成物中の固形分含有量が20質量%以上であり、
前記感活性光線性又は感放射線性樹脂組成物によって形成されるレジストパターンの軟化点が130℃以上170℃以下である、感活性光線性又は感放射線性樹脂組成物。 - 前記化合物(B)が樹脂である、請求項1に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記化合物(B)としての樹脂の重量平均分子量が1000~18000である、請求項2に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記樹脂(B)がヒドロキシスチレンに由来する繰り返し単位を有する、請求項2又は3に記載の感活性光線性又は感放射線性樹脂組成物。
- 化合物(B)がポリエーテル系化合物である、請求項1に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記ポリエーテル系化合物の分子量が100~5000である、請求項5に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記感活性光線性又は感放射線性樹脂組成物の粘度が100~500mPa・sである、請求項1~6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。
- 前記樹脂(A)のガラス転移温度が170℃以上である、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。
- 前記樹脂(A)の重量平均分子量が18000以上である、請求項1~8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。
- 前記樹脂(A)がヒドロキシスチレンに由来する繰り返し単位を有する、請求項1~9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。
- 請求項1~10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より形成された感活性光線性又は感放射線性膜。
- (i)請求項1~10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によって基板上に膜厚が1μm以上の感活性光線性又は感放射線性膜を形成する工程、
(ii)前記感活性光線性又は感放射線性膜に活性光線又は放射線を照射する工程、及び、
(iii)前記活性光線又は放射線が照射された感活性光線性又は感放射線性膜を、現像液を用いて現像する工程、を有するパターン形成方法。 - 請求項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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KR20200016350A (ko) * | 2017-08-31 | 2020-02-14 | 후지필름 가부시키가이샤 | 감활성광선성 또는 감방사선성 수지 조성물, 레지스트막, 패턴 형성 방법, 고체 촬상 소자의 제조 방법 |
CN110914757A (zh) * | 2017-08-31 | 2020-03-24 | 富士胶片株式会社 | 感光化射线性或感放射线性树脂组合物、抗蚀剂膜、图案形成方法及固体摄像元件的制造方法 |
JPWO2019044270A1 (ja) * | 2017-08-31 | 2020-03-26 | 富士フイルム株式会社 | 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、固体撮像素子の製造方法 |
WO2019044270A1 (ja) * | 2017-08-31 | 2019-03-07 | 富士フイルム株式会社 | 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、固体撮像素子の製造方法 |
US11187981B2 (en) | 2017-12-25 | 2021-11-30 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition and method of forming resist pattern |
JP2019113773A (ja) * | 2017-12-25 | 2019-07-11 | 東京応化工業株式会社 | レジスト組成物及びレジストパターン形成方法 |
JP7080046B2 (ja) | 2017-12-25 | 2022-06-03 | 東京応化工業株式会社 | レジスト組成物及びレジストパターン形成方法 |
JPWO2019187783A1 (ja) * | 2018-03-30 | 2021-03-25 | 富士フイルム株式会社 | 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 |
JP7128885B2 (ja) | 2018-03-30 | 2022-08-31 | 富士フイルム株式会社 | 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 |
WO2019187783A1 (ja) * | 2018-03-30 | 2019-10-03 | 富士フイルム株式会社 | 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 |
WO2020137921A1 (ja) * | 2018-12-28 | 2020-07-02 | 富士フイルム株式会社 | 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、及び、電子デバイスの製造方法 |
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US11009791B2 (en) | 2021-05-18 |
JP6688811B2 (ja) | 2020-04-28 |
JPWO2017110352A1 (ja) | 2018-11-01 |
KR102125252B1 (ko) | 2020-06-22 |
TW201736953A (zh) | 2017-10-16 |
US20180299777A1 (en) | 2018-10-18 |
TWI702470B (zh) | 2020-08-21 |
CN108431690B (zh) | 2021-11-26 |
KR20180086222A (ko) | 2018-07-30 |
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