WO2017056805A1 - パターン形成方法、電子デバイスの製造方法、及び積層体 - Google Patents
パターン形成方法、電子デバイスの製造方法、及び積層体 Download PDFInfo
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- WO2017056805A1 WO2017056805A1 PCT/JP2016/074957 JP2016074957W WO2017056805A1 WO 2017056805 A1 WO2017056805 A1 WO 2017056805A1 JP 2016074957 W JP2016074957 W JP 2016074957W WO 2017056805 A1 WO2017056805 A1 WO 2017056805A1
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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
- 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
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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
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
- G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
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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
- G03F7/325—Non-aqueous compositions
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
Definitions
- the present invention relates to a pattern forming method, an electronic device manufacturing method, and a laminate. More specifically, the present invention relates to a pattern forming method used in a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board such as a liquid crystal or a thermal head, and a lithography process for other photo applications. The present invention relates to a method for manufacturing an electronic device including the pattern forming method, and a laminate.
- a semiconductor manufacturing process such as an IC (Integrated Circuit)
- a circuit board such as a liquid crystal or a thermal head
- lithography process for other photo applications.
- the present invention relates to a method for manufacturing an electronic device including the pattern forming method, and a laminate.
- Patent Document 1 describes an upper layer film-forming composition that is coated on a photoresist film.
- the upper layer film-forming composition includes a resin that dissolves in a developer that develops a photoresist film, an acid, and radiation sensitivity. It is described that it contains at least one acidic acid generator, has excellent ArF permeability, does not cause intermixing with a photoresist film, and is easily dissolved in an alkaline developer.
- Patent Document 2 includes a resin whose polarity is increased by the action of an acid to reduce solubility in a developer containing an organic solvent, and a compound that decomposes upon irradiation with actinic rays or radiation to generate an acid. After forming a resist film and forming a protective film on the resist film, the resist film is exposed to an electron beam or extreme ultraviolet (EUV), and developed using a developer containing an organic solvent. A forming method is described. According to Patent Document 2, it is described that a pattern forming method excellent in resolving power can be provided in forming an isolated space pattern having an extremely fine space width.
- EUV extreme ultraviolet
- Patent Document 2 discusses resolution in forming an isolated space pattern.
- an extremely fine remaining pattern for example, a dot pattern with a diameter of 30 nm or less or an isolated line pattern with a line width of 30 nm or less
- a pattern formation method in which development is performed using a developer containing a solvent is conceivable.
- pattern thinning tends to occur, which is a high solution in the formation of an extremely fine residual pattern. It is difficult to obtain image quality.
- the present invention provides a pattern forming method capable of obtaining a high resolving power in the formation of a very fine remaining pattern (for example, a dot pattern having a diameter of 30 nm or less or an isolated line pattern having a line width of 30 nm or less), and the pattern forming method described above.
- An object of the present invention is to provide a method for manufacturing an electronic device including the electronic device.
- a step of forming an actinic ray-sensitive or radiation-sensitive film with an actinic ray-sensitive or radiation-sensitive composition (b) an upper layer film-forming composition on the actinic ray-sensitive or radiation-sensitive film; A step of forming an upper layer film, (c) a step of exposing the actinic ray-sensitive or radiation-sensitive film on which the upper layer film is formed, and (d) an exposed actinic ray-sensitive or radiation-sensitive film.
- a pattern forming method comprising a step of developing with a developer containing an organic solvent, wherein the upper layer film-forming composition is a compound that generates an acid by actinic rays or radiation, a compound that generates an acid by heat, and an acid.
- a pattern forming method comprising at least one of the following.
- the pattern formation method according to [1], wherein the composition for forming an upper layer film contains an anion represented by the following general formula (AN1).
- each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R 1 and R 2 , they may be the same or different.
- L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
- A represents a cyclic organic group.
- x represents an integer of 1 to 20
- y represents an integer of 0 to 10
- z represents an integer of 0 to 10.
- the actinic ray-sensitive or radiation-sensitive film is formed of an actinic ray-sensitive or radiation-sensitive composition, and the actinic ray-sensitive or radiation-sensitive composition includes a resin containing a repeating unit having an aromatic ring.
- the developer containing the organic solvent contains at least one solvent selected from ester solvents, ketone solvents, ether solvents, and hydrocarbon solvents, and any one of [1] to [6] The pattern forming method according to item.
- the present invention it is possible to provide a pattern forming method capable of obtaining a high resolving power, and a method for manufacturing an electronic device including the pattern forming method and a laminate, particularly in the formation of an extremely fine pattern.
- the description which is not describing substitution and no substitution includes not only what does not have a substituent but what has 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).
- Actinic light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like.
- light means actinic rays or radiation.
- exposure in this specification is not limited to exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, X-rays, EUV light, etc., but also particles such as electron beams and ion beams. Line drawing is also included in the exposure.
- (meth) acrylate and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.
- the weight average molecular weight of the resin is a polystyrene equivalent value measured by a GPC (gel permeation chromatography) method.
- GPC uses HLC-8120 (manufactured by Tosoh Corporation), TSK gel Multipore HXL-M (Tosoh Corporation, 7.8 mm ID ⁇ 30.0 cm) as a column, and THF (tetrahydrofuran) as an eluent. You can follow the same method.
- the pattern forming method of the present invention comprises (a) a step of forming an actinic ray-sensitive or radiation-sensitive film with an actinic ray-sensitive or radiation-sensitive composition, and (b) on the actinic ray-sensitive or radiation-sensitive film. (C) a step of exposing the actinic ray-sensitive or radiation-sensitive film, and (d) an exposed actinic ray-sensitive or radiation-sensitive film.
- a pattern forming method including a step of developing with a developer containing an organic solvent,
- the composition for forming an upper layer film is a pattern forming method comprising at least one of a compound that generates an acid by actinic rays or radiation, a compound that generates an acid by heat, and an acid.
- the step (a) of the pattern forming method of the present invention is to form an actinic ray-sensitive or radiation-sensitive film from an actinic ray-sensitive or radiation-sensitive composition, preferably an actinic ray-sensitive or sensitive layer on a substrate.
- This is a step of forming an actinic ray-sensitive or radiation-sensitive film by applying a radiation composition.
- the actinic ray-sensitive or radiation-sensitive composition is preferably a resist composition
- the actinic ray-sensitive or radiation-sensitive film is preferably a resist film.
- Actinic ray-sensitive or radiation-sensitive composition In the pattern forming method of the present invention, it is preferable to form an actinic ray-sensitive or radiation-sensitive film by applying an actinic ray-sensitive or radiation-sensitive composition onto a substrate.
- the actinic ray-sensitive or radiation-sensitive composition is preferably an actinic ray-sensitive or radiation-sensitive composition for organic solvent development using a developer containing an organic solvent.
- the term “for organic solvent development” means an application that is used in a step of developing using a developer containing at least an organic solvent.
- the actinic ray-sensitive or radiation-sensitive composition is preferably a resist composition, more preferably a chemically amplified resist composition.
- the actinic ray-sensitive or radiation-sensitive composition in the present invention may be a positive resist composition or a negative resist composition, but is preferably a negative resist composition.
- the radiation-sensitive or actinic ray-sensitive composition in the present invention is preferably used for electron beam or extreme ultraviolet exposure.
- the actinic ray-sensitive or radiation-sensitive composition is preferably an actinic ray-sensitive or radiation-sensitive resin composition.
- the actinic ray-sensitive or radiation-sensitive composition preferably contains the resin (A).
- Resin (A) is at least (i) a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group (may further have a repeating unit having a phenolic hydroxyl group), or at least (ii) It preferably has a repeating unit having a phenolic hydroxyl group.
- the resin (A) preferably includes a resin containing a repeating unit having an aromatic ring.
- the resin (A) contains a repeating unit having an aromatic ring
- the effect of increasing sensitivity and resolution can be expected during pattern formation.
- action of an acid and has a carboxyl group the solubility with respect to an organic solvent reduces by the effect
- Examples of the repeating unit having a phenolic hydroxyl group that the resin (A) can have include a repeating unit represented by the following general formula (I).
- R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 42 may form a ring with Ar 4, R 42 in this case represents a single bond or an alkylene group.
- X 4 represents a single bond, —COO—, or —CONR 64 —, and R 64 represents a hydrogen atom or an alkyl group.
- L 4 represents a single bond or an alkylene group.
- Ar 4 represents an (n + 1) -valent aromatic ring group, and when bonded to R 42 to form a ring, represents an (n + 2) -valent aromatic ring group.
- n represents an integer of 1 to 5.
- the alkyl group represented by R 41 , R 42 and R 43 in the general formula (I) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- which may have a substituent.
- alkyl groups having 20 or less carbon atoms such as butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, particularly preferably alkyl groups having 3 or less carbon atoms.
- the cycloalkyl group represented by R 41 , R 42 and R 43 in the general formula (I) may be monocyclic or polycyclic. Preferred examples include a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
- Examples of the halogen atom of R 41 , R 42 and R 43 in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
- the alkyl group contained in the alkoxycarbonyl group of R 41 , R 42 and R 43 in the general formula (I) the same alkyl groups as those described above for R 41 , R 42 and R 43 are preferable.
- Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups and the like, and the substituent preferably has 8 or less carbon atoms.
- Ar 4 represents an (n + 1) -valent aromatic ring group.
- the divalent aromatic ring group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, an anthracenylene group, or the like.
- Examples of preferred aromatic ring groups include heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.
- n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group.
- the group formed can be preferably mentioned.
- the (n + 1) -valent aromatic ring group may further have a substituent.
- Examples of the substituent that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1) -valent aromatic ring group may have include R 41 , R 42 , and R 43 in formula (I).
- Examples include alkyl groups such as alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, and butoxy groups; aryl groups such as phenyl groups; and the like.
- R 64 represents a hydrogen atom, an alkyl group
- the alkyl group for R 64 in, preferably an optionally substituted methyl group, ethyl group, propyl Group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like, more preferably an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms.
- X 4 is preferably a single bond, —COO— or —CONH—, and more preferably a single bond or —COO—.
- the alkylene group for L 4 is preferably an alkylene group having 1 to 8 carbon atoms such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group.
- Ar 4 an optionally substituted aromatic ring group having 6 to 18 carbon atoms is more preferable, and a benzene ring group, a naphthalene ring group, and a biphenylene ring group are particularly preferable.
- the repeating unit represented by the general formula (I) preferably has a hydroxystyrene structure, and more preferably a benzene ring group.
- the repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (1).
- A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
- R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group or an aryloxycarbonyl group. In some cases, they may be the same or different. In the case of having a plurality of Rs, they may form a ring together.
- R is preferably a hydrogen atom.
- a represents an integer of 1 to 3, and is preferably 1.
- b represents an integer of 0 to (3-a).
- the repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (p1).
- R represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. As R in the general formula (p1), a hydrogen atom is particularly preferable.
- Ar in the general formula (p1) represents an 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 heterocycles include aromatic heterocycles. Of these, a benzene ring is most preferable.
- M in the general formula (p1) represents an integer of 1 to 5, preferably 1.
- a 1 or 2.
- the content of the repeating unit having a phenolic hydroxyl group is preferably from 0 to 50 mol%, more preferably from 0 to 45 mol%, still more preferably from 0 to 40 mol%, based on all repeating units in the resin (A). is there.
- the repeating unit having a group capable of decomposing by the action of an acid that can have a resin (A) to generate a carboxyl group has a group in which the hydrogen atom of the carboxyl group is substituted with a group that decomposes and leaves by the action of an acid It is a repeating unit.
- 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.
- a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group a repeating unit represented by the following general formula (AI) is preferable.
- Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.
- 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). However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. Two of Rx 1 to Rx 3 may combine to form a cycloalkyl group (monocyclic or polycyclic).
- Examples of the optionally substituted alkyl group represented by Xa 1 include a methyl group or a group represented by —CH 2 —R 11 .
- R 11 is a monovalent organic group such as a halogen atom (such as a fluorine atom), a hydroxyl group, or an alkyl group having 5 or less carbon atoms or an acyl group having 5 or less carbon atoms, preferably an alkyl having 3 or less carbon atoms. Group, 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.
- the repeating unit represented by formula (AI) is preferably an acid-decomposable (meth) acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T is a single bond. Is a repeating unit). More preferably, Rx 1 to Rx 3 are each independently a repeating unit representing a linear or branched alkyl group, and more preferably, Rx 1 to Rx 3 are each independently a repeating unit representing a linear alkyl group. Unit.
- 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 content of the repeating unit having a group capable of decomposing by the action of an acid to generate a carboxyl group is preferably 20 to 90 mol%, more preferably 25 to 80 mol%, based on all repeating units in the resin (A). More preferably, it is 30 to 70 mol%.
- the resin (A) preferably further contains a repeating unit having a lactone group.
- the lactone group any group having a lactone structure can be used, but a group containing a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed to form a spiro structure are preferred. It is more preferable to have a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). Further, a group having a lactone structure may be directly bonded to the main chain.
- Preferred lactone structures are those represented by the general formula (LC1-1), It is a group represented by (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14).
- the lactone structure moiety may or may not have have a substituent (Rb 2).
- Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like.
- n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb 2 may be the same or different, and a plurality of Rb 2 may be bonded to form a ring.
- Examples of the repeating unit having a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-17) include a repeating unit represented by the following general formula (AI). Can do.
- Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
- substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
- the halogen atom for Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Rb 0 is preferably a hydrogen atom or a methyl group.
- Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent group obtained by combining these. Preferably, it is a single bond or a linking group represented by —Ab 1 —CO 2 —.
- Ab 1 is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
- V represents a group represented by any one of the general formulas (LC1-1) to (LC1-17).
- the repeating unit having a group having a lactone structure 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.
- Rx represents a hydrogen atom, —CH 3 , —CH 2 OH or —CF 3 .
- the content of the repeating unit having a lactone group is preferably from 1 to 30 mol%, more preferably from 5 to 25 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the resin (A). .
- the resin (A) can further have a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.
- the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diadamantyl group or a norbornane group.
- the polar group is preferably a hydroxyl group or a cyano group. Specific examples of the repeating unit having a polar group are listed below, but the present invention is not limited thereto.
- the content thereof is preferably 1 to 30 mol%, more preferably 5%, based on all repeating units in the resin (A). It is ⁇ 25 mol%, more preferably 5 to 20 mol%.
- the resin (A) can further contain a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (photoacid generating group) as a repeating unit other than the above.
- a repeating unit having this photoacid-generating group corresponds to a compound that generates an acid upon irradiation with actinic rays or radiation.
- Examples of such a repeating unit include a repeating unit represented by the following general formula (4).
- R 41 represents a hydrogen atom or a methyl group.
- L 41 represents a single bond or a divalent linking group.
- L 42 represents a divalent linking group.
- R 40 represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.
- examples of the repeating unit represented by the general formula (4) include the repeating units described in paragraphs ⁇ 0094> to ⁇ 0105> of JP-A No. 2014-041327.
- the resin (A) may contain a repeating unit represented by the following general formula (VI).
- R 61 , R 62 and R 63 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
- R 62 may be bonded to Ar 6 to form a ring, and R 62 in this case represents a single bond or an alkylene group.
- X 6 represents a single bond, —COO—, or —CONR 64 —.
- R 64 represents a hydrogen atom or an alkyl group.
- L 6 represents a single bond or an alkylene group.
- Ar 6 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R 62 to form a ring.
- Y 2 each independently represents a group or a hydrogen atom that is eliminated by the action of an acid when n ⁇ 2. However, at least one of Y 2 represents a group capable of leaving by the action of an acid.
- n represents an integer of 1 to 4.
- a structure represented by the following general formula (VI-A) is more preferable.
- L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
- M represents a single bond or a divalent linking group.
- Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. At least two of Q, M, and L 1 may combine to form a ring (preferably a 5-membered or 6-membered ring).
- the repeating unit represented by the general formula (VI) is preferably a repeating unit represented by the following general formula (3). * In the formula represents a bond.
- Ar 3 represents an aromatic ring group.
- R 3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
- M 3 represents a single bond or a divalent linking group.
- Q 3 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. At least two of Q 3 , M 3 and R 3 may be bonded to form a ring.
- the aromatic ring group represented by Ar 3 is the same as Ar 6 in the general formula (VI) when n in the general formula (VI) is 1, more preferably a phenylene group or a naphthylene group, A phenylene group is preferred.
- repeating unit represented by the general formula (VI) are shown below, but the present invention is not limited thereto. * In a specific example represents a bond.
- Resin (A) also preferably contains a repeating unit represented by the following general formula (5).
- R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 42 may be bonded to L 4 to form a ring, and R 42 in this case represents an alkylene group.
- L 4 represents a single bond or a divalent linking group, and in the case of forming a ring with R 42 , represents a trivalent linking group.
- R 44 and R 45 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
- M 4 represents a single bond or a divalent linking group.
- Q 4 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. At least two of Q 4 , M 4 and R 44 may be bonded to form a ring.
- R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 42 may be bonded to L 4 to form a ring, and R 42 in this case represents an alkylene group.
- L 4 represents a single bond or a divalent linking group, and in the case of forming a ring with R 42 , represents a trivalent linking group.
- R 44 and R 45 have the same meaning as R 3 in the general formula (3), and the preferred range is also the same.
- M 4 has the same meaning as M 3 in the general formula (3), and the preferred range is also the same.
- Q 4 has the same meaning as Q 3 in the general formula (3), and the preferred range is also the same.
- Examples of the ring formed by combining at least two of Q 4 , M 4 and R 44 include rings formed by combining at least two of Q 3 , M 3 and R 3 , and the preferred range is the same. It is.
- the alkyl group of R 41 to R 43 in the general formula (5) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, and particularly preferably alkyl groups having 3 or less carbon atoms.
- the alkyl group contained in the alkoxycarbonyl group the same alkyl groups as those described above for R 41 to R 43 are preferable.
- the cycloalkyl group may be monocyclic or polycyclic. Preferred examples include a monocyclic cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which 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 particularly preferable.
- Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls.
- 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. Groups. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable.
- the ring formed by combining R 42 and L 4 is particularly preferably a 5- or 6-membered ring.
- R 41 and R 43 are more preferably a hydrogen atom, an alkyl group, or a halogen atom.
- a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF 3 ), a hydroxymethyl group (—CH 2 —OH), A chloromethyl group (—CH 2 —Cl) and a fluorine atom (—F) are particularly preferred.
- R 42 is more preferably a hydrogen atom, an alkyl group, a halogen atom, or an alkylene group (forming a ring with L 4 ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF 3 ), a hydroxymethyl group Particularly preferred are (—CH 2 —OH), chloromethyl group (—CH 2 —Cl), fluorine atom (—F), methylene group (forms a ring with L 4 ), and ethylene group (forms a ring with L 4 ). .
- L 1 represents an alkylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which an alkylene group and a divalent aromatic ring group are combined.
- L 4 is preferably a single bond, a group represented by —COO—L 1 —, or a divalent aromatic ring group.
- L 1 is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene or propylene group.
- examples of the trivalent linking group represented by L 4 from the embodiment described above of the divalent linking group represented by L 4 1 single Preferable examples include groups formed by removing any hydrogen atom.
- the resin (A) may contain a repeating unit represented by the following general formula (BZ). * In the formula represents a bond.
- 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.
- repeating unit represented by the general formula (BZ) are shown below, but are not limited thereto.
- the above repeating unit having an acid-decomposable group may be one type or a combination of two or more types.
- the content of the repeating unit having an acid-decomposable group in the resin (A) (when there are a plurality of types) is 5 mol% or more and 80 mol% or less with respect to all the repeating units in the resin (A). It is preferably 5 mol% or more and 75 mol% or less, more preferably 10 mol% or more and 65 mol% or less.
- the resin (A) may contain a repeating unit represented by the following general formula (V-1) or the following general formula (V-2).
- R 6 and R 7 are each independently a hydrogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, It represents a halogen atom, an ester group (—OCOR or —COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
- n 3 represents an integer of 0 to 6.
- n 4 represents an integer of 0 to 4.
- X 4 is a methylene group, an oxygen atom or a sulfur atom.
- Specific examples of the repeating unit represented by the general formula (V-1) or (V-2) are shown below, but are not limited thereto.
- the resin (A) may further have a repeating unit having a silicon atom in the side chain.
- a (meth) acrylate repeating unit having a silicon atom, a vinyl repeating unit having a silicon atom, and the like can be given.
- the repeating unit (b) having a silicon atom in the side chain is typically a repeating unit having a group having a silicon atom in the side chain. Examples of the group having a silicon atom include a trimethylsilyl group and a triethylsilyl group.
- Triphenylsilyl group tricyclohexylsilyl group, tristrimethylsiloxysilyl group, tristrimethylsilylsilyl group, methylbistrimethylsilylsilyl group, methylbistrimethylsiloxysilyl group, dimethyltrimethylsilylsilyl group, dimethyltrimethylsiloxysilyl group, Examples thereof include a group having a cyclic or linear polysiloxane structure, or a group having a cage type, ladder type or random type silsesquioxane structure.
- R and R1 each independently represent a monovalent substituent. * Represents a bond.
- repeating unit having the above group for example, a repeating unit derived from an acrylate or methacrylate compound having the above group or a repeating unit derived from a compound having the above group and a vinyl group can be preferably exemplified.
- the repeating unit having a silicon atom is preferably a repeating unit having a silsesquioxane structure, whereby it is ultrafine (for example, a line width of 50 nm or less), and the cross-sectional shape has a high aspect ratio (for example, In the formation of a pattern having a film thickness / line width of 3 or more, a very excellent pattern collapse prevention performance can be exhibited.
- the silsesquioxane structure include a cage silsesquioxane structure, a ladder silsesquioxane structure, and a random silsesquioxane structure. Of these, a cage-type silsesquioxane structure is preferable.
- the cage silsesquioxane structure is a silsesquioxane structure having a cage structure.
- the cage silsesquioxane structure may be a complete cage silsesquioxane structure or an incomplete cage silsesquioxane structure, but may be a complete cage silsesquioxane structure.
- the ladder-type silsesquioxane structure is a silsesquioxane structure having a ladder-like skeleton.
- the random silsesquioxane structure is a silsesquioxane structure having a random skeleton.
- the cage silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).
- R represents a monovalent organic group.
- a plurality of R may be the same or different.
- the organic group is not particularly limited, and specific examples include hydroxy group, nitro group, carboxy group, alkoxy group, amino group, mercapto group, blocked mercapto group (for example, mercapto group protected with acyl group), acyl Group, an imide group, a phosphino group, a phosphinyl group, a silyl group, a vinyl group, a hydrocarbon group which may have a hetero atom, a (meth) acryl group-containing group and an epoxy group-containing group.
- hetero atom of the hydrocarbon group that may have a hetero atom examples include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.
- hydrocarbon group of the hydrocarbon group that may have a hetero atom examples include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group in which these are combined.
- the aliphatic hydrocarbon group may be linear, branched or cyclic.
- Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (particularly 1 to 30 carbon atoms), a linear or branched alkenyl group (particularly 2 to 30 carbon atoms), Examples thereof include a linear or branched alkynyl group (particularly 2 to 30 carbon atoms).
- aromatic hydrocarbon group examples include aromatic hydrocarbon groups having 6 to 18 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
- the content of the repeating unit having a photoacid-generating group is preferably 1 to 40 mol% with respect to all the repeating units in the resin (A). More preferably, it is 5 to 35 mol%, and still more preferably 5 to 30 mol%.
- Resin (A) 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 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 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; And a solvent for dissolving the resist composition of the present invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone. More preferably, the polymerization is performed using the same solvent as that used in the resist composition of the present invention. Thereby, generation
- the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
- a polymerization initiator a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization.
- azo initiator 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.
- concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass.
- the reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.
- Purification can be accomplished by using a liquid-liquid extraction method that removes residual monomers and oligomer components by washing with water or an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less.
- the weight average molecular weight of the resin (A) is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, most preferably from 5,000 to 15, as a polystyrene converted value by the GPC method. 000.
- the weight average molecular weight is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, most preferably from 5,000 to 15, as a polystyrene converted value by the GPC method. 000.
- Another particularly preferable form of the weight average molecular weight of the resin (A) is 3,000 to 9,500 in terms of polystyrene by GPC method.
- the degree of dispersion is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. .
- the smaller the degree of dispersion the better the resolution and the resist shape, the smoother the side wall of the resist pattern, and the better the roughness.
- the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass in the total solid content.
- the resin (A) may be used alone or in combination.
- the actinic ray-sensitive or radiation-sensitive composition preferably contains a compound that generates an acid by actinic rays or radiation (“compound (B)”).
- the compound (B) is the same as the photoacid generator that can be contained in the composition for forming an upper layer film.
- a compound (B) can be used individually by 1 type or in combination of 2 or more types.
- the content of the compound (B) in the actinic ray-sensitive or radiation-sensitive composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, based on the total solid content of the composition. More preferably, it is 8 to 40% by mass.
- the content of the photoacid generator is preferably high, more preferably 10 to 40% by mass, and most preferably 10 to 35% by mass.
- the actinic ray-sensitive or radiation-sensitive composition preferably contains a solvent (also referred to as “resist solvent”).
- the solvent is a group consisting of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable that at least one of at least one selected from more is included.
- the solvent may further contain components other than the components (M1) and (M2).
- the coating property of the actinic ray-sensitive or radiation-sensitive composition is improved and a pattern with a small number of development defects can be formed. To find out. The reason for this is not necessarily clear, but the present inventors have a good balance of solubility, boiling point, and viscosity of the resin (A). It is thought that it originates in being able to suppress generation
- Component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate is particularly preferable.
- the component (M2) the following are preferable.
- propylene glycol monoalkyl ether propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
- lactic acid ester ethyl lactate, butyl lactate or propyl lactate is preferable.
- acetate ester methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferable.
- butyl butyrate is also preferred.
- alkoxypropionate methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
- chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, Acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone are preferred.
- cyclic ketone methylcyclohexanone, isophorone, or cyclohexanone is preferable.
- lactone ⁇ -butyrolactone is preferable.
- alkylene carbonate propylene carbonate is preferable.
- Component (M2) is more preferably propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, ⁇ -butyrolactone or propylene carbonate.
- an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10) and a hetero atom number of 2 or less.
- ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, and butyl propionate. , Isobutyl isobutyrate, heptyl propionate, butyl butanoate and the like, and it is particularly preferable to use isoamyl acetate.
- component (M2) one having a flash point (hereinafter also referred to as fp) of 37 ° C. or higher is preferably used.
- component (M2) include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), methyl amyl ketone (fp: 42 ° C), cyclohexanone (fp: 44 ° C), pentyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), ⁇ -butyrolactone (fp: 101 ° C) or propylene carbonate (fp: 132 ° C) ) Is preferred.
- propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.
- flash point means a value described in a reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma Aldrich.
- the solvent preferably contains the component (M1). It is more preferable that the solvent consists essentially of the component (M1) or a mixed solvent of the component (M1) and other components. In the latter case, it is more preferable that the solvent contains both the component (M1) and the component (M2).
- the mass ratio of the component (M1) and the component (M2) is preferably in the range of 100: 0 to 15:85, more preferably in the range of 100: 0 to 40:60, and 100: More preferably, it is in the range of 0 to 60:40. That is, it is preferable that a solvent consists only of a component (M1) or contains both a component (M1) and a component (M2), and those mass ratios are as follows. That is, in the latter case, the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and further preferably 60/40 or more. preferable. Employing such a configuration makes it possible to further reduce the number of development defects.
- mass ratio of the component (M1) with respect to a component (M2) shall be 99/1 or less, for example.
- the solvent may further contain components other than the components (M1) and (M2).
- the content of components other than components (M1) and (M2) is preferably in the range of 5 to 30% by mass with respect to the total amount of the solvent.
- the content of the solvent in the actinic ray-sensitive or radiation-sensitive composition is preferably determined so that the solid content concentration of all components is 0.5 to 30% by mass, and is preferably 1 to 20% by mass. More preferably, it is determined. If it carries out like this, the applicability
- the actinic ray-sensitive or radiation-sensitive composition preferably contains (E) a basic compound in order to reduce a change in performance over time from exposure to heating.
- a basic compound in order to reduce a change in performance over time from exposure to heating.
- Preferred examples of the basic compound include compounds having structures represented by the following general formulas (E-1) to (E-5).
- R 200 , R 201 and R 202 may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 carbon atoms). To 20) or an aryl group (preferably having 6 to 20 carbon atoms), wherein R 201 and R 202 may be bonded to each other to form a ring.
- 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.
- 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 groups in the general formulas (E-1) and (E-5) 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.
- Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like.
- Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. And undeca-7-ene.
- Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium.
- Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide.
- the compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate.
- Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
- aniline compounds include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
- alkylamine derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine.
- aniline derivatives having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline.
- Preferred examples of the basic compound further include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy 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 an oxyalkylene group 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 an oxyalkylene group Ethylene group.
- the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable.
- the halogen atom is particularly preferably chloride, bromide or iodide
- the sulfonate is particularly preferably an organic sulfonate having 1 to 20 carbon atoms.
- the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.
- the alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups.
- alkyl sulfonate examples include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.
- aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring.
- the benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.
- the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-hexyl, cyclohexyl and the like.
- the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.
- An amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound.
- the phenoxy group may have a substituent.
- the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group.
- the substitution position of the substituent may be any of the 2-6 positions.
- the number of substituents may be any in the range of 1 to 5.
- oxyalkylene group between the phenoxy group and the nitrogen atom.
- 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 an oxyalkylene group Ethylene group.
- the amine compound having a phenoxy group is prepared by reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether by heating, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can be obtained by extraction with an organic solvent such as ethyl acetate or chloroform.
- an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium is added, and then ethyl acetate, It can be obtained by extraction with an organic solvent such as chloroform.
- the actinic ray-sensitive or radiation-sensitive composition has a proton acceptor functional group as a basic compound and is decomposed by irradiation with an actinic ray or radiation to decrease, disappear, or proton
- a compound that generates a compound that has been changed from an acceptor property to an acidity [hereinafter also referred to as a compound (PA)] may be further included.
- 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 general 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 actinic rays or radiation to generate a compound whose 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.
- a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.
- Specific examples of the compound (PA) include the following compounds. Furthermore, as specific examples of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP2014-41328A and paragraphs 0108 to 0116 of JP2014-134686A can be used. The contents of which are incorporated herein.
- the content of the basic compound is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the solid content of the actinic ray-sensitive or radiation-sensitive composition.
- the photoacid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.
- Examples of the basic compound include paragraphs 0140 to 0 of JP2013-11833A.
- 144 compounds amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc. can be used.
- the actinic ray-sensitive or radiation-sensitive composition may contain a hydrophobic resin different from the resin (A), and the hydrophobic resin may be a resin that the upper-layer film-forming composition may contain. Similar ones can also be used.
- hydrophobic resin those described in JP 2011-248019 A, JP 2010-175859 A, and JP 2012-032544 A can also be preferably used.
- the actinic ray-sensitive or radiation-sensitive composition may further contain a surfactant (F).
- a surfactant By containing a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.
- the surfactant it is particularly preferable to use a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in ⁇ 0276> of US Patent Application Publication No. 2008/0248425.
- F top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); 01 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or
- the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991. Further, surfactants other than fluorine-based and / or silicon-based surfactants described in ⁇ 0280> of US Patent Application Publication No. 2008/0248425 may be used.
- surfactants may be used alone or in combination of two or more.
- the content thereof is preferably 0 to 2% by mass based on the total solid content of the actinic ray-sensitive or radiation-sensitive composition. More preferably, the content is 0.0001 to 2% by mass, and still more preferably 0.0005 to 1% by mass.
- the actinic ray-sensitive or radiation-sensitive composition is a compound that promotes solubility in a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a developer (for example, a phenol having a molecular weight of 1000 or less).
- the actinic ray-sensitive or radiation-sensitive composition may further contain a dissolution inhibiting compound.
- the “dissolution inhibiting compound” is a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce the solubility in an organic developer.
- the actinic ray-sensitive or radiation-sensitive composition may contain (G) a carboxylic acid onium salt.
- the carboxylic acid onium salt include a carboxylic acid sulfonium salt, a carboxylic acid iodonium salt, and a carboxylic acid ammonium salt.
- the (G) carboxylic acid onium salt is preferably an iodonium salt or a sulfonium salt.
- the carboxylate residue of the (G) carboxylic acid onium salt does not contain an aromatic group or a carbon-carbon double bond.
- a particularly preferred anion moiety is a linear, branched, monocyclic or polycyclic alkylcarboxylic acid anion having 1 to 30 carbon atoms. More preferably, an anion of a carboxylic acid in which some or all of these alkyl groups are fluorine-substituted is preferable.
- the alkyl chain may contain an oxygen atom. This ensures transparency with respect to light of 220 nm or less, improves sensitivity and resolution, and improves density dependency and exposure margin.
- Fluorine-substituted carboxylic acid anions include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, perfluorotridecanoic acid, perfluorocyclohexanecarboxylic acid, 2 , Anions of 2-bistrifluoromethylpropionic acid, and the like.
- (G) 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 of the carboxylic acid onium salt in the composition is generally from 0.1 to 20% by mass, preferably from 0.5 to 20%, based on the total solid content of the actinic ray-sensitive or radiation-sensitive composition. It is 10% by mass, more preferably 1 to 7% by mass.
- each component is dissolved in a solvent and the actinic ray-sensitive or radiation-sensitive composition is formed. It is preferable to apply this to a substrate after preparing and filtering through a filter as necessary.
- the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and still more preferably 0.03 ⁇ m or less.
- the actinic ray-sensitive or radiation-sensitive composition is applied to a substrate (eg, silicon, silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate application method such as a spinner or a coater. Is preferred. Thereafter, it is preferably dried to form an actinic ray-sensitive or radiation-sensitive film. If necessary, various base films (inorganic films, organic films, antireflection films) may be formed below the actinic ray-sensitive or radiation-sensitive film. Moreover, it is preferable to dry the actinic ray-sensitive or radiation-sensitive film before forming the upper layer film.
- 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 heating temperature is preferably 80 to 150 ° C., more preferably 80 to 140 ° C., and still more preferably 80 to 130 ° C.
- the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.
- the thickness of the actinic ray-sensitive or radiation-sensitive film is generally 200 nm or less, preferably 10 to 100 nm. More preferably, the film thickness ranges from 15 nm to 45 nm. If the film thickness is 15 nm or more, sufficient etching resistance can be obtained. More preferably, the film thickness ranges from 15 nm to 40 nm. When the film thickness is in this range, etching resistance and better resolution performance can be satisfied at the same time.
- Step (b) of the pattern forming method of the present invention is a step of forming an upper layer film on the actinic ray-sensitive or radiation-sensitive film with the upper layer film-forming composition.
- the composition for forming an upper layer film is applied on the actinic ray-sensitive or radiation-sensitive film formed in the step (a), and then heated as necessary (pre-baking (PB; Prebake)).
- pre-baking PB; Prebake
- the pre-baking temperature in the step (b) (hereinafter also referred to as “PB temperature”) is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably 110 ° C. or higher. 120 ° C. or higher is most preferable.
- the upper limit of PB temperature is not specifically limited, For example, 150 degrees C or less is mentioned, 140 degrees C or less is preferable.
- composition for forming an upper layer film used in the pattern forming method of the present invention.
- the composition for forming an upper layer film includes at least one of a compound that generates an acid by actinic rays or radiation, a compound that generates an acid by heat, and an acid.
- the upper layer formed by the composition for forming an upper layer film By having the film on the actinic ray-sensitive or radiation-sensitive film, acid generated on the surface of the actinic ray-sensitive or radiation-sensitive film can be increased, and dissolution of the pattern portion can be suppressed. It is considered that the resolution of fine dots and isolated patterns can be improved.
- the composition for forming an upper layer film used in the pattern forming method of the present invention may be a composition further containing a resin and a solvent in order to uniformly form the actinic ray-sensitive or radiation-sensitive film. preferable.
- the acid which may be contained in the composition for forming an upper layer film will be described.
- the acid that can be contained in the composition for forming an upper layer film is not particularly limited.
- an organic acid such as sulfonic acid or carboxylic acid can be used, and an acid generated from a compound that generates an acid by actinic rays or radiation, an activity
- a compound in which an anion of a compound that generates an acid by light or radiation is protonated can be preferably used. Specific examples include the following compounds.
- An acid can be used individually by 1 type or in combination of 2 or more types.
- the content of the acid in the composition for forming an upper layer film is preferably 0.1 to 50% by mass, more preferably 1 to 50% by mass, and further preferably 1 to 40% by mass based on the total solid content of the composition. %.
- the acid content is more preferably 1 to 30% by mass, and most preferably 1 to 20% by mass in order to achieve both high sensitivity and high resolution upon exposure to electron beams and extreme ultraviolet rays.
- the composition for forming an upper layer film may contain a compound that generates an acid by actinic rays or radiation (also referred to as a “photoacid generator” or “PAG (Photo Acid Generator)”).
- the photoacid generator may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Further, the form of the low molecular compound and the form incorporated in a part of the polymer may be used in combination.
- the photoacid generator is in 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 photoacid generator When the photoacid generator is incorporated into a part of the polymer, it may be incorporated into a part of the resin that can be contained in the composition for forming the upper layer film, or incorporated into a resin different from the above resin. May be.
- the photoacid generator is preferably in the form of a low molecular compound.
- the photoacid generator is not particularly limited as long as it is a known one, but upon irradiation with actinic rays or radiation, preferably electron beams or extreme ultraviolet rays, an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or Compounds that generate at least one of tris (alkylsulfonyl) methides are preferred. More preferable examples of the photoacid generator include compounds represented by the following general formula (ZI), (ZII), or (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 (an anion having an extremely low ability to cause a nucleophilic reaction).
- Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). Carboxylate anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.
- the aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. Examples include 3 to 30 cycloalkyl groups.
- the aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
- the alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms).
- an alkylthio group preferably having 1 to 15 carbon atoms
- an alkylsulfonyl group preferably having 1 to 15 carbon atoms
- an alkyliminosulfonyl group preferably having 1 to 15 carbon atoms
- an aryloxysulfonyl group preferably having carbon atoms Number 6 to 20
- alkylaryloxysulfonyl group preferably having 7 to 20 carbon atoms
- cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like.
- examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).
- aralkyl group in the aralkyl carboxylate anion preferably an aralkyl group having 7 to 12 carbon atoms such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group and the like can be mentioned.
- Examples of the sulfonylimide anion include saccharin anion.
- the alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
- substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like.
- a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
- the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
- non-nucleophilic anions examples include fluorinated phosphorus (eg, PF 6 ⁇ ), fluorinated boron (eg, BF 4 ⁇ ), fluorinated antimony (eg, SbF 6 ⁇ ), and the like. .
- non-nucleophilic anion 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, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom.
- the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane.
- the pKa of the generated acid is preferably ⁇ 1 or less in order to improve sensitivity.
- an anion represented by the following general formula (AN1) can be mentioned as a preferred embodiment.
- each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R 1 and R 2 , they may be the same or different.
- L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
- A represents a cyclic organic group.
- x represents an integer of 1 to 20
- y represents an integer of 0 to 10
- z represents an integer of 0 to 10.
- the alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
- 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.
- Xf include a fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , 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 may be mentioned, among which a fluorine atom and CF 3 are preferable. In particular, it is preferable that both Xf are fluorine atoms.
- the alkyl group of R 1 and R 2 may have a substituent (preferably a fluorine atom), and 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 having a substituent for R 1 and R 2 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , and C 7 F 15.
- R 1 and R 2 are preferably a fluorine atom or CF 3 .
- x is preferably from 1 to 10, and more preferably from 1 to 5.
- y is preferably 0 to 4, more preferably 0.
- z is preferably 0 to 5, and more preferably 0 to 3.
- the divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred.
- —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.
- the cyclic organic group 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 aromaticity but also aromaticity). And the like).
- 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 tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group.
- a polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred.
- an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like is present in the film in the post-exposure heating step Can suppress diffusivity, MEEF (Mask This is preferable from the viewpoint of improving the error enhancement factor.
- Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
- Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.
- examples of the cyclic organic group include lactone structures, and specific examples include lactone structures represented by the general formulas (LC1-1) to (LC1-17).
- 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 having 1 to 12 carbon atoms), cyclo Alkyl group (which may be monocyclic, polycyclic or spiro ring, preferably having 3 to 20 carbon atoms), 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 cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.
- Examples of the organic group for R 201 , R 202, and R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
- R 201 , R 202 and R 203 at least one is preferably an aryl group, more preferably all three are aryl groups.
- aryl group in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.
- Preferred examples of the alkyl group and cycloalkyl group represented by R 201 to R 203 include a straight-chain or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- These groups may further have a substituent.
- substituents include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.
- anion represented by the general formula (AN1) include the following.
- A represents a cyclic organic group. SO 3 —CF 2 —CH 2 —OCO-A, SO 3 —CF 2 —CHF—CH 2 —OCO—A, SO 3 —CF 2 —COO—A, SO 3 —CF 2 —CF 2 —CH 2 — A, SO 3 —CF 2 —CH (CF 3 ) —OCO-A
- R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
- the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the compound (ZI).
- the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent. Examples of the substituent include those that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the compound (ZI) may have.
- Z ⁇ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ⁇ in formula (ZI).
- the photoacid generator has a volume of 130 to 3 or more by irradiation with an electron beam or extreme ultraviolet rays from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution.
- the compound generate an acid (more preferably sulfonic acid) having a size of more than 1, more preferably a compound that generates an acid having a volume of 190 3 or more (more preferably sulfonic acid).
- more preferably 270 ⁇ 3 (more preferably sulfonic acid) or a size of the acid is a compound that generates, be (more preferably sulfonic acid) acid volume 400 ⁇ 3 or more in size is a compound capable of generating an Particularly preferred.
- the volume is preferably 2000 3 or less, and more preferably 1500 3 or less.
- the volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.
- the calculated value of the volume is appended to a part of the example (unit 3 3 ).
- required here is a volume value of the acid which the proton couple
- One foot is 1 ⁇ 10 ⁇ 10 m.
- Examples of the photoacid generator include paragraphs ⁇ 0368> to ⁇ 0377> of JP2014-41328A, paragraphs ⁇ 0240> to ⁇ 0262> of JP2013-228881A (corresponding US Patent Application Publication No. 2015/004533).
- ⁇ 0339> of the specification can be incorporated, the contents of which are incorporated herein.
- the following compounds are mentioned as a preferable specific example, it is not limited to these.
- a photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
- the content in the composition for forming an upper layer film of the photoacid generator is preferably 0.1 to 50% by mass, more preferably 1 to 50% by mass, and still more preferably 1 based on the total solid content of the composition. ⁇ 40% by weight.
- the content of the photoacid generator is more preferably 1 to 30% by mass and most preferably 1 to 20% by mass in order to achieve both high sensitivity and high resolution upon exposure to electron beams and extreme ultraviolet rays. It is.
- the composition for forming an upper layer film may contain a compound that generates an acid by heat (also referred to as “thermal acid generator” or “TAG (Thermal Acid Generator)”).
- thermal acid generator that can be contained in the composition for forming an upper layer film
- ammonium salts and phenacylsulfonium salts are preferable.
- the thermal acid generator preferably contains an anion represented by the general formula (AN1) as a non-nucleophilic anion.
- the temperature at which the thermal acid generator generates an acid is preferably 100 ° C or higher, more preferably 120 ° C or higher.
- the step of applying heat may be PB, PEB, or a step different from these.
- the compound shown below is mentioned, for example.
- a thermal acid generator can be used individually by 1 type or in combination of 2 or more types.
- the content of the thermal acid generator in the composition for forming the upper layer film is preferably 0.1 to 50% by mass, more preferably 1 to 50% by mass, and still more preferably 1 based on the total solid content of the composition. ⁇ 40% by weight.
- the content of the thermal acid generator is more preferably 1 to 30% by mass, most preferably 1 to 20% by mass in order to achieve both high sensitivity and high resolution upon exposure to electron beams and extreme ultraviolet rays. It is.
- the composition for forming an upper layer film includes at least one of a compound that generates an acid by actinic rays or radiation, a compound that generates an acid by heat, and an acid, but two or more kinds may be used in combination.
- a photoacid generator or a thermal acid generator is preferred.
- a thermal acid generator is preferred from the viewpoint that it does not depend on the sensitivity of the actinic ray-sensitive or radiation-sensitive film as the lower layer and can provide a certain effect.
- the composition for forming an upper layer film can contain a solvent.
- the solvent contained in the composition for forming an upper layer film is also referred to as a topcoat solvent.
- the topcoat solvent is preferably a solvent that does not dissolve the actinic ray-sensitive or radiation-sensitive film. More preferably, the solvent is different from the liquid.
- the top coat solvent preferably has a low solubility in the immersion liquid, and more preferably has a low solubility in water. In the present specification, “low solubility in immersion liquid” indicates that the immersion liquid is insoluble.
- low solubility in water indicates water insolubility.
- the boiling point of the solvent is preferably 90 ° C to 200 ° C.
- the low solubility in the immersion liquid means that, for example, the solubility in water, the composition for forming an upper layer film is applied onto a silicon wafer, dried to form a film, and then added to pure water. It means that the decrease rate of the film thickness after dipping for 10 minutes at ° C. and drying is within 3% of the initial film thickness (typically 50 nm).
- the composition for forming the upper layer film preferably has a solid content concentration of 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and more preferably 1 to More preferably, it is 10 mass%.
- the topcoat solvent is not particularly limited as long as it dissolves the resin contained in the composition for forming the upper layer film and does not dissolve the actinic ray-sensitive or radiation-sensitive film, for example, alcohol solvents, ether solvents, Preferable examples include ester solvents, fluorine solvents, hydrocarbon solvents and the like.
- the alcohol solvent is preferably a monohydric alcohol, more preferably a monohydric alcohol having 4 to 8 carbon atoms, from the viewpoint of coatability.
- a monohydric alcohol having 4 to 8 carbon atoms a linear, branched or cyclic alcohol can be used, but a linear or branched alcohol is preferred.
- alcohol solvents examples include 1-butanol, 2-butanol, 3-methyl-1-butanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, isobutyl alcohol, tert- Butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4 -Alcohols such as octanol; glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether Glycol ethers such as triethylene glycol monoethyl ether and methoxymethylbutanol can be used.
- alcohol and glycol ether are preferable, and 1-butanol, 1-hexanol, 1-pentanol, and 3-methyl-1 are preferable. -Butanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, and propylene glycol monomethyl ether are more preferable.
- a non-fluorinated alcohol solvent as the alcohol solvent, which further improves the insolubility in the actinic ray-sensitive or radiation-sensitive film, and activates the composition for forming the upper layer film.
- the upper layer film can be formed more uniformly without dissolving the actinic light-sensitive or radiation-sensitive film.
- fluorine-based solvent examples include 2,2,3,3,4,4-hexafluoro-1-butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol.
- 2-fluoroanisole, 2,3-difluoroanisole, perfluorohexane, perfluoroheptane, perfluoro-2-pentanone, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, perful B tributylamine include perfluor
- hydrocarbon solvent examples include aromatic hydrocarbon solvents such as toluene, xylene, and anisole; n-heptane, n-nonane, n-octane, n-decane, 2-methylheptane, 3-methylheptane, 3 Aliphatic hydrocarbon solvents such as 1,3-dimethylhexane, 2,3,4-trimethylpentane and undecane.
- ether solvent include dioxane, tetrahydrofuran, isoamyl ether, disoamyl ether and the like in addition to the glycol ether solvent.
- ether solvents ether solvents having a branched structure are preferable.
- ester solvents include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate (n-butyl acetate), pentyl acetate, hexyl acetate, isoamyl acetate, butyl propionate (n-butyl propionate), butyl butyrate, butyric acid Isobutyl, butyl butanoate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3- Methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate,
- a topcoat solvent individually by 1 type or in mixture of multiple.
- the mixing ratio is usually 0 to 30% by mass, preferably 0 to 20% by mass, and more preferably 0 to 10% by mass with respect to the total amount of the solvent for the upper layer film-forming composition. %.
- the content of the solvent having a hydroxyl group is preferably 50% by mass or less, more preferably 40% by mass or less, and more preferably 30% by mass or less with respect to the total solvent contained in the upper layer film-forming composition. Is more preferable.
- the content of the solvent having a hydroxyl group in the upper layer film-forming composition is 50% by mass or less, the resin in the actinic ray-sensitive or radiation-sensitive composition is dissolved in the topcoat solvent in the upper layer film-forming composition. Can be prevented, and the resolution can be improved.
- composition for forming an upper layer film may further contain a compound represented by any of the following (A1) to (A4) in addition to the resin and the topcoat solvent.
- A1 Basic compound or base generator
- A2 Compound containing a bond or group selected from the group consisting of ether bond, thioether bond, hydroxyl group, thiol group, carbonyl bond and ester bond
- A3 Ionic compound
- A4 Compound having a radical trap group
- composition for forming an upper layer film preferably further contains at least one of a basic compound and a base generator (hereinafter, these may be collectively referred to as “compound (A1)”).
- the basic compound that can be contained in the composition for forming an upper layer film is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound.
- organic basic compound preferably an organic basic compound
- nitrogen-containing basic compound preferably an organic basic compound.
- those described as basic compounds that may be contained in an actinic ray-sensitive or radiation-sensitive composition can be used, and specifically, structures represented by formulas (E-1) to (E-5) Preferred examples include compounds having the following. Further, for example, compounds classified into the following (1) to (7) can be used.
- Each R independently represents a hydrogen atom or an organic group. However, at least one of the three Rs is an organic group. This organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.
- the number of carbon atoms of the alkyl group as R is not particularly limited, but is usually 1 to 20, and preferably 1 to 12.
- the number of carbon atoms of the cycloalkyl group as R is not particularly limited, but is usually 3 to 20, and preferably 5 to 15.
- the number of carbon atoms of the aryl group as R is not particularly limited, but is usually 6 to 20, and preferably 6 to 10. Specific examples include a phenyl group and a naphthyl group.
- the number of carbon atoms of the aralkyl group as R is not particularly limited, but is usually 7 to 20, preferably 7 to 11. Specific examples include a benzyl group.
- a hydrogen atom may be substituted with a substituent.
- substituents include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.
- Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-isopropylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, Isodecylamine, dicyclohexylmethylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N -Dibutylaniline, N, N-dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tri (t-butyl) aniline.
- preferred basic compounds represented by the general formula (BS-1) include those in which at least one R is an alkyl group substituted with a hydroxy group. Specific examples include triethanolamine and N, N-dihydroxyethylaniline.
- the alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxyalkylene chain may be formed.
- an oxyalkylene chain As the oxyalkylene chain, —CH 2 CH 2 O— is preferable.
- tris (methoxyethoxyethyl) amine and compounds exemplified in the 60th and subsequent lines of column 3 of US6040112 can be mentioned.
- Examples of the basic compound represented by the general formula (BS-1) include the following.
- a compound having a proton acceptor functional group and generating a compound which is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from proton acceptor property to acidity ( PA) This is the same as that described as the basic compound that can be contained in the actinic ray-sensitive or radiation-sensitive composition.
- the compounding ratio of the compound (PA) in the whole composition is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass in the total solid content.
- composition for forming an upper layer film may contain a guanidine compound having a structure represented by the following formula as a basic compound.
- the guanidine compound exhibits strong basicity because the positive charge of the conjugate acid is dispersed and stabilized by three nitrogens.
- the basicity of the guanidine compound is preferably such that the pKa of the conjugate acid is 6.0 or more, and preferably 7.0 to 20.0 because of high neutralization reactivity with the acid and excellent roughness characteristics. More preferably, it is 8.0 to 16.0.
- log P is a logarithmic value of n-octanol / water partition coefficient (P), and is an effective parameter that can characterize the hydrophilicity / hydrophobicity of a wide range of compounds.
- P n-octanol / water partition coefficient
- the distribution coefficient is obtained by calculation without experimentation.
- CSChemDrawUltraVer The value calculated by 8.0 software package (Crippen's fragmentation method) is shown.
- logP of the guanidine compound is preferably 10 or less. It can be made to contain uniformly in an actinic-ray-sensitive or radiation-sensitive film by being below the said value.
- the log P of the guanidine compound is preferably in the range of 2 to 10, more preferably in the range of 3 to 8, and still more preferably in the range of 4 to 8.
- the guanidine compound in the present invention preferably has no nitrogen atom other than the guanidine structure.
- guanidine compound examples include compounds described in paragraphs ⁇ 0765> to ⁇ 0768> of JP2013-83966A, but are not limited thereto.
- Low molecular compound having a nitrogen atom and having a group capable of leaving by the action of an acid comprises a low molecular compound having a nitrogen atom and having a group that can be eliminated by the action of an acid (in the following, a “low molecular compound (D)” or “compound (D)” may be contained.
- the low molecular compound (D) preferably has basicity after the group capable of leaving by the action of an acid is eliminated.
- the group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.
- the molecular weight of the low molecular compound (D) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
- the compound (D) is preferably an amine derivative having a group on the nitrogen atom that is eliminated by the action of an acid.
- Compound (D) 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).
- R ′ each independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R ′ may be bonded to each other to form a ring.
- R ′ 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.
- the compound (D) can also be constituted by arbitrarily combining the basic compound and the structure represented by the general formula (d-1).
- the compound (D) has a structure represented by the following general formula (J).
- the compound (D) may correspond to the above basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid.
- General formula (J)
- Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
- n 2
- the two Ras may be the same or different, and the two Ras are bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof. May be formed.
- Rb each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkoxyalkyl group.
- Rb when one or more Rb is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group, a 1-alkoxyalkyl group or an aryl group.
- At least two Rb may combine to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.
- N represents an integer of 0 to 2
- m represents an integer of 1 to 3
- n + m 3.
- an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group represented by Ra and Rb are functional groups such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, and an oxo group.
- An alkoxy group and a halogen atom may be substituted. The same applies to the alkoxyalkyl group represented by Rb.
- particularly preferable compound (D) in the present invention include compounds described in paragraphs ⁇ 0786> to ⁇ 0788> of JP2013-83966A, but the present invention is not limited thereto. It is not something.
- the compound represented by the general formula (J) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
- the low molecular compound (D) can be used singly or in combination of two or more.
- a photosensitive basic compound may be used as the basic compound.
- the photosensitive basic compound include JP-T-2003-524799 and J. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) and the like can be used.
- a so-called photodegradable base may be used as the basic compound.
- the photodegradable base include onium salts of carboxylic acids and onium salts of sulfonic acids that are not fluorinated at the ⁇ -position.
- Specific examples of photodegradable bases are WO2014 / 1. No. 33048A1, paragraph 0145, Japanese Patent Application Laid-Open No. 2008-158339, and Japanese Patent No. 399146.
- the content of the basic compound in the upper layer film-forming composition is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the solid content of the upper layer film-forming composition. More preferably, it is ⁇ 5% by mass.
- Base generator examples of base generators (preferably photobase generators) that can be contained in the composition for forming an upper layer film include, for example, JP-A-4-151156, JP-A-4-162040, JP-A-5-197148, JP-A-5-5995, Examples thereof include compounds described in JP-A-6-194634, JP-A-8-146608, JP-A-10-83079, and European Patent No. 622682. In addition, compounds described in JP 2010-243773 A are also used as appropriate.
- the photobase generator examples include 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide and 1,1-dimethyl-2-phenylethyl.
- Preferred examples include —N-isopropylcarbamate, but are not limited thereto.
- the content of the base generator in the upper layer film-forming composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the solid content of the upper layer film-forming composition. More preferably, it is ⁇ 5% by mass.
- ⁇ (A2) Compound containing a bond or group selected from the group consisting of ether bond, thioether bond, hydroxyl group, thiol group, carbonyl bond and ester bond>
- a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond (hereinafter also referred to as compound (A2)) will be described below.
- the compound (A2) is a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond. Since the oxygen atom or sulfur atom contained in these groups or bonds has an unshared electron pair, the acid can be trapped by interaction with the acid diffused from the actinic ray-sensitive or radiation-sensitive film.
- the compound (A2) preferably has two or more groups or bonds selected from the above group, more preferably three or more, and still more preferably four or more.
- groups or bonds selected from an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond contained in a plurality of compounds (A2) may be the same or different. Good.
- the compound (A2) preferably has a molecular weight of 3000 or less, more preferably 2500 or less, still more preferably 2000 or less, and particularly preferably 1500 or less.
- the number of carbon atoms contained in the compound (A2) is preferably 8 or more, more preferably 9 or more, and still more preferably 10 or more. In one embodiment of the present invention, the number of carbon atoms contained in the compound (A2) is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
- the compound (A2) is preferably a compound having a boiling point of 200 ° C. or higher, more preferably a compound having a boiling point of 220 ° C. or higher, and a compound having a boiling point of 240 ° C. or higher. More preferably it is.
- the compound (A2) is preferably a compound having an ether bond, preferably two or more ether bonds, more preferably three or more, and four or more. More preferably. In one embodiment of the present invention, the compound (A2) further preferably contains a repeating unit containing an oxyalkylene structure represented by the following general formula (1).
- R 11 represents an alkylene group which may have a substituent
- n represents an integer of 2 or more
- * represents a bond.
- the number of carbon atoms of the alkylene group represented by R 11 in the general formula (1) is not particularly limited, but is preferably 1 to 15, more preferably 1 to 5, and preferably 2 or 3. More preferably, 2 is particularly preferable.
- the alkylene group has a substituent, the substituent is not particularly limited, but is preferably an alkyl group (preferably having 1 to 10 carbon atoms).
- n 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.
- the average value of n is preferably 20 or less, more preferably 2 to 10, more preferably 2 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. preferable.
- the “average value of n” means the value of n determined so that the weight average molecular weight of the compound (A2) is measured by GPC and the obtained weight average molecular weight matches the general formula. If n is not an integer, round it off.
- a plurality of R 11 may be the same or different.
- the compound having the partial structure represented by the general formula (1) is preferably a compound represented by the following general formula (1-1) because the DOF becomes larger.
- 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.
- R 12 and R 13 may combine with each other to form a ring.
- m represents an integer of 1 or more.
- m is preferably an integer of 1 to 20, and among them, it is more preferably 10 or less for the reason that DOF becomes larger.
- the average value of m is preferably 20 or less, more preferably 1 to 10, more preferably 1 to 8, and particularly preferably 4 to 6 because the DOF becomes larger. preferable.
- the “average value of m” is synonymous with the “average value of n” described above.
- a plurality of R 11 may be the same or different.
- the compound having a partial structure represented by the general formula (1) is preferably an alkylene glycol containing at least two ether bonds.
- Compound (A2) may be a commercially available product, or may be synthesized by a known method.
- the content of the compound (A2) is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, still more preferably 2 to 20% by mass, based on the total solid content in the upper layer film. 18% by mass is particularly preferred.
- the composition for forming an upper layer film may contain an ionic compound that becomes a weak acid relative to the acid generator in the actinic ray-sensitive or radiation-sensitive composition or the composition for forming an upper layer film.
- An onium salt is preferred as the ionic compound.
- 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.
- sulfonium cation or iodonium cation represented by M + include a sulfonium cation exemplified by the general formula (ZI) and an iodonium cation exemplified by the general formula (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 structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.
- the onium salt that is a weak acid relative to the acid generator is a compound (C) having a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety being linked by a covalent bond (Hereinafter also referred to as “compound (CA)”).
- the compound (CA) 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 in the upper layer film-forming composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and more preferably 2.5% by mass or more, based on the solid content of the upper layer film-forming composition. Is more preferable.
- the upper limit of the content of the onium salt is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and more preferably 8% by mass based on the solid content of the composition for forming an upper layer film. The following are particularly preferred:
- a compound having a radical trap group is also referred to as a compound (A4).
- the radical trap group is a group that traps an active radical and stops a radical reaction.
- examples of such radical trap groups include groups that react with active radicals to be converted into stable free radicals, and groups that have stable free radicals.
- the radical trap group having no basicity is, for example, at least one selected from the group consisting of a hindered phenol group, a hydroquinone group, an N-oxyl free radical group, a nitroso group, and a nitrone group.
- the group is preferably exemplified.
- the number of radical trap groups possessed by the compound (A4) is not particularly limited, but when the compound (A4) is a compound other than the above polymer compound, the number of radical trap groups is preferably 1 to 10 per molecule. ⁇ 5 are more preferred, and 1 to 3 are even more preferred.
- the repeating unit having a radical trap group preferably has 1 to 5 radical trap groups, and has 1 to 3 radical trap groups. It is more preferable.
- the composition ratio of the repeating unit having a radical trap group in the polymer compound is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, and still more preferably 30 to 100 mol%.
- a compound having a nitrogen-oxygen bond is preferable because the effect of the present invention is more excellent, and the following general formulas (1) to (3) are preferable because the effect of the present invention is further improved.
- the compound represented by either of these is more preferable.
- the compound represented by the following general formula (1) corresponds to a compound having an N-oxyl free radical group
- the compound represented by the following general formula (2) corresponds to a compound having a nitroso group
- a compound represented by the following general formula (3) corresponds to a compound having a nitrone group.
- R 1 to R 6 each independently represents an alkyl group, a cycloalkyl group, or an aryl group.
- R 1 and R 2 may be bonded to form a ring, and in formula (3), at least two of R 4 to R 6 may be bonded to form a ring.
- An alkyl group, a cycloalkyl group, and an aryl group represented by R 1 to R 6 a ring that R 1 and R 2 may be bonded to each other, and at least two of R 4 to R 6 are bonded to each other;
- the ring which may be formed may have a substituent.
- the compound represented by any one of the general formulas (1) to (3) may be in the form of a resin.
- at least one of R 1 to R 6 is a main chain or a side chain of the resin. It may be bound to.
- the compound (A4) may be a polymer compound having a repeating unit.
- the specific example of the repeating unit which the compound (A4) which is a high molecular compound has is shown below, this invention is not limited to this.
- the molecular weight of the compound having a radical trap group is not particularly limited, and is preferably 100 to 5000, more preferably 100 to 2000, and still more preferably 100 to 1000. Further, when the compound having a radical trap group is a polymer compound having a repeating unit, the weight average molecular weight is preferably 5000 to 20000, and more preferably 5000 to 10,000.
- the compound having a radical trap group a commercially available compound may be used, or a compound synthesized by a known method may be used.
- Compound A is synthesized by a reaction between a commercially available low molecular compound having a radical trap group and a high molecular compound having a reactive group such as an epoxy group, a halogenated alkyl group, an acid halide group, a carboxyl group, or an isocyanate group. May be.
- the content of the compound having a radical trap group is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solid content of the composition for forming an upper layer film.
- the composition for forming an upper layer film may contain a plurality of one kind of compounds among the compounds represented by (A1) to (A4). For example, two or more compounds (A1) distinguished from each other may be included. Further, the composition for forming an upper layer film may contain two or more compounds represented by (A1) to (A4). For example, you may contain both a compound (A1) and a compound (A2).
- the composition for forming an upper layer film includes a plurality of compounds represented by (A1) to (A4), the total content of these compounds is based on the total solid content of the composition for forming an upper layer film of the present invention. Usually, it is 0.001 to 20% by mass, preferably 0.01 to 10% by mass, and more preferably 1 to 8% by mass.
- the resin (X) that can be suitably used for the composition for forming the upper layer film is transparent to the exposure light source to be used because light reaches the actinic ray-sensitive or radiation-sensitive film through the upper layer film during exposure. Is preferred.
- the resin When used in ArF immersion exposure, the resin preferably has substantially no aromatic group from the viewpoint of transparency to ArF light.
- the resin (X) preferably has a fluorine atom content of 20% by mass or less.
- the fluorine atom content in the resin (X) is preferably 20% by mass or less, more preferably 10% by mass or less, ideally substantially with respect to the weight average molecular weight of the resin (X). 0 mass%.
- the resin (X) is preferably a resin having a CH 3 partial structure in the side chain portion.
- the CH 3 partial structure of the side chain portion in the resin (X) includes the CH 3 partial structure of an ethyl group, a propyl group, or the like. Is.
- a methyl group directly bonded to the main chain of the resin (X) (for example, an ⁇ -methyl group of a repeating unit having a methacrylic acid structure) is not included in the CH 3 partial structure in the present invention.
- the resin (X) 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 is as true for 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.
- Examples of 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 resin (X) 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 It is more preferable to have at least one repeating unit (x) among the repeating units represented by the general formula (III).
- the resin (X) can suitably contain a repeating unit represented by the general 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 decomposed by the action of “acid” described in the acid-decomposable resin contained in the actinic ray-sensitive or radiation-sensitive resin composition described later. It is preferable that the organic group does not have a group that generates an alkali-soluble group.
- 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 examples 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.
- the above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group may further have an alkyl group as a substituent.
- 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 3 or more and 8 or less.
- the alkyl group having one or more CH 3 partial structures in R 2 is preferably a branched alkyl group having 3 to 20 carbon atoms.
- preferable alkyl groups include isopropyl group, isobutyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, and 3-methyl-4.
- the cycloalkyl group having one or more CH 3 partial structures in R 2 may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The number of carbon atoms is preferably 6-30, and particularly preferably 7-25.
- Preferred cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclododecanyl group, and tricyclodecanyl group.
- R 2 is preferably a cycloalkyl group having one or more CH 3 partial structures. More preferred are polycyclic cycloalkyl groups having one or more CH 3 partial structures, more preferred are polycyclic cycloalkyl groups having two or more CH 3 partial structures, and three or more CH 3 partial structures. Polycyclic cycloalkyl groups are particularly preferred. Of these, a polycyclic cycloalkyl group substituted with three or more alkyl groups is preferred.
- the alkenyl group having one or more CH 3 partial structures in R 2 is preferably a linear or branched alkenyl group having 1 to 20 carbon atoms, and more preferably a branched alkenyl group.
- the aryl group having one or more CH 3 partial structures in R 2 is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. is there.
- the aralkyl group having one or more CH 3 partial structures in R 2 is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
- hydrocarbon group having two or more CH 3 partial structures in R 2 include isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, 2-methyl-3-butyl. Group, 3-hexyl group, 2,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, Examples include 3,5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group, and isobornyl group.
- the repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, and 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.
- 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.
- R 3 is an organic group that is stable to acid, and more specifically, does not have a “group that decomposes by the action of an acid to generate an alkali-soluble group”, which will be described later in the acid-decomposable resin.
- An organic group is preferred.
- 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.
- the alkyl group having one or more CH 3 partial structures in R 3 is preferably a branched alkyl group having 3 to 20 carbon atoms.
- preferable alkyl groups include isopropyl group, isobutyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, and 3-methyl-4.
- alkyl group having two or more CH 3 partial structures in R 3 include isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, 2,3-dimethylbutyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4, 4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, etc. .
- it has 5 to 20 carbon atoms, and is an isopropyl group, t-butyl group, 2-methyl-3-butyl group, 2-methyl-3-pentyl group, or 3-methyl-4-hexyl group. 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3, 5,7-tetramethyl-4-heptyl group and 2,6-dimethylheptyl group.
- 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, and 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 content of at least one repeating unit (x) among the repeating units represented by (III) is preferably 90 mol% or more and 95 mol% or more with respect to all repeating units of the resin (X). It is more preferable that The content is usually 100 mol% or less with respect to all repeating units of the resin (X).
- Resin (X) is a repeating unit represented by general formula (II), and at least one repeating unit (x) among repeating units represented by general formula (III)
- the surface free energy of the resin (X) increases.
- the resin (X) is less likely to be unevenly distributed on the surface of the actinic ray-sensitive or radiation-sensitive composition film, and the static / dynamic contact angle of the actinic ray-sensitive or radiation-sensitive film with respect to water is ensured. It is possible to improve the immersion liquid followability.
- the resin (X) is preferably a resin containing a repeating unit derived from a monomer containing at least one fluorine atom and / or at least one silicon atom. More preferably, it is a water-insoluble resin containing a repeating unit derived from a monomer containing one fluorine atom and / or at least one silicon atom.
- a repeating unit derived from a monomer containing at least one fluorine atom and / or at least one silicon atom good solubility in an organic solvent developer can be obtained, and the effects of the present invention can be sufficiently obtained. .
- the fluorine atom or silicon atom in the resin (X) may be contained in the main chain of the resin or may be substituted with a side chain.
- the resin (X) is preferably 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) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.
- 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 another substituent.
- aryl group having a fluorine atom examples 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 another substituent.
- alkyl group having a fluorine atom the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom are shown below, but the present invention is not limited thereto.
- R 57 to R 64 each independently represents a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R 57 to R 61 and R 62 to R 64 represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably having 1 to 4 carbon atoms). R 57 to R 61 are preferably all fluorine atoms. R 62 and R 63 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 more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. 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 trifluoroethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 1,3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like.
- Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
- Resin (X) is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom.
- Examples of the resin (X) include resins having at least one selected from the group of repeating units represented by the following general formulas (CI) to (CV).
- R 1 to R 3 each independently represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms. Represents a group.
- W 1 and W 2 represent an organic group having at least one of a fluorine atom and a silicon atom.
- R 4 to R 7 are each independently a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms. Represents a group. However, at least one of R 4 to R 7 represents a fluorine atom. R 4 and R 5 or R 6 and R 7 may form a ring.
- R 8 represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
- R 9 represents a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms.
- L 1 and L 2 represent a single bond or a divalent linking group, and are the same as L 3 to L 5 described above.
- Q represents a monocyclic or polycyclic cycloaliphatic group. That is, it represents an atomic group that contains two bonded carbon atoms (C—C) and forms an alicyclic structure.
- R 30 and R 31 each independently represents a hydrogen atom or a fluorine atom.
- R 32 and R 33 each independently represents an alkyl group, a cycloalkyl group, a fluorinated alkyl group or a fluorinated cycloalkyl group.
- the repeating unit represented by the general formula (CV) has at least one fluorine atom in at least one of R 30 , R 31 , R 32 and R 33 .
- the resin (X) preferably has a repeating unit represented by the general formula (CI), and further has a repeating unit represented by the following general formulas (C-Ia) to (C-Id). preferable.
- R 10 and R 11 represent a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched fluorinated alkyl group having 1 to 4 carbon atoms.
- W 3 to W 6 each represents an organic group having at least one of a fluorine atom and a silicon atom.
- W 1 to W 6 are organic groups having a fluorine atom, they are fluorinated linear, branched alkyl or cycloalkyl groups having 1 to 20 carbon atoms, or fluorinated having 1 to 20 carbon atoms. It is preferably a linear, branched, or cyclic alkyl ether group.
- Examples of the fluorinated alkyl group of W 1 to W 6 include trifluoroethyl group, pentafluoropropyl group, hexafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, heptafluorobutyl group, heptafluoroisopropyl group, octafluoro Examples thereof include an isobutyl group, a nonafluorohexyl group, a nonafluoro-t-butyl group, a perfluoroisopentyl group, a perfluorooctyl group, and a perfluoro (trimethyl) hexyl group.
- W 1 to W 6 are an organic group having a silicon atom, it is preferably an alkylsilyl structure or a cyclic siloxane structure. Specific examples include groups represented by the above general formulas (CS-1) to (CS-3).
- X represents a hydrogen atom, —CH 3 , —F, or —CF 3 .
- Resin (X) may have a repeating unit represented by the following general formula (Ia) in order to adjust the solubility in an organic solvent developer.
- Rf represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
- R 1 represents an alkyl group.
- R 2 represents a hydrogen atom or an alkyl group.
- the alkyl group in which at least one hydrogen atom of Rf is substituted with a fluorine atom preferably has 1 to 3 carbon atoms, and more preferably a trifluoromethyl group.
- the alkyl group for R 1 is preferably a linear or branched alkyl group having 3 to 10 carbon atoms, A branched alkyl group having 3 to 10 carbon atoms is more preferable.
- R 2 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and 3 to 1 carbon atoms. A linear or branched alkyl group of 0 is more preferable.
- Resin (X) may further have a repeating unit represented by the following general formula (III).
- R 4 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a trialkylsilyl group, or a group having a cyclic siloxane structure.
- L 6 represents a single bond or a divalent linking group.
- the alkyl group of R 4 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
- the cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.
- the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.
- the cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
- the trialkylsilyl group is preferably a trialkylsilyl group having 3 to 20 carbon atoms.
- the group having a cyclic siloxane structure is preferably a group having a cyclic siloxane structure having 3 to 20 carbon atoms.
- the divalent linking group of L 6 is preferably an alkylene group (preferably having 1 to 5 carbon atoms) or an oxy group.
- Resin (X) may have a lactone group, an ester group, an acid anhydride, or a group similar to the acid-decomposable group in the acid-decomposable resin described later. Resin (X) may further have a repeating unit represented by the following general formula (VIII).
- Resin (X) preferably contains a repeating unit (d) derived from a monomer having an alkali-soluble group.
- Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) Imido 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, tris (alkylsulfonyl) methylene group, tris (alky
- the monomer having an alkali-soluble group is preferably a monomer having an acid dissociation index pKa of 4 or more, more preferably a monomer having a pKa of 4 to 13, and most preferably a monomer having a pKa of 8 to 13.
- pKa contains a monomer of 4 or more, swelling during negative-type and positive-type development is suppressed, and not only good developability for an organic solvent developer but also a weakly basic alkaline developer is used. Also good developability can be obtained.
- the acid dissociation constant pKa is described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.), and the pKa value of a monomer containing an alkali-soluble group is, for example, infinite It can measure at 25 degreeC using a dilution solvent.
- the monomer having a pKa of 4 or more is not particularly limited, and examples thereof include monomers having an acid group (alkali-soluble group) such as a phenolic hydroxyl group, a sulfonamide group, —COCH 2 CO—, a fluoroalcohol group, and a carboxylic acid group. Can be mentioned.
- a monomer containing a fluoroalcohol group is preferred.
- the fluoroalcohol group is a fluoroalkyl group substituted with at least one hydroxyl group, preferably having 1 to 10 carbon atoms, more preferably having 1 to 5 carbon atoms.
- fluoroalcohol group examples include, for example, —CF 2 OH, —CH 2 CF 2 OH, —CH 2 CF 2 CF 2 OH, —C (CF 3 ) 2 OH, —CF 2 CF (CF 3 ) OH. , —CH 2 C (CF 3 ) 2 OH, and the like.
- fluoroalcohol group is a hexafluoroisopropanol group.
- the total amount of repeating units derived from the monomer having an alkali-soluble group in the resin (X) is preferably 0 to 90 mol%, more preferably 0 to 80 mol, based on all repeating units constituting the resin (X).
- the mol% is even more preferably 0 to 70 mol%.
- the monomer having an alkali-soluble group may contain only one acid group or two or more acid groups.
- the repeating unit derived from this monomer preferably has two or more acid groups per repeating unit, more preferably 2 to 5 acid groups, and 2 to 3 acid groups. It is particularly preferred.
- the resin (X) is preferably any resin selected from the following (X-1) to (X-8).
- (X-3) a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), a branched alkyl group (preferably having 4 to 20 carbon atoms), a cycloalkyl group (preferably having 4 carbon atoms) To 20), a repeating unit (c) having a branched alkenyl group (preferably having 4 to 20 carbon atoms), a cycloalkenyl group (preferably having 4 to 20 carbon atoms) or an aryl group (preferably having 4 to 20 carbon atoms) More preferably, a copolymer resin of the repeating unit (a) and the repeating unit (c).
- (X-4) a repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, a branched alkyl group (preferably having 4 to 20 carbon atoms), a cycloalkyl group (preferably having 4 to 20 carbon atoms), Resin having a repeating unit (c) having a branched alkenyl group (preferably having 4 to 20 carbon atoms), a cycloalkenyl group (preferably having 4 to 20 carbon atoms) or an aryl group (preferably having 4 to 20 carbon atoms) More preferably, a copolymer resin of the repeating unit (b) and the repeating unit (c).
- (X-5) a resin having a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms) and a repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, more preferably a repeating unit Copolymer resin of unit (a) and repeating unit (b).
- (X-6) a repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), a repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, and a branched alkyl group (preferably Is a C4-20), cycloalkyl group (preferably C4-20), branched alkenyl group (preferably C4-20), cycloalkenyl group (preferably C4-20) or aryl
- Repeating unit (c) having a branched alkyl group, cycloalkyl group, branched alkenyl group, cycloalkenyl group or aryl group in resins (X-3), (X-4) and (X-6)
- an appropriate functional group can be introduced.
- the repeating unit constituting each of the above (X-1) to (X-6) further has a repeating unit having an alkali-soluble group (d) (preferably having an alkali-soluble group having a pKa of 4 or more. Resin having a repeating unit).
- Resins (X-3), (X-4), (X-6), and (X-7) have a repeating unit (a) having a fluoroalkyl group and / or a trialkylsilyl group, or a cyclic siloxane structure
- the repeating unit (b) is preferably 10 to 99 mol%, more preferably 20 to 80 mol%.
- Resin (X) is preferably solid at room temperature (25 ° C.). Further, the glass transition temperature (Tg) is preferably 50 to 200 ° C., more preferably 80 to 160 ° C.
- Solid at 25 ° C.” means that the melting point is 25 ° C. or higher.
- the glass transition temperature (Tg) can be measured by scanning calorimetry (Differential Scanning Calorimeter). For example, the specific volume changed when the sample was heated once, cooled and then heated again at 5 ° C./min. It can be measured by analyzing the value.
- Resin (X) is preferably insoluble in an immersion liquid (preferably water) and soluble in an organic solvent developer (preferably a developer containing an ester solvent).
- an organic solvent developer preferably a developer containing an ester solvent
- the resin (X) can be used with respect to the alkaline developer from the viewpoint of being able to develop and peel off using the alkaline developer. It is preferably soluble.
- the content of the silicon atom is preferably 2 to 50% by mass and more preferably 2 to 30% by mass with respect to the molecular weight of the resin (X).
- the repeating unit containing a silicon atom is preferably 10 to 100% by mass in the resin (X), and more preferably 20 to 100% by mass.
- the weight average molecular weight in terms of standard polystyrene of the resin (X) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, still more preferably 2,000 to 15,000, particularly preferably. Is between 3,000 and 15,000.
- the resin (X) has few impurities such as metals, but from the viewpoint of reducing elution from the upper layer film to the immersion liquid, the residual monomer amount is preferably 0 to 10% by mass, more preferably. Is more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass.
- the molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 1.5.
- resin (X) various commercial products can be used, and ⁇ 0017> to ⁇ 0023> of JP 2013-61647 A (corresponding ⁇ 0017> to ⁇ 0023 of US Published Patent Application 2013/244438. >), ⁇ 0016> to ⁇ 0165> of JP-A-2014-56194, and ⁇ 0014> to ⁇ 0077> of JP-A-2015-152773 can also be used.
- These resins can be synthesized according to 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 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 examples include ethers such as tetrahydrofuran, 1,4-dioxane, 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.
- a polymerization initiator a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization.
- azo initiator 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.
- a chain transfer agent can also be used as needed.
- the concentration of the reaction is usually 5 to 50% by mass, preferably 20 to 50% by mass, more preferably 30 to 50% by mass.
- the reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.
- Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less.
- Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent
- a normal method such as a method can be applied.
- the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times the volume of the reaction solution.
- the solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for this polymer.
- hydrocarbons penentane, hexane, Aliphatic hydrocarbons such as heptane and octane; Cycloaliphatic hydrocarbons such as cyclohexane and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene and xylene), halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, etc.) Halogenated aliphatic hydrocarbons; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, etc.), nitriles (acetonitrile, benzonitrile, etc.), ethers (diethyl ether, diisopropyl ether, dimeth
- a solvent containing at least an alcohol (particularly methanol or the like) or water is preferable.
- the amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally, 100 to 10,000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300 to 1000 parts by mass.
- the diameter of the nozzle when the polymer solution is supplied into the precipitation or reprecipitation solvent (poor solvent) is preferably 4 mm ⁇ or less (for example, 0.2 to 4 mm ⁇ ).
- the supply speed (dropping speed) of the polymer solution into the poor solvent is, for example, about 0.1 to 10 m / second, preferably about 0.3 to 5 m / second as the linear speed.
- Precipitation or reprecipitation operation is preferably performed with stirring.
- a stirring blade used for stirring for example, a desk turbine, a fan turbine (including a paddle), a curved blade turbine, an arrow blade turbine, a fiddler type, a bull margin type, an angled blade fan turbine, a propeller, a multistage type, an anchor type (or Horseshoe type), gate type, double ribbon, screw, etc. can be used.
- Stirring is preferably further performed for 10 minutes or more, particularly 20 minutes or more after the supply of the polymer solution.
- the stirring time is short, the monomer content in the polymer particles may not be sufficiently reduced.
- the polymer solution and the poor solvent can be mixed and stirred using a line mixer instead of the stirring blade.
- the temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.).
- the precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.
- Precipitated or re-precipitated particulate polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).
- the resin may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent.
- step a After completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is contacted to precipitate the resin (step a), the resin is separated from the solution (step b), and the resin solution A is dissolved again in the solvent.
- the solvent used in the preparation of the resin solution A can be the same solvent as the solvent that dissolves the monomer in the polymerization reaction, and may be the same as or different from the solvent used in the polymerization reaction.
- Resin (X) may be used alone or in combination.
- the topcoat composition contains a plurality of resins (X), it is preferable to contain at least one resin (XA) having fluorine atoms and / or silicon atoms.
- the topcoat composition contains at least one resin (XA) having a fluorine atom and / or silicon atom, and a resin (XB) having a fluorine atom and / or silicon atom content smaller than that of the resin (XA). More preferred.
- the resin (XA) is unevenly distributed on the surface of the topcoat film, so that performance such as development characteristics and immersion liquid followability can be improved.
- the content of the resin (XA) is preferably 0.01 to 30% by mass, more preferably 0.1 to 10% by mass, and more preferably 0.1 to 8% by mass, based on the total solid content contained in the topcoat composition. % Is more preferable, and 0.1 to 5% by mass is particularly preferable.
- the content of the resin (XB) is preferably 50.0 to 99.9% by mass, more preferably 60 to 99.9% by mass, based on the total solid content in the topcoat composition, and 70 to 99.99%. 9% by mass is more preferable, and 80 to 99.9% by mass is particularly preferable.
- the preferable range of the content of fluorine atoms and silicon atoms contained in the resin (XA) is the same as the preferable range when the resin (X) has a fluorine atom and when the resin (X) has a silicon atom.
- the resin (XB) a form that substantially does not contain a fluorine atom and a silicon atom is preferable.
- the total content of the repeating unit having a fluorine atom and the repeating unit having a silicon atom is, It is preferably 0 to 20 mol%, more preferably 0 to 10 mol%, still more preferably 0 to 5 mol%, particularly preferably 0 to 3 mol%, ideally with respect to all repeating units in the resin (XB). Is 0 mol%, that is, does not contain fluorine atoms or silicon atoms.
- the compounding amount of the resin (X) in the entire top coat composition is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass in the total solid content.
- the composition for forming an upper layer film is preferably filtered by dissolving each component in a solvent.
- the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and still more preferably 0.03 ⁇ m or less. Note that a plurality of types of filters may be connected in series or in parallel.
- the composition may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step. Furthermore, you may perform a deaeration process etc. with respect to a composition before and after filter filtration.
- the composition for forming an upper layer film of the present invention does not contain impurities such as metals.
- the content of the metal component contained in these materials is preferably 10 ppm or less, more preferably 5 ppm or less, still more preferably 1 ppm or less, and particularly preferably (not more than the detection limit of the measuring device). .
- the upper layer film is disposed between the actinic ray-sensitive or radiation-sensitive film and the immersion liquid, and the actinic ray-sensitive or radiation-sensitive film is directly It also functions as a layer that is not in contact with the immersion liquid.
- preferable properties of the upper layer film include suitability for application to an actinic ray-sensitive or radiation-sensitive film, transparency to radiation, particularly 193 nm, and immersion liquid (preferably Poorly soluble in water). Further, it is preferable that the upper layer film is not mixed with the actinic ray-sensitive or radiation-sensitive film and can be uniformly applied to the surface of the actinic-ray-sensitive or radiation-sensitive film.
- the composition for forming the upper layer film is used.
- the composition for forming the upper layer film is used.
- the solvent that does not dissolve the actinic ray-sensitive or radiation-sensitive film it is more preferable to use a solvent having a component different from that of the developer containing the organic solvent (organic developer).
- the method for applying the composition for forming the upper layer film is not particularly limited, and a conventionally known spin coat method, spray method, roller coat method, dipping method, or the like can be used.
- the thickness of the upper layer film is not particularly limited, but is usually 5 nm to 300 nm, preferably 10 nm to 300 nm, more preferably 20 nm to 200 nm, still more preferably 30 nm to 100 nm from the viewpoint of transparency to the exposure light source. .
- the substrate is heated (PB) as necessary.
- the refractive index of the upper layer film is preferably close to the refractive index of the actinic ray-sensitive or radiation-sensitive film from the viewpoint of resolution.
- the upper layer film is preferably insoluble in the immersion liquid, and more preferably insoluble in water.
- the receding contact angle of the upper layer film is preferably 50 to 100 degrees, more preferably 80 to 100 degrees, from the viewpoint of immersion liquid followability. More preferred.
- immersion exposure 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 an exposure pattern.
- the contact angle of the immersion liquid with respect to the light-sensitive or radiation-sensitive film is important, and in order to obtain better resist performance, it is preferable to have a receding contact angle in the above range.
- an organic developer may be used, or a separate release agent may be used.
- a solvent having a small penetration into the actinic ray sensitive or radiation sensitive film is preferable.
- the upper layer film can be peeled off with an organic developer in that the upper layer film can be peeled off simultaneously with the development of the actinic ray-sensitive or radiation-sensitive film.
- the organic developer used for peeling is not particularly limited as long as it can dissolve and remove the low-exposed portion of the actinic ray-sensitive or radiation-sensitive film.
- the dissolution rate of the upper layer film in the organic developer is preferably 1 to 300 nm / sec, more preferably 10 to 100 nm / sec.
- the dissolution rate of the upper layer film with respect to the organic developer is a rate of film thickness reduction when the upper layer film is formed and then exposed to the developer.
- the film was immersed in butyl acetate at 23 ° C. Speed.
- the line edge of the pattern after developing the actinic ray-sensitive or radiation-sensitive film probably due to the effect of reducing the exposure unevenness during the immersion exposure. There is an effect that the roughness becomes better.
- the upper layer film may be removed using another known developer, for example, an alkaline aqueous solution.
- the aqueous alkali solution that can be used include an aqueous solution of tetramethylammonium hydroxide.
- the pre-wet solvent is not particularly limited as long as it has low solubility in the actinic ray-sensitive or radiation-sensitive film, but it is not limited to alcohol solvents, fluorine solvents, ether solvents, hydrocarbon solvents, ester solvents.
- a pre-wet solvent for the upper layer film containing one or more compounds selected from can be used.
- the alcohol solvent is preferably a monohydric alcohol, more preferably a monohydric alcohol having 4 to 8 carbon atoms, from the viewpoint of coatability.
- a monohydric alcohol having 4 to 8 carbon atoms a linear, branched or cyclic alcohol can be used, but a linear or branched alcohol is preferred.
- alcohol solvents examples include 1-butanol, 2-butanol, 3-methyl-1-butanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, isobutyl alcohol, tert- Butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4 -Alcohols such as octanol; glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether Glycol ethers such as triethylene glycol monoethyl ether and methoxymethylbutanol can be used.
- alcohol and glycol ether are preferable, and 1-butanol, 1-hexanol, 1-pentanol, and 3-methyl-1 are preferable.
- -Butanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, and propylene glycol monomethyl ether are more preferable.
- ether solvents include dipropyl ether, diisopropyl ether, butyl methyl ether, butyl ethyl ether, butyl propyl ether, dibutyl ether, diisobutyl ether, tert-butyl methyl ether, tert-butyl ethyl ether, tert-butyl propyl ether, di -Tert-butyl ether, dipentyl ether, diisoamyl ether, cyclopentyl methyl ether, cyclohexyl methyl ether, cyclopentyl ethyl ether, cyclohexyl ethyl ether, cyclopentyl propyl ether, cyclopentyl-2-propyl ether, cyclohexyl propyl ether, cyclohexyl -2-propyl ether, cyclopentyl butyl ether,
- fluorine-based solvent examples include 2,2,3,3,4,4-hexafluoro-1-butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol.
- 2-fluoroanisole, 2,3-difluoroanisole, perfluorohexane, perfluoroheptane, perfluoro-2-pentanone, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, perful B tributylamine include perfluor
- hydrocarbon solvent examples include aromatic hydrocarbon solvents such as toluene, xylene, and anisole; n-heptane, n-nonane, n-octane, n-decane, 2-methylheptane, 3-methylheptane, 3 Aliphatic hydrocarbon solvents such as 1,3-dimethylhexane and 2,3,4-trimethylpentane.
- ester solvents include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate (n-butyl acetate), pentyl acetate, hexyl acetate, isoamyl acetate, butyl propionate (n-butyl propionate), butyl butyrate, butyric acid Isobutyl, butyl butanoate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3- Methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate,
- solvents may be used singly or in combination.
- solubility in the actinic ray-sensitive or radiation-sensitive film solubility of the resin in the composition for forming the upper layer film, elution characteristics from the actinic ray-sensitive or radiation-sensitive film, Etc. can be adjusted appropriately.
- Step (c) of the pattern forming method of the present invention is a step of exposing the actinic ray-sensitive or radiation-sensitive film on which the upper layer film is formed, and can be performed by, for example, the following method.
- the actinic ray-sensitive or radiation-sensitive film having the upper layer film formed as described above is irradiated with actinic rays or radiation through a predetermined mask. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common.
- actinic light or radiation examples include KrF excimer laser, ArF excimer laser, extreme ultraviolet (EUV, Extreme Ultra Violet), an electron beam (EB, Electron Beam), etc., and extreme ultraviolet rays or an electron beam is especially preferable.
- the exposure may be immersion exposure.
- baking is preferably performed after exposure and before development.
- the reaction of the exposed part is promoted by baking, and the sensitivity and pattern shape become better.
- the heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and still more preferably 80 to 130 ° C.
- the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds. Heating can be performed by normal exposure or by means provided in a developing machine, and may be performed using a hot plate or the like.
- Step (d) of the pattern forming method of the present invention is a step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer containing an organic solvent.
- the developer used in the development step (d) contains an organic solvent, it can also be referred to as an organic developer.
- the vapor pressure of the organic solvent (the vapor pressure as a whole in the case of a mixed solvent) 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 solvent is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
- An ester solvent is a solvent having an ester bond in the molecule
- a ketone solvent is a solvent having a ketone group in the molecule
- an alcohol solvent is a solvent having an alcoholic hydroxyl group in the molecule.
- An amide solvent is a solvent having an amide group in the molecule
- an ether solvent is a solvent having an ether bond in the molecule.
- diethylene glycol monomethyl ether corresponds to both alcohol solvents and ether solvents in the above classification.
- the hydrocarbon solvent is a hydrocarbon solvent having no substituent.
- the developer preferably contains at least one solvent selected from ester solvents, ketone solvents, ether solvents, and hydrocarbon solvents, and is preferably a developer containing an ester solvent. Is more preferable.
- ester solvent examples include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentyl acetate, 3-methylbutyl acetate), acetic acid 2 -Methylbutyl, 1-methylbutyl acetate, hexyl acetate, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, butyl butyrate, methyl 2-hydroxyisobutyrate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2- Acetoxypropane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether a
- butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, and butyl butanoate are preferably used, and isoamyl acetate is particularly preferable. Preferably used.
- ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, Phenyl acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, ⁇ -butyrolactone, etc. Heptanone and ⁇ -butyrolactone are preferred.
- alcohol solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1 -Hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pen Tanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2- Pentanol, 3-methyl-3-pentanol, 4-methyl- -Pentanol, 4-methyl-3-pentanol,
- ether solvents include glycol ether solvents that contain hydroxyl groups, glycol ether solvents that do not contain hydroxyl groups such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, anisole, and phenetole.
- aromatic ether solvents dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane and the like.
- an glycol ether solvent or an aromatic ether solvent such as anisole is used.
- amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
- hydrocarbon solvent examples include pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, perfluoroheptane.
- Aliphatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, dipropylbenzene, etc.
- aromatic hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene and the like.
- the unsaturated hydrocarbon solvent may have a plurality of double bonds and triple bonds, and may be present at any position of the hydrocarbon chain.
- the hydrocarbon solvent may be a mixture of compounds having the same carbon number and different structures.
- decane when decane is used as an aliphatic hydrocarbon solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isodecane, which are compounds having the same carbon number and different structures, are aliphatic hydrocarbon solvents. May be included.
- the compounds having the same number of carbon atoms and different structures may include only one kind or plural kinds as described above.
- the developer has 7 or more carbon atoms (preferably 7 to 14, preferably 7 to 14) from the viewpoint that the actinic ray-sensitive or radiation-sensitive film can be prevented from swelling. 12 is more preferable, and 7 to 10 is more preferable), and it is preferable to use an ester solvent having 2 or less heteroatoms.
- the hetero atom of the ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, and a sulfur atom.
- the number of heteroatoms is preferably 2 or less.
- ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, Examples thereof include butyl propionate, isobutyl isobutyrate, heptyl propionate, and butyl butanoate, and it is particularly preferable to use isoamyl acetate.
- the developer is a mixture of the ester solvent and the hydrocarbon solvent instead of the ester solvent having 7 or more carbon atoms and 2 or less hetero atoms.
- a solvent or a mixed solvent of the ketone solvent and the hydrocarbon solvent may be used. Even in this case, it is effective in suppressing swelling of the actinic ray-sensitive or radiation-sensitive film.
- isoamyl acetate is preferably used as the ester solvent.
- a saturated hydrocarbon solvent for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.
- 2-heptanone is preferably used as the ketone solvent.
- a saturated hydrocarbon solvent for example, octane, nonane, decane, dodecane, undecane, hexadecane, etc.
- the content of the hydrocarbon solvent is not particularly limited because it depends on the solvent solubility of the actinic ray-sensitive or radiation-sensitive film. That's fine.
- a plurality of the above organic solvents may be mixed, or may be used by mixing with other solvents 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.
- the concentration of the organic solvent (total in the case of a plurality of mixtures) in the developer is preferably 50% by mass or more, more preferably 50 to 100% by mass, further preferably 85 to 100% by mass, and even more preferably 90 to 100% by mass. %, Particularly preferably 95 to 100% by mass. Most preferably, it consists essentially of an organic solvent.
- the case where it consists only of an organic solvent includes the case where a trace amount surfactant, antioxidant, stabilizer, an antifoamer, etc. are contained.
- the developer preferably contains an antioxidant.
- an antioxidant thereby, generation
- the antioxidant known ones can be used, but when used for semiconductor applications, amine-based antioxidants and phenol-based antioxidants are preferably used.
- the content of the antioxidant is not particularly limited, but is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, and 0.0001 to 0% with respect to the total mass of the developer. More preferred is 0.01 mass%. When it is 0.0001% by mass or more, a more excellent antioxidant effect is obtained, and when it is 1% by mass or less, development residue tends to be suppressed.
- the developer may contain a basic compound, and specific examples thereof include the same basic compounds that may be contained in the actinic ray-sensitive or radiation-sensitive composition.
- the developer may contain a surfactant.
- a surfactant When the developer contains a surfactant, the wettability with respect to the actinic ray-sensitive or radiation-sensitive film is improved, and development proceeds more effectively.
- the surfactant the same surfactants that can be contained in the actinic ray-sensitive or radiation-sensitive composition can be used.
- the surfactant content is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, based on the total mass of the developer. %, More preferably 0.01 to 0.5% by mass.
- 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.
- the development time is not particularly limited, and is usually 10 to 300 seconds, preferably 20 to 120 seconds.
- the temperature of the developer is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
- development with an alkali developer may be performed in addition to development using a developer containing an organic solvent.
- the pattern forming method of the present invention preferably has, after step (d), a step (e) of rinsing (washing) the developed actinic ray-sensitive or radiation-sensitive film with a rinsing liquid.
- a step (e) of rinsing (washing) the developed actinic ray-sensitive or radiation-sensitive film with a rinsing liquid it is preferable to use a rinse liquid containing a hydrocarbon solvent for the reason that the effects of the present invention are more excellent.
- a rinsing liquid which is a kind of organic processing liquid is used in the rinsing process and contains an organic solvent, and can also be referred to as an organic rinsing liquid.
- This rinsing liquid is preferably used for “cleaning” (that is, “rinsing” the actinic ray-sensitive or radiation-sensitive film) of the actinic ray-sensitive or radiation-sensitive film using an organic treatment liquid.
- the vapor pressure of the rinsing liquid (the vapor pressure as a whole in the case of a mixed 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, and 0.12 kPa or more at 20 ° C. Most preferably, it is 3 kPa or less.
- Organic solvent Various organic solvents are used as the organic solvent contained in the rinsing liquid, and are selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. It is preferable to use at least one organic solvent. Specific examples of these organic solvents are the same as those described for the developer.
- the organic solvent contained in the rinsing liquid when EUV light or EB is used in the exposure step, it is preferable to use a hydrocarbon solvent among the above organic solvents, and it is more preferable to use an aliphatic hydrocarbon solvent.
- an aliphatic hydrocarbon solvent having 5 or more carbon atoms for example, pentane, hexane, octane, decane, undecane, dodecane, Hexadecane, etc.
- aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred
- aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred.
- the upper limit of the carbon atom number of the said aliphatic hydrocarbon solvent is not specifically limited, For example, 16 or less is mentioned, 14 or less is preferable and 12 or less is more preferable.
- the aliphatic hydrocarbon solvents decane, undecane, and dodecane are particularly preferable, and undecane is most preferable.
- a hydrocarbon solvent particularly an aliphatic hydrocarbon solvent
- the developer slightly soaked in the actinic ray-sensitive or radiation-sensitive film after development is washed away. Thus, the effect of further suppressing swelling and suppressing pattern collapse is further exhibited.
- hydrocarbon solvent examples include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene and the like.
- unsaturated hydrocarbon solvent may have a plurality of double bonds and triple bonds, and may be present at any position of the hydrocarbon chain. Cis and trans isomers having a double bond may be mixed.
- the hydrocarbon solvent may be a mixture of compounds having the same carbon number and different structures.
- decane when used as an aliphatic hydrocarbon solvent, 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isodecane, which are compounds having the same carbon number and different structures, are aliphatic hydrocarbon solvents. May be included.
- the compounds having the same number of carbon atoms and different structures may include only one kind or plural kinds as described above.
- a plurality of organic solvents may be mixed, or may be used by mixing with an organic solvent other than the above.
- the solvent may be mixed with water, but the water content in the rinsing liquid is usually 60% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less. is there.
- a favorable rinse characteristic can be acquired by making a moisture content into 60 mass% or less.
- the rinse liquid contains a surfactant.
- a surfactant the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive composition can be used.
- the content of the surfactant 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 mass of the rinse liquid. .
- the rinse liquid preferably contains an antioxidant. Thereby, generation
- Specific examples and contents of the antioxidant are as described in the above developer.
- the developed wafer is cleaned using the above rinsing liquid.
- the method of the cleaning process 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), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time. Examples thereof include a method (dip method) and a method (spray method) in which a rinse liquid is sprayed onto the substrate surface. Among these, it is preferable to remove the rinse liquid from the substrate by performing a cleaning process by a spin coating method and then rotating the substrate at a rotational speed of 2000 rpm to 4000 rpm.
- the developer and the rinsing liquid are stored in a waste liquid tank through a pipe after use.
- a hydrocarbon solvent is used as the rinsing liquid
- the resist dissolves again in order to prevent the dissolved resist from being deposited in the developer and adhering to the back surface of the wafer or the side of the pipe.
- As a method of passing through the piping after washing with a rinsing solution, cleaning the back and side surfaces of the substrate with a solvent that dissolves the resist, or passing the solvent through which the resist dissolves without contacting the resist. The method of flowing in is mentioned.
- development may be performed using an alkaline developer after development using an organic developer.
- a portion with low exposure intensity is removed by development using an organic solvent, but a portion with high exposure intensity is also removed by development using an alkaline developer.
- a pattern can be formed without dissolving only an intermediate exposure intensity region, so that a finer pattern than usual can be formed (paragraph of JP 2008-292975 A).
- a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used.
- an alkaline aqueous solution such as an inorganic alkali, a primary to tertiary amine, an alcohol amine, or a cyclic amine is also used. Is possible.
- an appropriate amount of alcohol or surfactant may be added to the alkaline developer.
- 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 development time using an alkali developer is usually 10 to 300 seconds.
- the alkali concentration (and pH) and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed. You may wash
- the rinse solution pure water can be used and an appropriate amount of a surfactant can be added. Further, after the development process or the rinsing process, a process of removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed. Further, after the rinsing process or the supercritical fluid process, a heat treatment can be performed to remove moisture remaining in the pattern.
- Actinic ray-sensitive or radiation-sensitive composition in the present invention and various materials used in the pattern forming method of the present invention (for example, a resist solvent, a developer, a rinse solution, an antireflection film-forming composition, an upper layer film)
- the forming composition or the like preferably does not contain impurities such as metals, metal salts containing halogens, acids (excluding acids contained in the upper film forming composition), and alkalis.
- the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
- Examples of the method for removing impurities such as metals from 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.
- an apparatus that selects a raw material having a low metal content as a raw material constituting each material, and performs filter filtration on the raw material constituting each material. Examples thereof include a method of performing distillation under a condition in which the inside is lined with Teflon (registered trademark) and contamination is suppressed as much as possible.
- Teflon registered trademark
- 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.
- the organic solvent (organic processing liquid) that can be used for the developer and the rinsing liquid it is possible to use one stored in a container for storing an organic processing liquid for patterning a chemically amplified resist film, which has a storage section. preferable.
- the inner wall of the container that comes into contact with the organic treatment liquid is subjected to a resin different from polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or subjected to rust prevention and metal elution prevention treatment.
- the container is a container for an organic processing solution for patterning a chemically amplified resist film formed from the formed metal.
- An organic solvent to be used as an organic processing liquid for patterning a chemically amplified resist film is stored in the container of the container and discharged from the container when patterning the chemically amplified resist film. Can be used.
- the seal part is also a resin different from polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or It is preferably formed from a metal that has been subjected to rust prevention and metal elution prevention treatment.
- a seal part means the member which can interrupt
- the resin different from the polyethylene resin, the polypropylene resin, and the polyethylene-polypropylene resin is preferably a perfluoro resin.
- Perfluoro resins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoride.
- PTFE tetrafluoroethylene resin
- PFA perfluoroalkyl vinyl ether copolymer
- FEP tetrafluoroethylene-hexafluoropropylene copolymer resin
- Ethylene-ethylene copolymer resin Ethylene-ethylene copolymer resin (ETFE), ethylene trifluoride-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride chloride copolymer resin (PCTFE), vinyl fluoride resin ( PVF) and the like.
- Particularly preferred perfluoro resins include tetrafluoroethylene resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.
- Examples of the metal in the metal subjected to the rust prevention / metal elution prevention treatment include carbon steel, alloy steel, nickel chromium steel, nickel chromium molybdenum steel, chromium steel, chromium molybdenum steel, manganese steel and the like.
- As the rust prevention / metal elution prevention treatment it is preferable to apply a film technology.
- Preferable film technology includes surface treatment with a rust preventive oil, a rust preventive agent, a corrosion inhibitor, a chelate compound, a peelable plastic, and a lining agent.
- a rust preventive oil various chromates, nitrites, silicates, phosphates, carboxylic acids such as oleic acid, dimer acid, naphthenic acid, carboxylic acid metal soaps, sulfonates, amine salts, esters (glycerin esters of higher fatty acids)
- chelating compounds such as ethylene diantetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethyl ethyl orange amine triacetic acid, diethylenetriamine pentaacetic acid, and fluororesin lining.
- pretreatment is a stage before rust prevention treatment. It is also preferable to adopt.
- a treatment for removing various corrosion factors such as chlorides and sulfates existing on the metal surface by washing and polishing can be preferably mentioned.
- the storage container include the following. ⁇ FluoroPure PFA composite drum manufactured by Entegris (Wetted inner surface; PFA resin lining) ⁇ JFE steel drums (wetted inner surface; zinc phosphate coating)
- Examples of the storage container that can be used in the present invention include containers described in JP-A-11-021393 ⁇ 0013> to ⁇ 0030> and JP-A-10-45961 ⁇ 0012> to ⁇ 0024>. be able to.
- the organic processing liquid in the present invention may be added with a conductive compound in order to prevent chemical piping and various parts (filters, O-rings, tubes, etc.) from being damaged due to electrostatic charging and subsequent electrostatic discharge. good.
- a conductive compound for example, methanol is mentioned.
- the addition amount is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of maintaining preferable development characteristics.
- SUS stainless steel
- various pipes coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) should be used. it can.
- polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used for the filter and O-ring.
- the pattern obtained by the pattern forming method of the present invention is generally suitably used as an etching mask for a semiconductor device or the like, but can also be used for other purposes.
- Other uses include, for example, guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4, No. 8, Page 4815-4823), use as a core material (core) of a so-called spacer process (for example, JP-A-3-270227, JP-A-2013-164509, etc.).
- the present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention.
- the electronic device manufactured by the method for manufacturing an electronic device according to the present invention is suitably mounted in the manufacture of electrical and electronic equipment (home appliances, OA (Office Appliance) / media related equipment, optical equipment, communication equipment, etc.). It is.
- electrical and electronic equipment home appliances, OA (Office Appliance) / media related equipment, optical equipment, communication equipment, etc.
- the present invention also relates to a laminate having an actinic ray-sensitive or radiation-sensitive film and a compound that generates an acid by actinic rays or radiation, a compound that generates an acid by heat, and an upper layer film containing at least one of the acids.
- the laminate of the present invention preferably comprises an actinic ray-sensitive or radiation-sensitive film on a substrate, a compound that generates an acid by actinic rays or radiation, a compound that generates an acid by heat, and an upper layer film containing at least one of acids. In this order, and can be suitably used as a resist material for pattern formation contained in semiconductor devices and the like.
- resins (A-1) to (A-8) and (A-13) to (A-17) were used as resins in the resist composition.
- photoacid generator As the photoacid generator, the following were used.
- SL-1 Propylene glycol monomethyl ether acetate (PGMEA)
- SL-2 Gamma butyrolactone
- SL-3 Cyclohexanone
- SL-4 Ethyl lactate
- PG-5 Propylene glycol monomethyl ether (PGME)
- the hydrophobic resin As the hydrophobic resin, the following resins (1b) to (4b) were used.
- the structures of the resins (1b) to (4b), the composition ratio of each repeating unit (molar ratio; corresponding in order from the left), weight average molecular weight (Mw), and dispersity (Mw / Mn) are shown below.
- composition for forming upper layer film Resin having a repeating unit content molar ratio (composition ratio), a weight average molecular weight (Mw), and a molecular weight distribution (Mw / Mn) shown in Table 3 below, and components shown in Table 4 below are dissolved in a solvent.
- MIBC Methyl isobutyl carbinol
- Y2 decane
- Y3 diisoamyl ether
- Y4 1-butanol
- Y5 isobutyl isobutyrate
- a resist pattern was formed by the following operation using the resist composition and the composition for forming an upper layer film.
- EUV exposure apparatus (Microtech made by Exitech Co., Ltd.) was applied to the wafer produced above. Pattern exposure was performed through a mask using Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). Specifically, in order to obtain a dot pattern after negative development, EUV exposure was carried out by changing the exposure amount through a dark mask containing a hole pattern having a pitch of 100 nm and a diameter of 20 nm. However, since only the comparative example 2 performs positive development, EUV exposure was performed by changing the exposure amount through a bright mask including a dot pattern having a pitch of 100 nm and a diameter of 20 nm.
- PEB Post-exposure bake
- SG-1 2-Heptanone (methyl amyl ketone)
- SG-2 Isoamyl acetate
- SG-3 Butyl acetate
- SG-4 2.38 mass% tetrabutylammonium aqueous solution
- SG-5 Diisobutyl ketone
- the patterns (Examples 1 to 13) formed by the pattern forming method of the present invention have excellent dot resolution, and in the formation of extremely fine residual patterns. High resolution was obtained.
- the patterns (Examples 14 to 25) formed by the pattern forming method of the present invention have excellent dot resolution, and in the formation of ultrafine residual patterns. High resolution was obtained.
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Abstract
Description
より詳細には、本発明は、IC(Integrated Circuit、集積回路)等の半導体製造工程、液晶、サーマルヘッド等の回路基板の製造、さらにはその他のフォトアプリケーションのリソグラフィー工程に使用されるパターン形成方法、上記パターン形成方法を含む電子デバイスの製造方法、及び積層体に関する。
(a)感活性光線性又は感放射線性組成物により感活性光線性又は感放射線性膜を形成する工程、(b)上記感活性光線性又は感放射線性膜上に上層膜形成用組成物により上層膜を形成する工程、(c)上記上層膜が形成された上記感活性光線性又は感放射線性膜を露光する工程、及び(d)露光された上記感活性光線性又は感放射線性膜を、有機溶剤を含有する現像液で現像する工程を含むパターン形成方法であって、上記上層膜形成用組成物が、活性光線又は放射線により酸を発生する化合物、熱により酸を発生する化合物及び酸の少なくとも1つを含む、パターン形成方法。
[2]
上記上層膜形成用組成物が、下記一般式(AN1)で表されるアニオンを含む、[1]に記載のパターン形成方法。
[3]
上記上層膜形成用組成物が熱により酸を発生する化合物を含む、[1]又は[2]に記載のパターン形成方法。
[4]
上記上層膜形成用組成物は溶剤を含有し、上記上層膜形成用組成物に含まれる全溶剤に対して、水酸基を有する溶剤の含有比率が50質量%以下である、[1]~[3]のいずれか一項に記載のパターン形成方法。
[5]
上記上層膜形成用組成物は、芳香環を有する繰り返し単位を含有する樹脂を含む、[1]~[4]のいずれか一項に記載のパターン形成方法。
[6]
上記感活性光線性又は感放射線性膜は感活性光線性又は感放射線性組成物により形成され、上記感活性光線性又は感放射線性組成物は、芳香環を有する繰り返し単位を含有する樹脂を含む、[1]~[5]のいずれか一項に記載のパターン形成方法。
[7]
上記有機溶剤を含有する現像液は、エステル系溶剤、ケトン系溶剤、エーテル系溶剤、及び炭化水素系溶剤から選択される少なくとも1種の溶剤を含む、[1]~[6]のいずれか一項に記載のパターン形成方法。
[8]
-上記有機溶剤を含有する現像液は、エステル系溶剤を含む、[1]~[7]のいずれか一項に記載のパターン形成方法。
[9]
上記工程(d)の後に、(e)現像された上記感活性光線性又は感放射線性膜をリンス液を用いてリンスする工程、
を含む、[1]~[8]のいずれか一項に記載のパターン形成方法。
[10]
上記リンス液が炭化水素系溶剤を含むリンス液である[9]に記載のパターン形成方法。
[11]
[1]~[10]のいずれか一項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。
[12]
感活性光線性又は感放射線性膜と、
活性光線又は放射線により酸を発生する化合物、熱により酸を発生する化合物及び酸の少なくとも1つを含む上層膜と
を有する積層体。
尚、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のみではなく、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。
本明細書中における「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、電子線等を意味する。本発明において光とは、活性光線又は放射線を意味する。本明細書中における「露光」とは、特に断らない限り、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、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。
本明細書では、「(メタ)アクリル系モノマー」とは、「CH2=CH-CO-」又は「CH2=C(CH3)-CO-」の構造を有するモノマーの少なくとも1種を意味する。同様に「(メタ)アクリレート」及び「(メタ)アクリル酸」とは、それぞれ「アクリレート及びメタクリレートの少なくとも1種」並びに「アクリル酸及びメタクリル酸の少なくとも1種」を意味する。
本明細書において、樹脂の重量平均分子量は、GPC(ゲルパーミエーションクロマトグラフィー)法により測定したポリスチレン換算値である。GPCは、HLC-8120(東ソー(株)製)を用い、カラムとしてTSK gel Multipore HXL-M (東ソー(株)製、7.8mmID×30.0cm)を、溶離液としてTHF(テトラヒドロフラン)を用いた方法に準ずる事ができる。
本発明のパターン形成方法は、(a)感活性光線性又は感放射線性組成物により感活性光線性又は感放射線性膜を形成する工程、(b)上記感活性光線性又は感放射線性膜上に上層膜形成用組成物により上層膜を形成する工程、(c)上記感活性光線性又は感放射線性膜を露光する工程、及び(d)露光された上記感活性光線性又は感放射線性膜を、有機溶剤を含有する現像液で現像する工程を含むパターン形成方法であって、
上記上層膜形成用組成物が、活性光線又は放射線により酸を発生する化合物、熱により酸を発生する化合物及び酸の少なくとも1つを含む、パターン形成方法である。
本発明のパターン形成方法の工程(a)は、感活性光線性又は感放射線性組成物により感活性光線性又は感放射線性膜を形成するであり、好ましくは基板上に感活性光線性又は感放射線性組成物を塗布することにより感活性光線性又は感放射線性膜を形成する工程である。
感活性光線性又は感放射線性組成物はレジスト組成物であることが好ましく、感活性光線性又は感放射線性膜はレジスト膜であることが好ましい。
本発明のパターン形成方法において、感活性光線性又は感放射線性組成物を基板上に塗布して感活性光線性又は感放射線性膜を形成することが好ましい。
感活性光線性又は感放射線性組成物は、有機溶剤を含む現像液を使用する有機溶剤現像用の感活性光線性又は感放射線性組成物であることが好ましい。ここで、有機溶剤現像用とは、少なくとも、有機溶剤を含む現像液を用いて現像する工程に供される用途を意味する。
感活性光線性又は感放射線性組成物は好ましくはレジスト組成物であり、より好ましくは化学増幅型レジスト組成物である。また、本発明における感活性光線性又は感放射線性組成物はポジ型レジスト組成物であってもネガ型レジスト組成物であってもよいが、ネガ型レジスト組成物であることが好ましい。
本発明における感放射線性又は感活性光線性組成物は、電子線又は極紫外線露光用であることが好ましい。
感活性光線性又は感放射線性組成物は、感活性光線性又は感放射線性樹脂組成物であることが好ましい。
感活性光線性又は感放射線性組成物は、樹脂(A)を含有することが好ましい。樹脂(A)は、少なくとも(i)酸の作用により分解してカルボキシル基を生じる基を有する繰り返し単位(さらに、フェノール性水酸基を有する繰り返し単位を有してもよい)、または、少なくとも(ii)フェノール性水酸基を有する繰り返し単位を有することが好ましい。
樹脂(A)は、芳香環を有する繰り返し単位を含有する樹脂を含むことが好ましい。樹脂(A)が芳香環を有する繰り返し単位を含有することで、特に電子線またはEUV露光の際に、二次電子の発生効率、及び活性光線又は放射線により酸を発生する化合物からの酸発生効率が高くなり、パターン形成時に高感度化、高解像化の効果が期待できる。
なお、酸の作用により分解してカルボキシル基を有する繰り返し単位を有すると、酸の作用により有機溶剤に対する溶解度が減少する。
X4は、単結合、-COO-、又は-CONR64-を表し、R64は、水素原子又はアルキル基を表す。
L4は、単結合又はアルキレン基を表す。
Ar4は、(n+1)価の芳香環基を表し、R42と結合して環を形成する場合には(n+2)価の芳香環基を表す。nは、1~5の整数を表す。
一般式(I)におけるR41、R42、R43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、フッ素原子が特に好ましい。
一般式(I)におけるR41、R42、R43の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R41、R42、R43におけるアルキル基と同様のものが好ましい。
(n+1)価の芳香環基は、更に置換基を有していてもよい。
X4により表される-CONR64-(R64は、水素原子、アルキル基を表す)におけるR64のアルキル基としては、好ましくは置換基を有していてもよいメチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、ヘキシル基、2-エチルヘキシル基、オクチル基、ドデシル基など炭素数20以下のアルキル基が挙げられ、より好ましくは炭素数8以下のアルキル基が挙げられる。
X4としては、単結合、-COO-、-CONH-が好ましく、単結合、-COO-がより好ましい。
Ar4としては、置換基を有していてもよい炭素数6~18の芳香環基がより好ましく、ベンゼン環基、ナフタレン環基、ビフェニレン環基が特に好ましい。
一般式(I)で表される繰り返し単位は、ヒドロキシスチレン構造を備えていることが好ましく、ベンゼン環基であることがより好ましい。
Rは、ハロゲン原子、アルキル基、シクロアルキル基、アリール基、アルケニル基、アラルキル基、アルコキシ基、アルキルカルボニルオキシ基、アルキルスルホニルオキシ基、アルキルオキシカルボニル基又はアリールオキシカルボニル基を表し、複数個ある場合には同じであっても異なっていてもよい。複数のRを有する場合には、互いに共同して環を形成していてもよい。Rとしては水素原子が好ましい。aは1~3の整数を表し、好ましくは1である。bは0~(3-a)の整数を表す。
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。
Xa1は、水素原子、又は置換基を有していてもよいアルキル基を表す。
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。ただし、Rx1~Rx3の全てがアルキル基(直鎖若しくは分岐)である場合、Rx1~Rx3のうち少なくとも2つはメチル基であることが好ましい。
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。
ラクトン基としては、ラクトン構造を有していればいずれの基でも用いることができるが、好ましくは5~7員環ラクトン構造を含有する基であり、5~7員環ラク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)のいずれかで表されるラクトン構造を有する基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、ラクトン構造を有する基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としては一般式(LC1-1)、
(LC1-4)、(LC1-5)、(LC1-6)、(LC1-13)、(LC1-14)で表される基である。
Rb0のアルキル基が有していてもよい好ましい置換基としては、水酸基、ハロゲン原子が挙げられる。
Rb0のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、沃素原子を挙げることができる。Rb0は、水素原子又はメチル基が好ましい。
Abは、単結合、アルキレン基、単環または多環の脂環炭化水素構造を有する2価の連結基、エーテル基、エステル基、カルボニル基、又はこれらを組み合わせた2価の基を表す。好ましくは、単結合、-Ab1-CO2-で表される連結基である。Ab1は、直鎖、分岐アルキレン基、単環または多環のシクロアルキレン基であり、好ましくは、メチレン基、エチレン基、シクロヘキシレン基、アダマンチレン基、ノルボルニレン基である。
Vは、一般式(LC1-1)~(LC1-17)のうちのいずれかで示される基を表す。
樹脂(A)は、極性基を有する有機基を含有する繰り返し単位、特に、極性基で置換された脂環炭化水素構造を有する繰り返し単位をさらに有することができる。
極性基で置換された脂環炭化水素構造としてはアダマンチル基、ジアダマンチル基、ノルボルナン基が好ましい。極性基としては水酸基、シアノ基が好ましい。
極性基を有する繰り返し単位の具体例を以下に挙げるが、本発明はこれらに限定されない。
このような繰り返し単位としては、例えば、下記一般式(4)で表される繰り返し単位が挙げられる。
X6は、単結合、-COO-、又は-CONR64-を表す。R64は、水素原子又はアルキル基を表す。 L6は、単結合又はアルキレン基を表す。Ar6は、(n+1)価の芳香環基を表し、R62と結合して環を形成する場合には(n+2)価の芳香環基を表す。Y2は、n≧2の場合には各々独立に、酸の作用により脱離する基又は水素原子を表す。但し、Y2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の整数を表す。
酸の作用により脱離する基としては、下記一般式(VI-A)で表される構造がより好ましい。
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R41~R43におけるアルキル基と同様のものが好ましい。
シクロアルキル基としては、単環型でも、多環型でもよい。好ましくは置換基を有していても良いシクロプロピル基、シクロペンチル基、シクロヘキシル基のような炭素数3~10個で単環型のシクロアルキル基が挙げられる。
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、フッ素原子が特に好ましい。
L4は、単結合、-COO-L1-で表される基又は2価の芳香環基が好ましい。L1は炭素数1~5のアルキレン基が好ましく、メチレン、プロピレン基がより好ましい。2価の芳香環基としては、1,4-フェニレン基、1,3-フェニレン基、1,2-フェニレン基、1,4-ナフチレン基が好ましく、1,4-フェニレン基がより好ましい。
L4がR42と結合して環を形成する場合における、L4で表される3価の連結基としては、L4で表される2価の連結基の上記した具体例から1個の任意の水素原子を除してなる基を好適に挙げることができる。
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。
R6及びR7は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数1~10の直鎖状、分岐状又は環状のアルキル基、アルコキシ基又はアシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基(-OCOR又は-COOR:Rは炭素数1~6のアルキル基又はフッ素化アルキル基)、又はカルボキシル基を表す。 n3は0~6の整数を表す。n4は0~4の整数を表す。X4はメチレン基、酸素原子又は硫黄原子である。一般式(V-1)又は(V-2)で表される繰り返し単位の具体例を下記に示すが、これらに限定されない。
樹脂(A)は、側鎖に珪素原子を有する繰り返し単位を更に有していても良い。例えば、珪素原子を有する(メタ)アクリレート系繰り返し単位、珪素原子を有するビニル系繰り返し単位などが挙げられる。側鎖に珪素原子を有する繰り返し単位(b)は、典型的には、側鎖に珪素原子を有する基を有する繰り返し単位であり、珪素原子を有する基としては、例えば、トリメチルシリル基、トリエチルシリル基、トリフェニルシリル基、トリシクロヘキシルシリル基、トリストリメチルシロキシシリル基、トリストリメチルシリルシリル基、メチルビストリメチルシリルシリル基、メチルビストリメチルシロキシシリル基、ジメチルトリメチルシリルシリル基、ジメチルトリメチルシロキシシリル基、下記のような環状もしくは直鎖状ポリシロキサン構造を有する基、またはカゴ型、はしご型又はランダム型シルセスキオキサン構造を有する基などが挙げられる。式中、R、及び、R1は各々独立に、1価の置換基を表す。*は、結合手を表す。
シルセスキオキサン構造としては、例えば、カゴ型シルセスキオキサン構造、はしご型シルセスキオキサン構造、ランダム型シルセスキオキサン構造などが挙げられる。なかでも、カゴ型シルセスキオキサン構造が好ましい。
ここで、カゴ型シルセスキオキサン構造とは、カゴ状骨格を有するシルセスキオキサン構造である。カゴ型シルセスキオキサン構造は、完全カゴ型シルセスキオキサン構造であっても、不完全カゴ型シルセスキオキサン構造であってもよいが、完全カゴ型シルセスキオキサン構造であることが好ましい。
また、はしご型シルセスキオキサン構造とは、はしご状骨格を有するシルセスキオキサン構造である。
また、ランダム型シルセスキオキサン構造とは、骨格がランダムのシルセスキオキサン構造である。
上記有機基は特に制限されないが、具体例としては、 ヒドロキシ基、ニトロ基、カルボキシ基、アルコキシ基、アミノ基、メルカプト基、ブロック化メルカプト基(例えば、アシル基で保護されたメルカプト基)、アシル基、イミド基、ホスフィノ基、ホスフィニル基、シリル基、ビニル基、ヘテロ原子を有していてもよい炭化水素基、(メタ)アクリル基含有基およびエポキシ基含有基などが挙げられる。
上記ヘテロ原子を有していてもよい炭化水素基のヘテロ原子としては、例えば、酸素原子、窒素原子、硫黄原子、リン原子などが挙げられる。
上記ヘテロ原子を有していてもよい炭化水素基の炭化水素基としては、例えば、脂肪族炭化水素基、芳香族炭化水素基、またはこれらを組み合わせた基などが挙げられる。
上記脂肪族炭化水素基は、直鎖状、分岐鎖状、環状のいずれであってもよい。上記脂肪族炭化水素基の具体例としては、直鎖状または分岐状のアルキル基(特に、炭素数1~30)、直鎖状または分岐状のアルケニル基(特に、炭素数2~30)、直鎖状または分岐状のアルキニル基(特に、炭素数2~30)などが挙げられる。
上記芳香族炭化水素基としては、例えば、フェニル基、トリル基、キシリル基、ナフチル基などの炭素数6~18の芳香族炭化水素基などが挙げられる。
反応溶媒としては、例えば、テトラヒドロフラン、1,4-ジオキサン、ジイソプロピルエーテルなどのエーテル類;メチルエチルケトン、メチルイソブチルケトンなどのケトン類;酢酸エチルなどのエステル溶媒;ジメチルホルムアミド、ジメチルアセトアミドなどのアミド溶剤;後述のプロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、シクロヘキサノンなどの本発明のレジスト組成物を溶解する溶媒;等が挙げられる。より好ましくは本発明のレジスト組成物に用いられる溶剤と同一の溶剤を用いて重合することが好ましい。これにより保存時のパーティクルの発生が抑制できる。
精製は、水洗や適切な溶媒を組み合わせることにより残留単量体やオリゴマー成分を除去する液液抽出法、特定の分子量以下のもののみを抽出除去する限外ろ過等の溶液状態での精製方法や、樹脂溶液を貧溶媒へ滴下することで樹脂を貧溶媒中に凝固させることにより残留単量体等を除去する再沈殿法や、濾別した樹脂スラリーを貧溶媒で洗浄する等の固体状態での精製方法等の通常の方法を適用できる。
樹脂(A)の重量平均分子量の特に好ましい別の形態は、GPC法によるポリスチレン換算値で3,000~9,500である。重量平均分子量を3,000~9,500にすることにより、特にレジスト残渣が抑制され、より良好なパターンを形成することができる。
分散度(分子量分布)は、通常1~5であり、好ましくは1~3、更に好ましくは1.2~3.0、特に好ましくは1.2~2.0の範囲のものが使用される。分散度の小さいものほど、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、感活性光線性又は感放射線性組成物において、樹脂(A)は、1種で使用してもよいし、複数併用してもよい。
感活性光線性又は感放射線性組成物は、活性光線又は放射線により酸を発生する化合物(「化合物(B)」)を含有することが好ましい。化合物(B)は上層膜形成用組成物中に含まれ得る光酸発生剤と同様である。
化合物(B)は1種類単独で又は2種類以上を組み合わせて使用することができる。
化合物(B)の感活性光線性又は感放射線性組成物中の含有量は、組成物の全固形分を基準として、0.1~50質量%が好ましく、より好ましくは5~50質量%、更に好ましくは8~40質量%である。特に、電子線や極紫外線露光の際に高感度化、高解像性を両立するには光酸発生剤の含有率は高いほうが好ましく、更に好ましくは10~40質量%、最も好ましくは10~35質量%である。
感活性光線性又は感放射線性組成物は、溶剤(「レジスト溶剤」ともいう)を含んでいることが好ましい。溶剤は、(M1)プロピレングリコールモノアルキルエーテルカルボキシレートと、(M2)プロピレングリコールモノアルキルエーテル、乳酸エステル、酢酸エステル、アルコキシプロピオン酸エステル、鎖状ケトン、環状ケトン、ラクトン、及びアルキレンカーボネートからなる群より選択される少なくとも1つとの少なくとも一方を含んでいることが好ましい。溶剤は、成分(M1)及び(M2)以外の成分を更に含んでいてもよい。
プロピレングリコールモノアルキルエーテルとしては、プロピレングリコールモノメチルエーテル又はプロピレングリコールモノエチルエーテルが好ましい。
乳酸エステルとしては、乳酸エチル、乳酸ブチル、又は乳酸プロピルが好ましい。
酢酸エステルとしては、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸プロピル、酢酸イソアミル、蟻酸メチル、蟻酸エチル、蟻酸ブチル、蟻酸プロピル、又は酢酸3-メトキシブチルが好ましい。
酪酸ブチルも好ましい。
アルコキシプロピオン酸エステルとしては、3-メトキシプロピオン酸メチル(MMP)、又は、3-エトキシプロピオン酸エチル(EEP)が好ましい。
鎖状ケトンとしては、1-オクタノン、2-オクタノン、1-ノナノン、2-ノナノン、アセトン、4-ヘプタノン、1-ヘキサノン、2-ヘキサノン、ジイソブチルケトン、フェニルアセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセトニルアセトン、イオノン、ジアセトニルアルコール、アセチルカービノール、アセトフェノン、メチルナフチルケトン、又はメチルアミルケトンが好ましい。
環状ケトンとしては、メチルシクロヘキサノン、イソホロン、又はシクロヘキサノンが好ましい。
ラクトンとしては、γ-ブチロラクトンが好ましい。
アルキレンカーボネートとしては、プロピレンカーボネートが好ましい。
感活性光線性又は感放射線性組成物は、露光から加熱までの経時による性能変化を低減するために、(E)塩基性化合物を含有することが好ましい。
塩基性化合物としては、好ましくは、下記一般式(E-1)~(E-5)で示される構造を有する化合物を挙げることができる。
一般式(E-5)中、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(E-1)及び(E-5)中のアルキル基は、無置換であることがより好ましい。
また、アミン化合物は、アルキル鎖中に、酸素原子を有し、オキシアルキレン基が形成されていることが好ましい。オキシアルキレン基の数は、分子内に1つ以上、好ましくは
3~9個、さらに好ましくは4~6個である。オキシアルキレン基の中でもオキシエチレン基(-CH2CH2O-)もしくはオキシプロピレン基(-CH(CH3)CH2O-もしくは-CH2CH2CH2O-)が好ましく、さらに好ましくはオキシエチレン基である。
アンモニウム塩化合物は、アルキル鎖中に、酸素原子を有し、オキシアルキレン基が形成されていることが好ましい。オキシアルキレン基の数は、分子内に1つ以上、好ましくは3~9個、さらに好ましくは4~6個である。オキシアルキレン基の中でもオキシエチレン基(-CH2CH2O-)もしくはオキシプロピレン基(-CH(CH3)CH2O-もしくは-CH2CH2CH2O-)が好ましく、さらに好ましくはオキシエチレン基である。
アンモニウム塩化合物のアニオンとしては、ハロゲン原子、スルホネート、ボレート、フォスフェート等が挙げられるが、中でもハロゲン原子、スルホネートが好ましい。ハロゲン原子としてはクロライド、ブロマイド、アイオダイドが特に好ましく、スルホネートとしては、炭素数1~20の有機スルホネートが特に好ましい。有機スルホネートとしては、炭素数1~20のアルキルスルホネート、アリールスルホネートが挙げられる。アルキルスルホネートのアルキル基は置換基を有していてもよく、置換基としては例えばフッ素、塩素、臭素、アルコキシ基、アシル基、アリール基等が挙げられる。アルキルスルホネートとして、具体的にはメタンスルホネート、エタンスルホネート、ブタンスルホネート、ヘキサンスルホネート、オクタンスルホネート、ベンジルスルホネート、トリフルオロメタンスルホネート、ペンタフルオロエタンスルホネート、ノナフルオロブタンスルホネート等が挙げられる。アリールスルホネートのアリール基としてはベンゼン環、ナフタレン環、アントラセン環が挙げられる。ベンゼン環、ナフタレン環、アントラセン環は置換基を有していてもよく、置換基としては炭素数1~6の直鎖若しくは分岐アルキル基、炭素数3~6のシクロアルキル基が好ましい。直鎖若しくは分岐アルキル基、シクロアルキル基として、具体的には、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、イソブチル、t-ブチル、n-ヘキシル、シクロヘキシル等が挙げられる。他の置換基としては炭素数1~6のアルコキシ基、ハロゲン原子、シアノ、ニトロ、アシル基、アシルオキシ基等が挙げられる。
感活性光線性又は感放射線性組成物は、塩基性化合物として、プロトンアクセプター性官能基を有し、かつ、活性光線又は放射線の照射により分解してプロトンアクセプター性が低下、消失、又はプロトンアクセプター性から酸性に変化した化合物を発生する化合物〔以下、化合物(PA)ともいう〕を更に含んでいてもよい。
144に記載の化合物(アミン化合物、アミド基含有化合物、ウレア化合物、含窒素複素環化合物等)を用いることができる。
感活性光線性又は感放射線性組成物は樹脂(A)とは異なる疎水性樹脂を含有していてもよく、疎水性樹脂としては、上層膜形成用組成物が含有していてもよい樹脂と同様のものを使用することもできる。
感活性光線性又は感放射線性組成物は、界面活性剤(F)を更に含んでいてもよい。界面活性剤を含有することにより、波長が250nm以下、特には220nm以下の露光光源を使用した場合に、良好な感度及び解像度で、密着性及び現像欠陥のより少ないパターンを形成することが可能となる。
界面活性剤としては、フッ素系及び/又はシリコン系界面活性剤を用いることが特に好ましい。
フッ素系及び/又はシリコン系界面活性剤としては、例えば、米国特許出願公開第2008/0248425号明細書の<0276>に記載の界面活性剤が挙げられる。また、エフトップEF301若しくはEF303(新秋田化成(株)製);フロラードFC430、431若しくは4430(住友スリーエム(株)製);メガファックF171、F173、F176、F189、F113、F110、F177、F120若しくはR08(DIC(株)製);サーフロンS-382、SC101、102、103、104、105若しくは106(旭硝子(株)製);トロイゾルS-366(トロイケミカル(株)製);GF-300若しくはGF-150(東亜合成化学(株)製)、サーフロンS-393(セイミケミカル(株)製);エフトップEF121、EF122A、EF122B、RF122C、EF125M、EF135M、EF351、EF352、EF801、EF802若しくはEF601((株)ジェムコ製);PF636、PF656、PF6320若しくはPF6520(OMNOVA社製);又は、FTX-204G、208G、218G、230G、204D、208D、212D、218D若しくは222D((株)ネオス製)を用いてもよい。なお、ポリシロキサンポリマーKP-341(信越化学工業(株)製)も、シリコン系界面活性剤として用いることができる。
また、米国特許出願公開第2008/0248425号明細書の<0280>に記載されているフッ素系及び/又はシリコン系以外の界面活性剤を使用してもよい。
感活性光線性又は感放射線性組成物は、溶解阻止化合物、染料、可塑剤、光増感剤、光吸収剤、及び/又は現像液に対する溶解性を促進させる化合物(例えば、分子量1000以下のフェノール化合物、又はカルボキシ基を含んだ脂環族若しくは脂肪族化合物)を更に含んでいてもよい。
感活性光線性又は感放射線性組成物は、(G)カルボン酸オニウム塩を含有してもよい。カルボン酸オニウム塩としては、カルボン酸スルホニウム塩、カルボン酸ヨードニウム塩、カルボン酸アンモニウム塩などを挙げることができる。特に、(G)カルボン酸オニウム塩としては、ヨードニウム塩、スルホニウム塩が好ましい。更に、(G)カルボン酸オニウム塩のカルボキシレート残基が芳香族基、炭素-炭素2重結合を含有しないことが好ましい。特に好ましいアニオン部としては、炭素数1~30の直鎖、分岐、単環または多環環状アルキルカルボン酸アニオンが好ましい。さらに好ましくはこれらのアルキル基の一部または全てがフッ素置換されたカルボン酸のアニオンが好ましい。アルキル鎖中に酸素原子を含んでいてもよい。これにより220nm以下の光に対する透明性が確保され、感度、解像力が向上し、疎密依存性、露光マージンが改良される。
(無機膜、有機膜、反射防止膜)を形成してもよい。また、上層膜の形成前に感活性光線性又は感放射線性膜を乾燥することが好ましい。
膜厚の範囲としてより好ましくは、15nm~45nmの範囲である。膜厚が15nm以上であれば、十分なエッチング耐性が得られる。膜厚の範囲として更に好ましくは、15nm~40nmである。膜厚がこの範囲にあると、エッチング耐性とより優れた解像性能とを同時に満足させることができる。
本発明のパターン形成方法の工程(b)は、感活性光線性又は感放射線性膜上に上層膜形成用組成物により上層膜を形成する工程である。
工程(b)では、工程(a)で形成した感活性光線性又は感放射線性膜上に、上層膜形成用組成物を塗布し、その後、必要に応じて加熱(プリベーク(PB;Prebake))することにより、上層膜を形成することが好ましい。
本発明の効果がより優れるという理由から、工程(b)におけるプリベークの温度(以下、「PB温度」ともいう)は、90℃以上が好ましく、100℃以上がより好ましく、110℃以上が更に好ましく、120℃以上が最も好ましい。
PB温度の上限値は、特に限定されないが、例えば、150℃以下が挙げられ、140℃以下が好ましい。
次に、本発明のパターン形成方法に用いられる上層膜形成用組成物について説明する。
上層膜形成用組成物は、活性光線又は放射線により酸を発生する化合物、熱により酸を発生する化合物及び酸の少なくとも1つを含むものであり、この上層膜形成用組成物により形成された上層膜を感活性光線性又は感放射線性膜の上に有することで、感活性光線性又は感放射線性膜の表面に発生する酸が増加し、パターン部の溶解を抑制することができるので、極微細なドット及び孤立パターンの解像性を向上させることができると考えられる。
上層膜形成用組成物が含有してもよい酸について説明する。上層膜形成用組成物に含有され得る酸としては特に限定されないが、例えばスルホン酸、カルボン酸等の有機酸を用いることができ、活性光線又は放射線により酸を発生する化合物から発生した酸、活性光線又は放射線により酸を発生する化合物のアニオンがプロトン化されたものを好適に使用することができる。具体的には、例えば、以下に示す化合物が挙げられる。
酸の上層膜形成用組成物中の含有量は、組成物の全固形分を基準として、0.1~50質量%が好ましく、より好ましくは1~50質量%、更に好ましくは1~40質量%である。特に、電子線や極紫外線露光の際に高感度化、高解像性を両立するには酸の含有率は、更に好ましくは1~30質量%、最も好ましくは1~20質量%である。
上層膜形成用組成物は、活性光線又は放射線により酸を発生する化合物(「光酸発生剤」、「PAG(Photo Acid Generator)」ともいう)を含有し得る。
光酸発生剤は、低分子化合物の形態であっても良く、重合体の一部に組み込まれた形態であっても良い。また、低分子化合物の形態と重合体の一部に組み込まれた形態を併用しても良い。
光酸発生剤が、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。
光酸発生剤が、重合体の一部に組み込まれた形態である場合、上層膜形成用組成物が含有し得る樹脂の一部に組み込まれても良く、上記樹脂とは異なる樹脂に組み込まれても良い。
光酸発生剤は低分子化合物の形態であることが好ましい。
光酸発生剤としては、公知のものであれば特に限定されないが、活性光線又は放射線、好ましくは電子線又は極紫外線の照射により、有機酸、例えば、スルホン酸、ビス(アルキルスルホニル)イミド、又はトリス(アルキルスルホニル)メチドの少なくともいずれかを発生する化合物が好ましい。
光酸発生剤としては、より好ましくは下記一般式(ZI)、(ZII)、又は(ZIII)で表される化合物を挙げることができる。
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(求核反応を起こす能力が著しく低いアニオン)を表す。
また、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、互いに結合して環構造を形成してもよい。これにより、酸強度が増加する。
xは1~20の整数を表し、yは0~10の整数を表し、zは0~10の整数を表す。
Xfのフッ素原子で置換されたアルキル基におけるアルキル基としては、好ましくは炭素数1~10であり、より好ましくは炭素数1~4である。また、Xfのフッ素原子で置換されたアルキル基は、パーフルオロアルキル基であることが好ましい。
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。Xfの具体例としては、フッ素原子、CF3、C2F5、C3F7、C4F9、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。
R1、R2としては、好ましくはフッ素原子又はCF3である。
yは0~4が好ましく、0がより好ましい。
zは0~5が好ましく、0~3がより好ましい。
Lの2価の連結基としては特に限定されず、―COO-、-OCO-、-CO-、-O-、-S―、-SO―、―SO2-、アルキレン基、シクロアルキレン基、アルケニレン基又はこれらの複数が連結した連結基などを挙げることができ、総炭素数12以下の連結基が好ましい。このなかでも―COO-、-OCO-、-CO-、-O-が好ましく、―COO-、-OCO-がより好ましい。
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、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、アダマンチル基などの多環のシクロアルキル基が好ましい。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、アダマンチル基等の炭素数7以上のかさ高い構造を有する脂環基が、露光後加熱工程での膜中拡散性を抑制でき、MEEF(Mask
Error Enhancement Factor)向上の観点から好ましい。
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。
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、ピリジン環由来のものが挙げられる。中でもフラン環、チオフェン環、ピリジン環由来のものが好ましい。
R201、R202及びR203のうち、少なくとも1つがアリール基であることが好ましく、三つ全てがアリール基であることがより好ましい。アリール基としては、フェニル基、ナフチル基などの他に、インドール残基、ピロール残基などのヘテロアリール基も可能である。R201~R203の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、炭素数3~10のシクロアルキル基を挙げることができる。アルキル基として、より好ましくはメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基等を挙げることができる。シクロアルキル基として、より好ましくは、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロへプチル基等を挙げることができる。これらの基は更に置換基を有していてもよい。その置換基としては、ニトロ基、フッ素原子などのハロゲン原子、カルボキシル基、水酸基、アミノ基、シアノ基、アルコキシ基(好ましくは炭素数1~15)、シクロアルキル基(好ましくは炭素数3~15)、アリール基(好ましくは炭素数6~14)、アルコキシカルボニル基(好ましくは炭素数2~7)、アシル基(好ましくは炭素数2~12)、アルコキシカルボニルオキシ基(好ましくは炭素数2~7)等が挙げられるが、これらに限定されるものではない。
SO3-CF2-CH2-OCO-A、SO3-CF2-CHF-CH2-OCO-A、SO3-CF2-COO-A、SO3-CF2-CF2-CH2-A、SO3-CF2-CH(CF3)-OCO-A
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、アルキル基、シクロアルキル基は、置換基を有していてもよい。この置換基としても、化合物(ZI)におけるR201~R203のアリール基、アルキル基、シクロアルキル基が有していてもよいものが挙げられる。
本発明においては、活性光線又は放射線の照射により以下に例示する酸を発生する光酸発生剤が好ましい。なお、例の一部には、体積の計算値を付記している(単位Å3)。なお、ここで求めた計算値は、アニオン部にプロトンが結合した酸の体積値である。
1Åは1×10-10mである。
光酸発生剤の上層膜形成用組成物中の含有量は、組成物の全固形分を基準として、0.1~50質量%が好ましく、より好ましくは1~50質量%、更に好ましくは1~40質量%である。特に、電子線や極紫外線露光の際に高感度化、高解像性を両立するには光酸発生剤の含有率は、更に好ましくは1~30質量%、最も好ましくは1~20質量%である。
上層膜形成用組成物は、熱により酸を発生する化合物(「熱酸発生剤」、「TAG(Thermmal Acid Generator)」ともいう)を含有し得る。上層膜形成用組成物に含有され得る熱酸発生剤としては、アンモニウム塩、フェナシルスルホニウム塩が好ましい。熱酸発生剤は、非求核性アニオンとして上記一般式(AN1)で表されるアニオンを含むことが好ましい。また、熱酸発生剤が酸を発生する温度、好ましくは100℃以上、より好ましくは120℃以上である。本発明の製造方法においては、熱酸発生剤を使用した場合に熱をかける工程はPBでもよいし、PEBでもよいし、これらとは別の工程でもよい。熱酸発生剤としては、例えば、以下に示す化合物が挙げられる。
熱酸発生剤の上層膜形成用組成物中の含有量は、組成物の全固形分を基準として、0.1~50質量%が好ましく、より好ましくは1~50質量%、更に好ましくは1~40質量%である。特に、電子線や極紫外線露光の際に高感度化、高解像性を両立するには熱酸発生剤の含有率は、更に好ましくは1~30質量%、最も好ましくは1~20質量%である。
上層膜形成用組成物の溶液保存安定性の観点からは光酸発生剤又は熱酸発生剤が好ましい。また、下層である感活性光線性又は感放射線性膜の感度依存が無く、一定の効果を付与できるという観点では熱酸発生剤が好ましい。
上層膜形成用組成物は溶剤を含有することができる。本明細書では、上層膜形成用組成物が含有する溶剤をトップコート溶剤とも呼ぶ。
感活性光線性又は感放射線性膜を溶解せずに良好なパターンを形成するために、トップコート溶剤は、感活性光線性又は感放射線性膜を溶解しない溶剤であることが好ましく、有機系現像液とは異なる溶剤であることがより好ましい。
また、液浸液への溶出防止の観点からは、トップコート溶剤は、液浸液への溶解性が低い方が好ましく、水への溶解性が低い方がさらに好ましい。本明細書においては、「液浸液への溶解性が低い」とは液浸液不溶性であることを示す。同様に、「水への溶解性が低い」とは水不溶性であることを示す。また、揮発性及び塗布性の観点から、溶剤の沸点は90℃~200℃が好ましい。
液浸液への溶解性が低いとは、水への溶解性を例にとると、上層膜形成用組成物をシリコンウエハ上に塗布、乾燥し、膜を形成させた後に、純水に23℃で10分間浸漬し、乾燥した後の膜厚の減少率が、初期膜厚(典型的には50nm)の3%以内であることをいう。
上層膜を均一に塗布する観点から、上層膜形成用組成物は固形分濃度が0.01~20質量%であることが好ましく、0.1~15質量%であることがより好ましく、1~10質量%であることが更に好ましい。
1000cP=1Pa・s。
また、アルコール系溶剤としては非フッ素系のアルコール系溶剤を用いることが好ましく、これにより、感活性光線性又は感放射線性膜に対する非溶解性がさらに向上し、上層膜形成用組成物を感活性光線性又は感放射線性膜上に塗布した際に、感活性光線性又は感放射線性膜を溶解することなく、より均一に、上層膜を形成できる。
炭化水素系溶剤としては、例えば、トルエン、キシレン、アニソールなどの芳香族炭化水素系溶剤;n-ヘプタン、n-ノナン、n-オクタン、n-デカン、2-メチルヘプタン、3-メチルヘプタン、3,3-ジメチルヘキサン、2,3,4-トリメチルペンタン、ウンデカンなどの脂肪族炭化水素系溶剤;等が挙げられる。
エーテル系溶剤としては、上記グリコールエーテル系溶剤の他、例えば、ジオキサン、テトラヒドロフラン、イソアミルエーテル、ジソアミルエーテル等が挙げられる。エーテル系溶剤のなかでも、分岐構造を有するエーテル系溶剤が好ましい。
エステル系溶剤としては、例えば、酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸ブチル(酢酸n-ブチル)、酢酸ペンチル、酢酸ヘキシル、酢酸イソアミル、プロピオン酸ブチル(プロピオン酸n-ブチル)、酪酸ブチル、酪酸イソブチル、ブタン酸ブチル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチルー3-エトキシプロピオネート、3-メトキシブチルアセテート、3-メチル-3-メトキシブチルアセテート、蟻酸メチル、蟻酸エチル、蟻酸ブチル、蟻酸プロピル、乳酸エチル、乳酸ブチル、乳酸プロピル、2-ヒドロキシイソ酪酸メチル、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が挙げられる。エステル系溶剤のなかでも、分岐構造を有するエステル系溶剤が好ましい。
上記以外の溶剤を混合する場合、その混合比は、上層膜形成用組成物の全溶剤量に対して、通常0~30質量%、好ましくは0~20質量%、更に好ましくは0~10質量%である。上記以外の溶剤を混合することで、感活性光線性又は感放射線性膜に対する溶解性、上層膜形成用組成物中の樹脂の溶解性、感活性光線性又は感放射線性膜からの溶出特性、などを適宜調整することができる。
(A1)塩基性化合物又は塩基発生剤
(A2)エーテル結合、チオエーテル結合、ヒドロキシル基、チオール基、カルボニル結合及びエステル結合からなる群より選択される結合又は基を含有する化合物
(A3)イオン性化合物
(A4)ラジカルトラップ基を有する化合物
上層膜形成用組成物は、さらに、塩基性化合物及び塩基発生剤の少なくともいずれか(以下、これらをまとめて「化合物(A1)」と呼ぶ場合がある)を含有することが好ましい。
上層膜形成用組成物が含有できる塩基性化合物としては、有機塩基性化合物であることが好ましく、含窒素塩基性化合物であることがより好ましい。例えば、感活性光線性又は感放射線性組成物が含有してもよい塩基性化合物として記載したものを使用でき、具体的には、式(E-1)~(E-5)で示される構造を有する化合物が好適に挙げられる。
また、例えば、以下の(1)~(7)に分類される化合物を用いることができる。
Rは、各々独立に、水素原子又は有機基を表す。但し、3つのRのうち少なくとも1つは有機基である。この有機基は、直鎖若しくは分岐鎖のアルキル基、単環若しくは多環のシクロアルキル基、アリール基又はアラルキル基である。
Rとしてのシクロアルキル基の炭素数は、特に限定されないが、通常3~20であり、好ましくは5~15である。
Rとしてのアラルキル基の炭素数は、特に限定されないが、通常7~20であり、好ましくは7~11である。具体的には、ベンジル基等が挙げられる。
感活性光線性又は感放射線性組成物が含有し得る塩基性化合物として説明したものと同様である。
感活性光線性又は感放射線性組成物が含有し得る塩基性化合物として説明したものと同様である。
感活性光線性又は感放射線性組成物が含有し得る塩基性化合物として説明したものと同様である。
上層膜形成用組成物は、塩基性化合物として、下記式で表される構造を有するグアニジン化合物を含んでいてもよい。
グアニジン化合物の塩基性としては、共役酸のpKaが6.0以上であることが好ましく、7.0~20.0であることが酸との中和反応性が高く、ラフネス特性に優れるため好ましく、8.0~16.0であることがより好ましい。
上層膜形成用組成物は、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(以下において、「低分子化合物(D)」又は「化合物(D)」ともいう)を含有することができる。低分子化合物(D)は、酸の作用により脱離する基が脱離した後は、塩基性を有することが好ましい。
R’は、それぞれ独立に、水素原子、直鎖状又は分岐状アルキル基、シクロアルキル基、アリール基、アラルキル基、又はアルコキシアルキル基を表す。R’は相互に結合して環を形成していても良い。
一般式(J)
本発明において、低分子化合物(D)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。
塩基性化合物として、感光性の塩基性化合物を用いてもよい。感光性の塩基性化合物としては、例えば、特表2003-524799号公報、及び、J.Photopolym.Sci&Tech.Vol.8,P.543-553(1995)等に記載の化合物を用いることができる。
塩基性化合物として、いわゆる光崩壊性塩基と呼ばれる化合物を使用してもよい。光崩壊性塩基としては、例えば、カルボン酸のオニウム塩、α位がフッ素化されていないスルホン酸のオニウム塩を挙げることができる。光崩壊性塩基の具体例は、WO2014/1
33048A1の段落0145、特開2008-158339及び特許399146を挙げることができる。
上層膜形成用組成物における塩基性化合物の含有量は、上層膜形成用組成物の固形分を基準として、0.01~20質量%が好ましく、0.1~10質量%がより好ましく、1~5質量%が更に好ましい。
上層膜形成用組成物が含有できる塩基発生剤(好ましくは光塩基発生剤)としては、例えば、特開平4-151156号、同4-162040号、同5-197148号、同5-5995号、同6-194834号、同8-146608号、同10-83079号、及び欧州特許622682号に記載の化合物が挙げられる。
また、特開2010-243773号公報に記載の化合物も適宜用いられる。
光塩基発生剤としては、具体的には、例えば、2-ニトロベンジルカルバメート、2,5-ジニトロベンジルシクロヘキシルカルバメート、N-シクロヘキシル-4-メチルフェニルスルホンアミド及び1,1-ジメチル-2-フェニルエチル-N-イソプロピルカーバメートが好適に挙げられるがこれらに限定されるものではない。
上層膜形成用組成物における塩基発生剤の含有量は、上層膜形成用組成物の固形分を基準として、0.01~20質量%が好ましく、0.1~10質量%がより好ましく、1~5質量%が更に好ましい。
エーテル結合、チオエーテル結合、ヒドロキシル基、チオール基、カルボニル結合及びエステル結合からなる群より選択される基又は結合を少なくとも一つ含む化合物(以下、化合物(A2)とも呼ぶ)について、以下に説明する。
また、本発明の一形態において、化合物(A2)に含まれる炭素原子数は、30個以下であることが好ましく、20個以下であることがより好ましく、15個以下であることが更に好ましい。
本発明の一形態において、化合物(A2)は、下記一般式(1)で表されるオキシアルキレン構造を含有する繰り返し単位を含有することが更に好ましい。
R11は、置換基を有してもよいアルキレン基を表し、
nは、2以上の整数を表し、
*は、結合手を表す。
n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。
nの平均値は、DOFがより大きくなる理由から、20以下であることが好ましく、2~10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、4~6であることが特に好ましい。ここで、「nの平均値」とは、化合物(A2)の重量平均分子量をGPCによって測定し、得られた重量平均分子量と一般式が整合するように決定されるnの値を意味する。nが整数でない場合は、四捨五入した値とする。
複数あるR11は同一であっても異なってもよい。
R11の定義、具体例および好適な態様は、上述した一般式(1)中のR11と同じである。
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。R12およびR13は、互いに結合して環を形成してもよい。
mは、1以上の整数を表す。mは、1~20の整数であることが好ましく、そのなかでも、DOF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。
mの平均値は、DOFがより大きくなる理由から、20以下であることが好ましく、1~10であることがより好ましく、1~8であることがさらに好ましく、4~6であることが特に好ましい。ここで、「mの平均値」は、上述した「nの平均値」と同義である。
mが2以上である場合、複数あるR11は同一であっても異なってもよい。
上層膜形成用組成物は、感活性光線性若しくは感放射線性組成物中又は上層膜形成用組成物中の酸発生剤に対して相対的に弱酸となるイオン性化合物を含有できる。イオン性化合物としてはオニウム塩が好ましい。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(CA)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。
上層膜形成用組成物におけるオニウム塩の含有量は、上層膜形成用組成物の固形分を基準として、0.5質量%以上が好ましく、1質量%以上がより好ましく、2.5質量%以上が更に好ましい。
一方、オニウム塩の含有量の上限は、上層膜形成用組成物の固形分を基準として、25質量%以下が好ましく、20質量%以下がより好ましく、10質量%以下が更に好ましく、8質量%以下が特に好ましい。
(A4)ラジカルトラップ基を有する化合物を化合物(A4)ともいう。
ラジカルトラップ基は、活性ラジカルを捕捉し、ラジカル反応を停止させる基である。このようなラジカルトラップ基としては、例えば、活性ラジカルと反応し、安定フリーラジカルへと変換される基、及び、安定フリーラジカルを有する基が挙げられる。塩基性を有さないラジカルトラップ基としては、具体的には、例えば、ヒンダードフェノール基、ヒドロキノン基、N-オキシルフリーラジカル基、ニトロソ基、および、ニトロン基からなる群から選ばれる少なくとも1種の基が好適に挙げられる。
R1~R6が表すアルキル基、シクロアルキル基、及び、アリール基、R1及びR2が結合して形成していてもよい環、並びに、R4~R6の少なくとも二つが結合して形成していてもよい環は、置換基を有していてもよい。
また、ラジカルトラップ基を有する化合物が、繰り返し単位を有する高分子化合物である場合、その重量平均分子量は、5000~20000が好ましく、5000~10000がより好ましい。
また、上層膜形成用組成物は、(A1)~(A4)で表される化合物を2種以上含んでも良い。例えば、化合物(A1)及び化合物(A2)の両方を含有しても良い。
上層膜形成用組成物が、(A1)~(A4)で表される化合物を複数含む場合、それら化合物の含有量の合計は、本発明の上層膜形成用組成物の全固形分を基準として、通常、0.001~20質量%であり、好ましくは0.01~10質量%であり、より好ましくは1~8質量%である。
上層膜形成用組成物に好適に使用し得る樹脂(X)は、露光時に光が上層膜を通して感活性光線性又は感放射線性膜に到達するため、使用する露光光源に対して透明であることが好ましい。ArF液浸露光に使用する場合は、ArF光への透明性の点から上記樹脂は実質的に芳香族基を有さないことが好ましい。
ここで、樹脂(X)中の側鎖部分が有するCH3部分構造(以下、単に「側鎖CH3部分構造」ともいう)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。
R11~R14は、各々独立に、側鎖部分を表す。
R57~R64は、それぞれ独立に、水素原子、フッ素原子又はアルキル基を表す。但し、R57~R61及びR62~R64の内、少なくとも1つは、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は、全てがフッ素原子であることが好ましい。R62及びR63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さらに好ましい。R62とR63は、互いに連結して環を形成してもよい。
R1~R3は、各々独立に、水素原子、フッ素原子、炭素数1~4個の、直鎖もしくは分岐のアルキル基、または炭素数1~4個の、直鎖もしくは分岐のフッ素化アルキル基を表す。
R10及びR11は、水素原子、フッ素原子、炭素数1~4個の、直鎖もしくは分岐のアルキル基、または炭素数1~4個の、直鎖もしくは分岐のフッ素化アルキル基を表す。
Rfは、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を表す。
炭素数3~10の分岐状のアルキル基がより好ましい。
0の直鎖若しくは分岐状のアルキル基がより好ましい。
R4は、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、トリアルキルシリル基又は環状シロキサン構造を有する基を表す。
上層膜形成用組成物は、各成分を溶剤に溶解し、フィルター濾過することが好ましい。フィルターとしては、ポアサイズ0.1μm以下、より好ましくは0.05μm以下、更に好ましくは0.03μm以下のポリテトラフロロエチレン製、ポリエチレン製、ナイロン製のものが好ましい。なお、フィルターは、複数種類を直列又は並列に接続して用いてもよい。また、組成物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。さらに、フィルター濾過の前後で、組成物に対して脱気処理などを行ってもよい。本発明の上層膜形成用組成物は、金属等の不純物を含まないことが好ましい。これら材料に含まれる金属成分の含有量としては、10ppm以下が好ましく、5ppm以下がより好ましく、1ppm以下が更に好ましく、実質的に含まないこと(測定装置の検出限界以下であること)が特に好ましい。
なお、上層膜形成用組成物を、感活性光線性又は感放射線性膜の表面に、感活性光線性又は感放射線性膜を溶解せずに均一に塗布するために、上層膜形成用組成物は、感活性光線性又は感放射線性膜を溶解しない溶剤を含有することが好ましい。感活性光線性又は感放射線性膜を溶解しない溶剤としては、有機溶剤を含有する現像液(有機系現像液)とは異なる成分の溶剤を用いることがさらに好ましい。
上層膜を形成後、必要に応じて基板を加熱(PB)する。
上層膜の屈折率は、解像性の観点から、感活性光線性又は感放射線性膜の屈折率に近いことが好ましい。
上層膜は液浸液に不溶であることが好ましく、水に不溶であることがより好ましい。
上層膜の後退接触角は、液浸液追随性の観点から、上層膜に対する液浸液の後退接触角(23℃)が50~100度であることが好ましく、80~100度であることがより好ましい。
液浸露光においては、露光ヘッドが高速でウエハ上をスキャンし露光パターンを形成していく動きに追随して、液浸液がウエハ上を動く必要があることから、動的な状態における感活性光線性又は感放射線性膜に対する液浸液の接触角が重要になり、より良好なレジスト性能を得るためには、上記範囲の後退接触角を有することが好ましい。
ここで、上層膜の有機系現像液に対する溶解速度とは、上層膜を成膜した後に現像液に暴露した際の膜厚減少速度であり、本発明においては23℃の酢酸ブチルに浸漬させた際の速度とする。
上層膜の有機系現像液に対する溶解速度を1/sec秒以上、好ましくは10nm/sec以上とすることによって、感活性光線性又は感放射線性膜を現像した後の現像欠陥発生が低減する効果がある。また、300nm/sec以下、好ましくは100nm/secとすることによって、おそらくは、液浸露光時の露光ムラが低減した影響で、感活性光線性又は感放射線性膜を現像した後のパターンのラインエッジラフネスがより良好になるという効果がある。
上層膜はその他の公知の現像液、例えば、アルカリ水溶液などを用いて除去してもよい。使用できるアルカリ水溶液として具体的には、テトラメチルアンモニウムヒドロキシドの水溶液が挙げられる。
プリウェット溶剤は、感活性光線性又は感放射線性膜に対する溶解性が小さいものであれば特に限定されないが、アルコール系溶剤、フッ素系溶剤、エーテル系溶剤、炭化水素系溶剤、エステル系溶剤の中から選ばれる一種以上の化合物を含有する上層膜用のプリウェット溶剤を用いることができる。
アルコール系溶剤としては、塗布性の観点から、1価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価アルコールである。炭素数4~8の1価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、直鎖状又は分岐状のアルコールが好ましい。このようなアルコール系溶剤としては、例えば、1-ブタノール、2-ブタノール、3-メチル-1-ブタノール、4-メチル-1-ペンタノール、4-メチル-2-ペンタノール、イソブチルアルコール、tert―ブチルアルコール、1-ペンタノール、2-ペンタノール、1-ヘキサノール、1-ヘプタノール、1-オクタノール、2-ヘキサノール、2-ヘプタノール、2-オクタノール、3-ヘキサノール、3-ヘプタノール、3-オクタノール、4-オクタノールなどのアルコール;エチレングリコール、プロピレングリコール、ジエチレングリコール、トリエチレングリコールなどのグリコール;エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、メトキシメチルブタノールなどのグリコールエーテル;等を用いることができ、なかでも、アルコール、グリコールエーテルが好ましく、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、4-メチル-1-ペンタノール、4-メチル-2-ペンタノール、プロピレングリコールモノメチルエーテルがより好ましい。
エーテル系溶剤としてはジプロピルエーテル、ジイソプロピルエーテル、ブチルメチルエーテル、ブチルエチルエーテル、ブチルプロピルエーテル、ジブチルエーテル、ジイソブチルエーテル、tert-ブチル-メチルエーテル、tert- ブチルエチルエーテル、tert-ブチルプロピルエーテル、ジ-tert-ブチルエー テル、ジペンチルエーテル、ジイソアミルエーテル、シクロペンチルメチルエーテル、シ クロヘキシルメチルエーテル、シクロペンチルエチルエーテル、シクロヘキシルエチルエ ーテル、シクロペンチルプロピルエーテル、シクロペンチル-2-プロピルエーテル、シ クロヘキシルプロピルエーテル、シクロヘキシル-2-プロピルエーテル、シクロペンチ ルブチルエーテル、シクロペンチル-tert-ブチルエーテル、シクロヘキシルブチル エーテル、シクロヘキシル-tert-ブチルエーテル等が挙げられる。
フッ素系溶剤としては、例えば、2,2,3,3,4,4-ヘキサフルオロ-1-ブタノール、2,2,3,3,4,4,5,5-オクタフルオロ-1-ペンタノール、2,2,3,3,4,4,5,5,6,6-デカフルオロ-1-ヘキサノール、2,2,3,3,4,4-ヘキサフルオロ-1,5-ペンタンジオール、2,2,3,3,4,4,5,5-オクタフルオロ-1,6-ヘキサンジオール、2,2,3,3,4,4,5,5,6,6,7,7-ドデカフルオロ-1,8-オクタンジオール、2-フルオロアニソール、2,3-ジフルオロアニソール、パーフルオロヘキサン、パーフルオロヘプタン、パーフルオロ-2-ペンタノン、パーフルオロ-2-ブチルテトラヒドロフラン、パーフルオロテトラヒドロフラン、パーフルオロトリブチルアミン、パーフルオロテトラペンチルアミン等が挙げられ、この中でも、フッ化アルコール又はフッ化炭化水素系溶剤を好適に用いることができる。
炭化水素系溶剤としては、例えば、トルエン、キシレン、アニソールなどの芳香族炭化水素系溶剤;n-ヘプタン、n-ノナン、n-オクタン、n-デカン、2-メチルヘプタン、3-メチルヘプタン、3,3-ジメチルヘキサン、2,3,4-トリメチルペンタンなどの脂肪族炭化水素系溶剤;等が挙げられる。
エステル系溶剤としては、例えば、酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸ブチル(酢酸n-ブチル)、酢酸ペンチル、酢酸ヘキシル、酢酸イソアミル、プロピオン酸ブチル(プロピオン酸n-ブチル)、酪酸ブチル、酪酸イソブチル、ブタン酸ブチル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、エチルー3-エトキシプロピオネート、3-メトキシブチルアセテート、3-メチル-3-メトキシブチルアセテート、蟻酸メチル、蟻酸エチル、蟻酸ブチル、蟻酸プロピル、乳酸エチル、乳酸ブチル、乳酸プロピル、2-ヒドロキシイソ酪酸メチル、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が挙げられる。
本発明のパターン形成方法の工程(c)は上層膜が形成された感活性光線性又は感放射線性膜を露光する工程であり、例えば次の方法により行うことができる。
上記のようにして形成した上層膜を有する感活性光線性又は感放射線性膜に、所定のマスクを通して活性光線又は放射線を照射する。なお、電子線の照射では、マスクを介さない描画(直描)が一般的である。
活性光線又は放射線としては特に限定されないが、例えばKrFエキシマレーザー、ArFエキシマレーザー、極紫外線(EUV、Extreme Ultra Violet)、電子線(EB、Electron Beam)等であり、極紫外線又は電子線が特に好ましい。露光は液浸露光であってもよい。
本発明のパターン形成方法においては、露光後、現像を行う前にベーク(加熱)を行うことが好ましい。ベークにより露光部の反応が促進され、感度やパターン形状がより良好となる。
加熱温度は80~150℃が好ましく、80~140℃がより好ましく、80~130℃が更に好ましい。
加熱時間は30~1000秒が好ましく、60~800秒がより好ましく、60~600秒が更に好ましい。
加熱は通常の露光又は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。
本発明のパターン形成方法の工程(d)は、露光された感活性光線性又は感放射線性膜を、有機溶剤を含有する現像液で現像する工程である。
上記現像工程(d)で用いられる現像液は、有機溶剤を含有することから有機系現像液ということもできる。
有機溶剤の蒸気圧(混合溶剤である場合は全体としての蒸気圧)は、20℃に於いて、5kPa以下が好ましく、3kPa以下が更に好ましく、2kPa以下が特に好ましい。有機溶剤の蒸気圧を5kPa以下にすることにより、現像液の基板上あるいは現像カップ内での蒸発が抑制され、ウエハ面内の温度均一性が向上し、結果としてウエハ面内の寸法均一性が良化する。
現像液に用いられる有機溶剤としては、種々の有機溶剤が広く使用されるが、たとえば、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤等の溶剤を用いることができる。
特に、エステル系溶剤、ケトン系溶剤、エーテル系溶剤、及び炭化水素系溶剤から選択される少なくとも1種の溶剤を含有する現像液であることが好ましく、エステル系溶剤を含有する現像液であることがより好ましい。
不飽和炭化水素溶剤が有する二重結合、三重結合は複数でもよく、炭化水素鎖のどの位置に有しても良い。二重結合を有することによるCis、trans体が混合しても良い。
なお、炭化水素系溶剤は、同じ炭素数で異なる構造の化合物の混合物であってもよい。例えば、脂肪族炭化水素系溶媒としてデカンを使用した場合、同じ炭素数で異なる構造の化合物である2-メチルノナン、2,2-ジメチルオクタン、4-エチルオクタン、イソデカンなどが脂肪族炭化水素系溶媒に含まれていてもよい。
また、上記同じ炭素数で異なる構造の化合物は、1種のみが含まれていてもよいし、上記のように複数種含まれていてもよい。
上記エステル系溶剤のヘテロ原子は、炭素原子および水素原子以外の原子であって、例えば、酸素原子、窒素原子、硫黄原子等が挙げられる。ヘテロ原子数は、2以下が好ましい。
エステル系溶剤と炭化水素系溶剤とを組み合わせて用いる場合には、エステル系溶剤として酢酸イソアミルを用いることが好ましい。また、炭化水素系溶剤としては、感活性光線性又は感放射線性膜の溶解性を調製するという観点から、飽和炭化水素溶剤(例えば、オクタン、ノナン、デカン、ドデカン、ウンデカン、ヘキサデカンなど)を用いることが好ましい。
ケトン系溶剤と炭化水素系溶剤とを組み合わせて用いる場合には、ケトン系溶剤として2-ヘプタノンを用いることが好ましい。また、炭化水素系溶剤としては、感活性光線性又は感放射線性膜の溶解性を調製するという観点から、飽和炭化水素溶剤(例えば、オクタン、ノナン、デカン、ドデカン、ウンデカン、ヘキサデカンなど)を用いることが好ましい。
上記の混合溶剤を用いる場合において、炭化水素系溶剤の含有量は、感活性光線性又は感放射線性膜の溶剤溶解性に依存するため、特に限定されず、適宜調製して必要量を決定すればよい。
界面活性剤としては、感活性光線性又は感放射線性組成物が含有し得る界面活性剤と同様のものを用いることができる。
現像液が界面活性剤を含有する場合、界面活性剤の含有量は、現像液の全質量に対して、0.001~5質量%であることが好ましく、より好ましくは0.005~2質量%であり、更に好ましくは0.01~0.5質量%である。
また、現像を行う工程の後に、他の溶媒に置換しながら、現像を停止する工程を実施してもよい。
現像時間は特に制限はなく、通常は10~300秒であり、好ましくは20~120秒である。
現像液の温度は0~50℃が好ましく、15~35℃がより好ましい。
本発明のパターン形成方法は、工程(d)の後に、現像された感活性光線性又は感放射線性膜をリンス液を用いてリンス(洗浄)する工程(e)を有することが好ましい。特に、炭化水素系溶剤を含むリンス液を用いて洗浄することが、本発明の効果がより優れるという理由から好ましい。
有機系処理液の一種であるリンス液は、リンス工程で用いられ、有機溶剤を含有することから有機系リンス液ということもできる。有機系処理液を用いた感活性光線性又は感放射線性膜の「洗浄」(すなわち、感活性光線性又は感放射線性膜の「リンス」)には、このリンス液が用いられることが好ましい。
上記リンス液に含まれる有機溶剤としては、種々の有機溶剤が用いられるが、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種の有機溶剤を用いることが好ましい。
これらの有機溶剤の具体例は、現像液で説明した有機溶剤と同様である。
なお、上記脂肪族炭化水素系溶剤の炭素原子数の上限値は特に限定されないが、例えば、16以下が挙げられ、14以下が好ましく、12以下がより好ましい。
上記脂肪族炭化水素系溶剤の中でも、特に好ましくは、デカン、ウンデカン、ドデカンであり、最も好ましくはウンデカンである。
このようにリンス液に含まれる有機溶剤として炭化水素系溶剤(特に脂肪族炭化水素系溶剤)を用いることで、現像後にわずかに感活性光線性又は感放射線性膜に染み込んでいた現像液が洗い流されて、膨潤がより抑制され、パターン倒れが抑制されるという効果が一層発揮される。
また、炭化水素系溶剤としては、オクテン、ノネン、デセン、ウンデセン、ドデセン、ヘキサデセンなどの不飽和炭化水素系溶剤も挙げられる。
不飽和炭化水素溶剤が有する二重結合、三重結合は複数でもよく、炭化水素鎖のどの位置に有しても良い。二重結合を有することによるCis、trans体が混合しても良い。
なお、炭化水素系溶剤は、同じ炭素数で異なる構造の化合物の混合物であってもよい。例えば、脂肪族炭化水素系溶媒としてデカンを使用した場合、同じ炭素数で異なる構造の化合物である2-メチルノナン、2,2-ジメチルオクタン、4-エチルオクタン、イソデカンなどが脂肪族炭化水素系溶媒に含まれていてもよい。
また、上記同じ炭素数で異なる構造の化合物は、1種のみが含まれていてもよいし、上記のように複数種含まれていてもよい。
界面活性剤としては、上記感活性光線または感放射線性組成物に用いられる界面活性剤と同様のものを用いることができる。
界面活性剤の含有量は、リンス液の全質量に対して、通常0.001~5質量%、好ましくは0.005~2質量%、更に好ましくは0.01~0.5質量%である。
アルカリ現像液としては、通常、テトラメチルアンモニウムヒドロキシドに代表される4級アンモニウム塩が用いられるが、これ以外にも無機アルカリ、1~3級アミン、アルコールアミン、環状アミン等のアルカリ水溶液も使用可能である。さらに、上記アルカリ現像液にアルコール類、界面活性剤を適当量添加してもよい。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。
アルカリ現像液を用いて現像を行う時間は、通常10~300秒である。
アルカリ現像液のアルカリ濃度(及びpH)及び現像時間は、形成するパターンに応じて、適宜調整することができる。
アルカリ現像液を用いた現像の後にリンス液を用いて洗浄してもよく、そのリンス液としては、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。
また、現像処理または、リンス処理の後に、パターン上に付着している現像液またはリンス液を超臨界流体により除去する処理を行うことができる。
更に、リンス処理または超臨界流体による処理の後、パターン中に残存する水分を除去するために加熱処理を行うことができる。
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、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、上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。
現像液及びリンス液に使用し得る有機溶剤(有機系処理液)としては、収容部を有する、化学増幅型レジスト膜のパターニング用有機系処理液の収容容器に保存されたものを使用することが好ましい。この収容容器としては、例えば、収容部の、有機系処理液に接触する内壁が、ポリエチレン樹脂、ポリプロピレン樹脂、及び、ポリエチレン-ポリプロピレン樹脂とは異なる樹脂、又は、防錆・金属溶出防止処理が施された金属から形成された、化学増幅型レジスト膜のパターニング用有機系処理液の収容容器であることが好ましい。この収容容器の上記収容部に、化学増幅型レジスト膜のパターニング用有機系処理液として使用される予定の有機溶剤を収容し、化学増幅型レジスト膜のパターニング時において、上記収容部から排出したものを使用することができる。
ここで、シール部とは、収容部と外気とを遮断可能な部材を意味し、パッキンやOリングなどを好適に挙げることができる。
特に好ましいパーフルオロ樹脂としては、四フッ化エチレン樹脂、四フッ化エチレン・パーフルオロアルキルビニルエーテル共重合体、四フッ化エチレン-六フッ化プロピレン共重合樹脂を挙げることができる。
防錆・金属溶出防止処理としては、皮膜技術を適用することが好ましい。
皮膜技術には、金属被覆(各種メッキ),無機被覆(各種化成処理,ガラス,コンクリート,セラミックスなど)および有機被覆(さび止め油,塗料,ゴム,プラスチックス)の3種に大別されている。
好ましい皮膜技術としては、錆止め油、錆止め剤、腐食抑制剤、キレート化合物、可剥性プラスチック、ライニング剤による表面処理が挙げられる。
中でも、各種のクロム酸塩、亜硝酸塩、ケイ酸塩、燐酸塩、オレイン酸、ダイマー酸、ナフテン酸等のカルボン酸、カルボン酸金属石鹸、スルホン酸塩、アミン塩、エステル(高級脂肪酸のグリセリンエステルや燐酸エステル)などの腐食抑制剤、エチレンジアンテトラ酢酸、グルコン酸、ニトリロトリ酢酸、ヒドロキシエチルエチオレンジアミン三酢酸、ジエチレントリアミン五酢酸などのキレート化合物及びフッ素樹脂ライニングが好ましい。特に好ましいのは、燐酸塩処理とフッ素樹脂ライニングである。
また、直接的な被覆処理と比較して、直接、錆を防ぐわけではないが、被覆処理による防錆期間の延長につながる処理方法として、防錆処理にかかる前の段階である「前処理」を採用することも好ましい。
このような前処理の具体例としては、金属表面に存在する塩化物や硫酸塩などの種々の腐食因子を、洗浄や研磨によって除去する処理を好適に挙げることができる。
・Entegris社製 FluoroPurePFA複合ドラム(接液内面;PFA樹脂ライニング)
・JFE社製 鋼製ドラム缶(接液内面;燐酸亜鉛皮膜)
本発明は、上記した本発明のパターン形成方法を含む、電子デバイスの製造方法にも関する。
本発明は、感活性光線性又は感放射線性膜と、活性光線又は放射線により酸を発生する化合物、熱により酸を発生する化合物及び酸の少なくとも1つを含む上層膜とを有する積層体にも関する。
本発明の積層体は好ましくは基板上に感活性光線性又は感放射線性膜と、活性光線又は放射線により酸を発生する化合物、熱により酸を発生する化合物及び酸の少なくとも1つを含む上層膜とをこの順に有する積層体であり、半導体デバイスなどに含まれるパターン形成用のレジスト材料として好適に用いることができる。
下記表1に示す成分を、表2に示す組成で溶剤に溶解させ、それぞれについて固形分濃度2.0質量%の溶液を調製し、これを0.04μm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てレジスト組成物を調製した。
SL-1:プロピレングリコールモノメチルエーテルアセテート(PGMEA)
SL-2:ガンマブチロラクトン
SL-3:シクロヘキサノン
SL-4:乳酸エチル
SL-5:プロピレングリコールモノメチルエーテル(PGME)
下記表3に示す繰り返し単位の含有モル比(組成比)、重量平均分子量(Mw)、及び分子量分布(Mw/Mn)を有する樹脂と、下記表4に示す成分を溶剤に溶解させ、それぞれについて固形分濃度2.0質量%の溶液を調製し、0.04μm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て上層膜形成用組成物を調製した。
Y1:メチルイソブチルカルビノール(MIBC)
Y2:デカン
Y3:ジイソアミルエーテル
Y4:1-ブタノール
Y5:イソブチルイソブチレート
シリコンウエハ上に有機反射防止膜ARC29SR(Brewer社製)を塗布し、205℃で60秒間ベークを行い膜厚86nmの反射防止膜を形成し、その上に、下記表5に示すレジスト組成物を塗布し、120℃で60秒間に亘ってベーク(PB:Prebake)を行い、膜厚40nmのレジスト膜を形成した。
レジスト膜上に下記表5に示す上層膜形成用組成物を塗布し、膜厚が30nmの上層膜を形成した。
上記で作成した得られたウエハに、EUV露光装置(Exitech社製 Micro
Exposure Tool、NA0.3、Quadrupole、アウターシグマ0.68、インナーシグマ0.36)を用い、マスクを介してパターン露光を行った。具体的には、ネガ現像後にドットパターンを得るため、ピッチが100nm、直径が20nmであるホールパターンが含まれたダークマスクを介して、露光量を変えてEUV露光を行った。ただし、比較例2のみはポジ現像を行うため、ピッチが100nm、直径が20nmであるドットパターンが含まれたブライトマスクを介して、露光量を変えてEUV露光を行った。
EUV露光後、シリコンウエハ、レジスト膜、及び上層膜を有する積層体をEUV露光装置から取り出し、ただちに、下記表5に示す温度の条件で60秒間加熱(PEB)した。
その後、シャワー型現像装置(ACTES(株)製ADE3000S)を用いて、50回転(rpm)でウエハを回転しながら下記表5に記載の現像液(23℃)を、200mL/分の流量で、所定時間スプレー吐出して、現像を行った。
その後、50回転(rpm)でウエハを回転しながら下記表5に記載のリンス液(23℃)を、200mL/分の流量で、所定時間スプレー吐出してリンス処理を行った。
最後に、2500回転(rpm)で120秒間高速回転してウエハを乾燥させた。
なお、表5にリンス液が記載されていない実施例及び比較例についてはリンスを行わなかった。
走査型電子顕微鏡((株)日立製作所製S-9380II)を用いて、得られたレジストパターンのドット径を測定し、所望のドットパターンが倒れや剥がれが発生することなく分離解像している最小寸法を算出し、ドット解像性とした。結果を下記表5に示す。
SG-1:2-ヘプタノン(メチルアミルケトン)
SG-2:酢酸イソアミル
SG-3:酢酸ブチル
SG-4:2.38質量%テトラブチルアンモニウム水溶液
SG-5:ジイソブチルケトン
L-1:ウンデカン
L-2:イソデカン
L-3:n-デカン
L-4:4-メチル-2-ペンタノール
L-5:純水
L-6:ジイソブチルケトン
EUV露光装置の代わりに電子線照射装置((株)JEOL製 JBX6000;加速電圧50keV)を用いて、先に説明したのと同様の方法により、パターンを形成し、得られたパターンについて、先に説明したのと同様の評価を行っても、ドット解像性が優れたものとなり、極微細の残しパターンの形成において高い解像力を得ることができた。
EUV露光装置の代わりにArFエキシマレーザー液浸スキャナー(ASML社製;XT1700i、NA1.20、C-Quad、アウターシグマ0.85、インナーシグマ0.75、XY偏光)を用いて、先に説明したのと同様の方法により、パターンを形成した。そして、得られたパターンについて、先に説明したのと同様の評価を行った。結果を表6に示す。
Claims (12)
- (a)感活性光線性又は感放射線性組成物により感活性光線性又は感放射線性膜を形成する工程、
(b)前記感活性光線性又は感放射線性膜上に上層膜形成用組成物により上層膜を形成する工程、
(c)前記上層膜が形成された前記感活性光線性又は感放射線性膜を露光する工程、及び
(d)露光された前記感活性光線性又は感放射線性膜を、有機溶剤を含有する現像液で現像する工程
を含むパターン形成方法であって、
前記上層膜形成用組成物が、活性光線又は放射線により酸を発生する化合物、熱により酸を発生する化合物及び酸の少なくとも1つを含む、パターン形成方法。 - 前記上層膜形成用組成物が熱により酸を発生する化合物を含む、請求項1又は2に記載のパターン形成方法。
- 前記上層膜形成用組成物は溶剤を含有し、前記上層膜形成用組成物に含まれる全溶剤に対して、水酸基を有する溶剤の含有比率が50質量%以下である、請求項1~3のいずれか一項に記載のパターン形成方法。
- 前記上層膜形成用組成物は、芳香環を有する繰り返し単位を含有する樹脂を含む、請求項1~4のいずれか一項に記載のパターン形成方法。
- 前記感活性光線性又は感放射線性組成物は、芳香環を有する繰り返し単位を含有する樹脂を含む、請求項1~5のいずれか一項に記載のパターン形成方法。
- 前記有機溶剤を含有する現像液は、エステル系溶剤、ケトン系溶剤、エーテル系溶剤、及び炭化水素系溶剤から選択される少なくとも1種の溶剤を含む、請求項1~6のいずれか一項に記載のパターン形成方法。
- 前記有機溶剤を含有する現像液は、エステル系溶剤を含む、請求項1~7のいずれか一項に記載のパターン形成方法。
- 前記工程(d)の後に、
(e)現像された前記感活性光線性又は感放射線性膜をリンス液を用いてリンスする工程、
を含む、請求項1~8のいずれか一項に記載のパターン形成方法。 - 前記リンス液が炭化水素系溶剤を含むリンス液である請求項9に記載のパターン形成方法。
- 請求項1~10のいずれか一項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。
- 感活性光線性又は感放射線性膜と、
活性光線又は放射線により酸を発生する化合物、熱により酸を発生する化合物及び酸の少なくとも1つを含む上層膜と
を有する積層体。
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