WO2021157551A1 - リソグラフィー用組成物及びパターン形成方法 - Google Patents
リソグラフィー用組成物及びパターン形成方法 Download PDFInfo
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- WO2021157551A1 WO2021157551A1 PCT/JP2021/003658 JP2021003658W WO2021157551A1 WO 2021157551 A1 WO2021157551 A1 WO 2021157551A1 JP 2021003658 W JP2021003658 W JP 2021003658W WO 2021157551 A1 WO2021157551 A1 WO 2021157551A1
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- 0 CCC(*)(CC)N(C(C(*)=C1*)=O)C1=O Chemical compound CCC(*)(CC)N(C(C(*)=C1*)=O)C1=O 0.000 description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-M [O-]C(c1ccccc1O)=O Chemical compound [O-]C(c1ccccc1O)=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
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- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/367—Halogenated derivatives polycyclic non-condensed, containing only six-membered aromatic rings as cyclic parts, e.g. halogenated poly-hydroxyphenylalkanes
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- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/38—Halogenated derivatives with at least one hydroxy group on a condensed ring system containing two rings
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- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/16—Halogens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
- C08F212/24—Phenols or alcohols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/09—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
- G03F7/094—Multilayer resist systems, e.g. planarising layers
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- 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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- 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
Definitions
- the present invention relates to a composition for lithography and a pattern forming method.
- the general resist material so far is a polymer-based resist material capable of forming an amorphous film.
- examples thereof include polymer-based resist materials such as polymethylmethacrylate and polyhydroxystyrene or polyalkylmethacrylate having an acid dissociation group (see, for example, Non-Patent Document 1).
- a line pattern of about 10 to 100 nm is formed by irradiating a resist thin film prepared by applying a solution of these resist materials on a substrate with ultraviolet rays, far ultraviolet rays, electron beams, extreme ultraviolet rays, or the like. ing.
- Non-Patent Document 2 the reaction mechanism of lithography using an electron beam or extreme ultraviolet rays is different from that of ordinary optical lithography (Non-Patent Document 2 and Non-Patent Document 3). Furthermore, in lithography using electron beams or extreme ultraviolet rays, the goal is to form fine patterns of several nm to ten and several nm. As the size of the resist pattern becomes smaller as described above, a resist composition having higher sensitivity to the exposure light source is required. In particular, in lithography using extreme ultraviolet rays, it is required to further increase the sensitivity in terms of throughput. As a resist material for improving the above-mentioned problems, an inorganic resist material having a metal element such as titanium, tin, hafnium or zirconium has been proposed (see, for example, Patent Document 1).
- the conventionally developed resist composition having high sensitivity characteristics has problems such as insufficient pattern quality such as large pattern defects and large roughness, insufficient sensitivity improvement, and insufficient etching resistance. Based on these circumstances, a lithography technology that achieves both high resolution and high sensitivity is required.
- the lithography using extreme ultraviolet rays uses a wavelength as short as 13.5 nm, the transparency of photons is higher and the number of photons at the same exposure intensity is smaller than that of the conventional exposure technique, so that extreme ultraviolet rays are efficiently exposed. Needs to be converted to the necessary protons. Furthermore, it is necessary to supply protons from the layer adjacent to the resist.
- the present invention provides a lithographic composition capable of forming a pattern having excellent exposure sensitivity, a composition for lithography for obtaining a film in contact with a resist layer (hereinafter referred to as "resist layer contact film”) and a lower layer film, and pattern formation.
- resist layer contact film a composition for lithography for obtaining a film in contact with a resist layer
- lower layer film a lower layer film
- the present inventors have obtained lithography by using a compound having a specific elemental composition or a resin containing the compound as a structural unit for a resist layer contact film or an underlayer film.
- the exposure sensitivity of the process can be increased, and have completed the present invention. That is, the present invention is as follows.
- a composition for lithography which comprises a compound having at least one element selected from the group consisting of iodine, tellurium and fluorine, or a resin having a structural unit derived from the compound.
- the composition for lithography in which the total mass of the atoms in the compound is 15% by mass or more and 75% by mass or less.
- composition for lithography according to any one of [1] to [3], wherein the compound is represented by the formula (A-4a).
- X indicates an oxygen atom, a sulfur atom, a single bond or no crosslink
- Y is a 2n-valent group or a single bond having 1 to 60 carbon atoms.
- X is non-crosslinked
- Y is the 2n-valent group.
- Each R 0 independently has an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, and a substituent.
- a thiol group or a hydroxyl group where, at least one of R 0 is a hydroxyl group, m is an integer from 1 to 9 independently.
- Q represents iodine, tellurium, fluorine, or an alkyl group having 1 to 30 carbon atoms containing at least iodine or tellurium or fluorine, or an aryl group having at least iodine or tellurium or fluorine and having 6 to 40 carbon atoms.
- n is an integer from 1 to 4
- p is an integer of 0 to 3 independently
- At least one of Q, R 0 and Y contains at least one element of iodine, tellurium and fluorine.
- q is an integer from 0 to (4 + 2 ⁇ pm) independently.
- [4-1] The lithographic composition according to [4], wherein X is an oxygen atom or non-crosslinked.
- [4-2] The lithographic composition according to [4] or [4-1], wherein Q is iodine.
- [4-3] The composition for lithography according to any one of [4] to [4-2], wherein at least one of Q, R 0, and Y contains iodine.
- [4-4] The composition for lithography according to any one of [4] to [4-3], wherein q is an integer of 1 to (4 + 2 ⁇ pm) independently.
- [5] The composition for lithography according to any one of [4] to [4-4], wherein Y is a 2n-valent hydrocarbon group having an aryl group having 6 to 60 carbon atoms which may have a substituent. .. [5-1]
- [5-2] The composition for lithography according to [5] or [5-1], wherein the aryl group having 6 to 60 carbon atoms is a phenyl group or a biphenyl group.
- [5-3] The composition for lithography according to any one of [5] to [5-2], wherein the substituent is iodine.
- [6] The composition for lithography according to any one of [1] to [3], wherein the compound is represented by the formula (A-4c).
- X indicates an oxygen atom, a sulfur atom, a single bond or no crosslink
- Y is a 2n-valent group or a single bond having 1 to 60 carbon atoms.
- Y is the 2n-valent group.
- Each R 0 independently has an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, and a substituent.
- a thiol group or a hydroxyl group where, at least one of R 0 is a hydroxyl group, At least one of R 0 is iodine, or an iodine-containing group.
- m is an integer from 1 to 9 independently.
- n is an integer from 1 to 4
- p is an integer of 0 to 3 independently.
- [6-1] The lithographic composition according to [6], wherein X is an oxygen atom or non-crosslinked.
- Y is a 2n-valent hydrocarbon group having an aryl group having 6 to 60 carbon atoms which may have a substituent. .. [7-1]
- [7-2] The composition for lithography according to [7] or [7-1], wherein the aryl group having 6 to 60 carbon atoms is a phenyl group or a biphenyl group.
- [7-3] The lithographic composition according to any one of [7] to [7-2], wherein the substituent is iodine.
- [8] The composition for lithography according to any one of [1] to [3], wherein the compound is represented by the general formula (AM1).
- R 1 represents a hydrogen atom, methyl, or halogen group.
- R 2 independently represents a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms.
- A represents an organic group having 1 to 30 carbon atoms.
- n 1 represents 0 or 1 and represents n 2 represents an integer from 1 to 20.
- [8-1] The lithographic composition according to [8], wherein R 1 is methyl.
- [8-2] The lithographic composition according to [8] or [8-1], wherein n 1 is 0.
- [8-3] The composition for lithography according to any one of [8] to [8-2], wherein A is an alicyclic hydrocarbon group.
- X independently represents an organic group having 1 to 5 carbon atoms and having 1 to 5 substituents selected from the group consisting of tellurium, I, F, or tellurium, I, and F, and X.
- At least one of the tellurium or I L 1 represents a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphoric acid group.
- n is an integer greater than or equal to 0 and Z is an alkoxy group, an ester group, an acetal group, or a carbonic acid ester group, respectively.
- r is an integer greater than or equal to 0 and A is an organic group having 1 to 30 carbon atoms.
- R a , R b , and R c are H, I, F, Cl, Br, or organic groups having 1 to 60 carbon atoms which may have a substituent, respectively, and p is an organic group having 1 to 60 carbon atoms. It is an integer of 1 or more.
- [9-3] The composition for lithography according to any one of [9] to [9-2], wherein Y is a hydroxyl group and n is an integer of 1 or more.
- [9-4] The composition for lithography according to any one of [9] to [9-3], wherein r is 0.
- [9-5] The composition for lithography according to any one of [9] to [9-4], wherein A is an aromatic ring having 6 to 14 carbon atoms.
- [9-6] The composition for lithography according to any one of [9] to [9-5], wherein R a , R b , and R c are hydrogen.
- Circuit pattern forming method including. [20] A compound represented by the formula (A-4a).
- X indicates an oxygen atom, a sulfur atom, a single bond or no crosslink
- Y is a 2n-valent group or a single bond having 1 to 60 carbon atoms.
- X is non-crosslinked
- Y is the 2n-valent group.
- Each R 0 independently has an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, and a substituent.
- a thiol group or a hydroxyl group where, at least one of R 0 is a hydroxyl group, m is an integer from 1 to 9 independently.
- Q represents iodine, tellurium, fluorine, or an alkyl group having 1 to 30 carbon atoms containing at least iodine or tellurium or fluorine, or an aryl group having at least iodine or tellurium or fluorine and having 6 to 40 carbon atoms.
- n is an integer from 1 to 4
- p is an integer of 0 to 3 independently
- At least one of Q, R 0 and Y contains at least one element of iodine, tellurium and fluorine.
- q is an integer from 0 to (4 + 2 ⁇ pm) independently.
- [20-2] The compound according to [20] or [20-1], wherein Q is iodine.
- [20-3] The compound according to any one of [20] to [20-2], wherein at least one of Q, R 0, and Y contains iodine.
- [20-4] The compound according to any one of [20] to [20-3], wherein q is an integer of 1 to (4 + 2 ⁇ pm) independently.
- [21] The compound according to any one of [20] to [20-4], wherein Y is a 2n-valent hydrocarbon group having an aryl group having 6 to 60 carbon atoms which may have a substituent.
- [21-1] The compound according to [21], wherein the 2n-valent hydrocarbon group is a methylene group.
- [21-2] The compound according to [21] or [21-1], wherein the aryl group having 6 to 60 carbon atoms is a phenyl group or a biphenyl group.
- [21-3] The compound according to any one of [21] to [21-2], wherein the substituent is iodine.
- X indicates an oxygen atom, a sulfur atom, a single bond or no crosslink
- Y is a 2n-valent group or a single bond having 1 to 60 carbon atoms.
- Y is the 2n-valent group.
- Each R 0 independently has an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, and a substituent.
- a thiol group or a hydroxyl group where, at least one of R 0 is a hydroxyl group, At least one of R 0 is iodine, or an iodine-containing group.
- m is an integer from 1 to 9 independently.
- n is an integer from 1 to 4
- p is an integer of 0 to 3 independently.
- [22-1] The compound according to [22], wherein X is an oxygen atom or non-crosslinked.
- Y is a 2n-valent hydrocarbon group having an aryl group having 6 to 60 carbon atoms which may have a substituent.
- the compound according to [23], wherein the 2n-valent hydrocarbon group is a methylene group.
- the aryl group having 6 to 60 carbon atoms is a phenyl group or a biphenyl group.
- [23-3] The compound according to any one of [23] to [23-2], wherein the substituent is iodine.
- composition for lithography capable of increasing the exposure sensitivity of a lithography process and a pattern forming method.
- the present embodiment is an example for explaining the present invention, and the present invention is not limited to the present embodiment.
- Compound (A) and Resin (A) include iodine, tellurium and It has at least one element selected from the group consisting of fluorine (preferably the group consisting of iodine and tellurium). Since iodine and tellurium have a high ability to absorb extreme ultraviolet rays, they can absorb extreme ultraviolet rays to ionize compound (A) and efficiently generate protons.
- the total content of iodine and tellurium atoms is 15% by mass or more and 75% by mass or less, preferably 20% by mass or more and 75% by mass or less of the whole compound (A).
- the total content of iodine and tellurium is 15% by mass or less, the absorption capacity of extreme ultraviolet rays is low, so that the efficiency of proton production is low.
- the total content of iodine and tellurium is 75% by mass or more, the stability of the compound becomes low and it becomes easy to decompose.
- the compound (A) preferably contains an aromatic ring from the viewpoint of high density. As the density increases, the absorption rate per length of passage of extreme ultraviolet rays improves. Further, the compound (A) preferably contains a hydrophilic group such as a hydroxyl group from the viewpoint of adhesion to the substrate and the resist layer.
- the "hydrophilic group” means a group that improves the affinity between the organic compound and water by binding to the organic compound.
- the hydrophilic group include a hydroxyl group, a nitro group, an amino group, a carboxyl group, a thiol group, a phosphine group, a phosphon group, a phosphoric acid group, an ether group, a thioether group, a urethane group, a urea group, an amide group and an imide group. Be done.
- the compound (A) preferably has curability and solvent resistance after curing so as to form a film and not to dissolve in the resist liquid when the resist is applied. Therefore, for example, compound (A) preferably contains a crosslinkable group or a polymerizable group.
- Crosslinkable group means a group that crosslinks in the presence of a catalyst or in the absence of a catalyst.
- the crosslinkable group is not particularly limited, and has, for example, an alkoxy group having 1 to 20 carbon atoms, a group having an allyl group, a group having a (meth) acryloyl group, a group having an epoxy (meth) acryloyl group, and a hydroxyl group. Examples thereof include a group having a urethane (meth) acryloyl group, a group having a glycidyl group, and a group having a vinylphenylmethyl group.
- polymerizable group means a group that polymerizes in the presence of a catalyst or in the absence of a catalyst.
- the polymerizable group is not particularly limited, and examples thereof include a group having a (meth) acrylic group, a group having an unsaturated double bond such as a vinyl group, and a group having an unsaturated triple bond such as a propagyl group.
- the compound (A) contains a dissociative group.
- “Dissociative group” means a group that dissociates in the presence of a catalyst or in the absence of a catalyst.
- the acid dissociative group refers to a characteristic group that cleaves in the presence of an acid and changes into an alkali-soluble group or the like. Specific examples of the acid dissociative group include those described in International Publication No. 2016/158168.
- Preferred examples of the acid dissociable group are a 1-substituted ethyl group, a 1-substituted-n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, and a 1-substituted alkoxymethyl group having the property of being dissociated by an acid.
- Examples thereof include a group selected from the group consisting of a group, a cyclic ether group, an alkoxycarbonyl group and an alkoxycarbonylalkyl group.
- the resin (A) in addition to the resin obtained by polymerizing the compound (A) alone, a resin polymerized using a cross-linking agent, a resin copolymerized with another compound, and the like can be used, and are particularly limited. Not done.
- the weight average molecular weight of the resin (A) is preferably 300 to 20000, more preferably 300 to 10000, and even more preferably 300 to 8000, from the viewpoint of reducing defects in the formed film and having a good pattern shape.
- a value obtained by measuring the polystyrene-equivalent weight average molecular weight using GPC can be used.
- a known method can be used without limitation as long as the method can produce a resin having the compound (A) as a constituent unit.
- a method of cross-linking with an aldehyde, a ketone, a carboxylic acid, a carboxylic acid halide, a halogen-containing compound, an amino compound, an imino compound, an isocyanate or the like, and a method of copolymerizing with an unsaturated hydrocarbon group-containing compound or the like can be mentioned.
- Examples of the "unsaturated hydrocarbon group-containing compound” are not particularly limited, but for example, a compound having a (meth) acrylic group, a compound having an unsaturated double bond such as a vinyl group, and an unsaturated triple bond such as a propagyl group. Examples thereof include compounds having.
- the resin (A) can also be obtained during the synthetic reaction of the compound (A).
- a method of obtaining the resin (A) from the raw material of the compound (A) may be adopted.
- the compound (A) is preferably a compound (A-1) represented by the formula (A-1), which comprises a predetermined amount of one or more selected from the group consisting of iodine, tellurium and fluorine.
- X independently represents an oxygen atom, a sulfur atom or no cross-linking
- R 1 is a single bond or a 2n-valent group having 1 to 30 carbon atoms.
- R 2 and R 3 are independently halogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and 2 to 10 carbon atoms.
- P are independently 0 or 1
- n is an integer of 1 to 4.
- at least one selected from the group consisting of R 1 , R 2 and R 3 is an iodine atom, tellurium.
- a group containing one or more selected from the group consisting of an atom and a fluorine atom, and at least one of R 2 and / or at least one of R 3 is one or more selected from a hydroxyl group and a thiol group.
- the compound (A) is also preferably a compound (A-2) represented by the formula (A-2), which comprises a predetermined amount of one or more selected from the group consisting of iodine, tellurium and fluorine.
- R 1 is a 2n-valent group having 1 to 30 carbon atoms
- R 2 to R 5 are independently linear, branched or cyclic groups having 1 to 10 carbon atoms.
- At least one is a group containing one or more selected from the group consisting of an integer atom, a tellurium atom and a fluorine atom, and at least one of R 4 and / or at least one of R 5 is one or more selected from a hydroxyl group and a thiol group.
- M 2 and m 3 are independently integers of 0 to 8
- m 4 and m 5 are independently integers of 0 to 9, except that m 4 and m 5 are 0 at the same time.
- N is an integer of 1 to 4
- p 2 to p 5 are independently integers of 0 to 2.
- the compound (A) is also preferably a compound (A-3) represented by the formula (A-3), which comprises a predetermined amount of one or more selected from the group consisting of iodine, tellurium and fluorine.
- R is independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an aryl group having 6 to 12 carbon atoms, and Z contains a hetero atom. It is an n-valent hydrocarbon group having 1 to 100 carbon atoms, n is 2 or more, and at least one selected from Z or R is one or more selected from the group consisting of iodine atom, tellurium atom and fluorine atom. Is a group containing.
- Compound (A) is a compound (A-4a) represented by the formula (A-4a) or the formula (A-4b) or containing a predetermined amount of one or more selected from the group consisting of iodine, tellurium and fluorine. It is also preferable that it is a compound (A-4b).
- the resin having a structural unit derived from the compound (A) of the present invention may be a polycyclic polyphenol resin having a structural unit derived from the compound (A-4a) and / or the compound (A-4b).
- the polycyclic polyphenol resin in the present embodiment is a polycyclic polyphenol resin having a repeating unit derived from at least one monomer selected from the group consisting of aromatic hydroxy compounds (A-4a) and (A-4b).
- the repeating units are connected to each other by a direct bond between aromatic rings. Since the film-forming composition of the present embodiment is configured in this way, it has excellent film-forming property, heat resistance, and sublimation resistance.
- X indicates an oxygen atom, a sulfur atom, a single bond or a non-crosslink
- Y is a 2n-valent group or a single bond having 1 to 60 carbon atoms, where X is When is non-crosslinked, Y is the 2n-valent group.
- A represents a benzene ring or a fused ring. Further, the formulas (A-4a) and the formula (A-).
- R 0 independently has an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, and a substituent.
- Q is iodine, tellurium, fluorine or iodine. Alternatively, it represents an alkyl group having 1 to 30 carbon atoms containing at least tellurium or fluorine, or an aryl group having 6 to 40 carbon atoms containing at least iodine, tellurium or fluorine.
- N is an integer of 1 to 4, and p is independent of each other.
- At least one of Q, R 0 , X, and Y contains at least one element of iodine, tellurium, and fluorine.
- q is an independently integer of 0 to (4 + 2 ⁇ pm)
- q is an independently of an integer of 0 to (2 + 2 ⁇ pm) (here).
- p represents the number of fused rings in the fused ring structure.)).
- X in the formula (A-4a) is preferably an oxygen atom from the viewpoint of heat resistance and reactivity.
- p of the formula (A-4a) is preferably 1 from the viewpoint of heat resistance and solubility.
- at least one of R 0 contains an iodine atom from the viewpoint of reactivity, and it is more preferable that Y does not contain an iodine atom from the viewpoint of storage stability.
- the formula (A-4a) is preferably the formula (A-4c).
- X indicates an oxygen atom, a sulfur atom, a single bond or no cross-linking
- Y is a 2n-valent group or single bond having 1 to 60 carbon atoms, where X is When is non-crosslinked, Y is the 2n-valent group, and R 0 independently has an alkyl group having 1 to 40 carbon atoms and a substituent which may have a substituent.
- the polyphenol resin in the present embodiment is not limited to the following, but typically has the following characteristics (1) to (5).
- the polycyclic polyphenol resin in the present embodiment has excellent solubility in an organic solvent (particularly a safe solvent). Therefore, for example, when the polyphenol resin of the present embodiment is used as a film forming material for lithography, a film for lithography can be formed by a wet process such as a spin coating method or screen printing.
- the carbon concentration is relatively high and the oxygen concentration is relatively low.
- the molecule has a phenolic hydroxyl group, it is useful for forming a cured product by reaction with a curing agent, but the cured product can be formed by the cross-linking reaction of the phenolic hydroxyl group at the time of high temperature baking alone. Due to these factors, the polycyclic polyphenol resin in the present embodiment can exhibit high heat resistance, and when used as a film forming material for lithography, deterioration of the film during high temperature baking is suppressed, and etching resistance to oxygen plasma etching and the like is suppressed. It is possible to form an excellent lithography film.
- the polycyclic polyphenol resin in the present embodiment can exhibit high heat resistance and etching resistance, and is excellent in adhesion to the resist layer and the resist intermediate layer film material. Therefore, when it is used as a film forming material for lithography, it is possible to form a film for lithography having excellent resist pattern forming property.
- resist pattern formability means a property in which no major defects are found in the resist pattern shape and both resolution and sensitivity are excellent.
- the polycyclic polyphenol resin in the present embodiment has a high refractive index due to its high aromatic ring density, and is suppressed in coloring even by a wide range of heat treatment from low temperature to high temperature, and is excellent in transparency.
- the polycyclic polyphenol resin in the present embodiment has Q as a functional group, so that the absorption rate for the EUV exposure light source can be improved, and the sensitivity is improved and the sensitivity is improved when used as an underlayer film for lithography. Productivity can be improved by suppressing pattern defects such as pattern collapse.
- the polycyclic polyphenol resin in the present embodiment can be preferably applied as a film-forming material for lithography due to such properties, and therefore the film-forming composition of the present embodiment is imparted with the above-mentioned desired properties.
- the composition for forming a film of the present embodiment is not particularly limited as long as it contains the above-mentioned polyphenolic polyphenol resin. That is, any arbitrary component may be contained in any blending ratio, and can be appropriately adjusted according to the specific use of the film-forming composition.
- X indicates an oxygen atom, a sulfur atom, a single bond or no crosslink.
- X an oxygen atom is preferable from the viewpoint of heat resistance.
- Y is a 2n-valent group or a single bond having 1 to 60 carbon atoms, and when X is non-crosslinked, Y is the 2n-valent group.
- the 2n-valent group having 1 to 60 carbon atoms is, for example, a 2n-valent hydrocarbon group, and the hydrocarbon group may have various functional groups described later as a substituent.
- an alkanehexayl group having 2 to 60, and an alkaneoctayl group having 3 to 60 carbon atoms when n 4.
- Examples of the 2n-valent hydrocarbon group include a group in which a 2n + 1-valent hydrocarbon group is bonded to a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group.
- the alicyclic hydrocarbon group the Aribashi alicyclic hydrocarbon group is also included.
- the 2n + 1-valent hydrocarbon group is not limited to the following, and examples thereof include a trivalent methine group and an ethine group.
- the 2n-valent hydrocarbon group may have a double bond, a heteroatom and / or an aryl group having 6 to 59 carbon atoms.
- Y may contain a group derived from a compound having a fluorene skeleton such as fluorene or benzofluorene, but in the present specification, the term "aryl group” refers to a fluorene skeleton such as fluorene or benzofluorene. It is used as a compound that does not contain a group derived from the compound.
- the 2n-valent group may contain a halogen group, a nitro group, an amino group, a hydroxyl group, an alkoxy group, a thiol group or an aryl group having 6 to 40 carbon atoms. Further, the 2n-valent group may contain an ether bond, a ketone bond, an ester bond or a double bond.
- the 2n-valent group preferably contains a branched hydrocarbon group or an alicyclic hydrocarbon group rather than a linear hydrocarbon group from the viewpoint of heat resistance, and may contain an alicyclic hydrocarbon group. More preferred. Further, in the present embodiment, it is particularly preferable that the 2n-valent group has an aryl group having 6 to 60 carbon atoms.
- the substituent which can be contained in the 2n-valent group and is not particularly limited as the alicyclic hydrocarbon group and the aromatic group having 6 to 60 carbon atoms is, for example, an unsubstituted phenyl group, a naphthalene group and a biphenyl.
- anthracyl group pyrenyl group, cyclohexyl group, cyclododecyl group, dicyclopentyl group, tricyclodecyl group, adamantyl group, phenylene group, naphthalenediyl group, biphenyldiyl group, anthracendyl group, pyrenedyl group, cyclohexanediyl group, cyclo Dodecandyl group, dicyclopentanediyl group, tricyclodecandyl group, adamantandiyl group, benzenetriyl group, naphthalentryyl group, biphenyltriyl group, anthracentlyyl group, pyrentryyl group, cyclohexanetriyl group, cyclododecane Triyl group, dicyclopentanetriyl group, tricyclodecantryyl group, adamantantri
- Each R 0 independently has an alkyl group having 1 to 40 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, and a substituent.
- a thiol group or a hydroxyl group may be linear, branched or cyclic.
- at least one of R 0 is a hydroxyl group.
- the alkyl group having 1 to 40 carbon atoms is not limited to the following, but for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, and the like. Examples thereof include an n-pentyl group, an n-hexyl group, an n-dodecyl group, and a barrel group.
- Examples of the aryl group having 6 to 40 carbon atoms include, but are not limited to, a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, a perylene group and the like.
- Examples of the alkenyl group having 2 to 40 carbon atoms include, but are not limited to, an ethynyl group, a propenyl group, a butynyl group, a pentynyl group and the like.
- Examples of the alkynyl group having 2 to 40 carbon atoms include, but are not limited to, an acetylene group and an ethynyl group.
- the alkoxy group having 1 to 40 carbon atoms is not limited to the following, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.
- M is an integer of 1 to 9 independently. From the viewpoint of solubility, 1 to 6 is preferable, 1 to 4 is more preferable, and 1 is further preferable from the viewpoint of raw material availability.
- N is an integer from 1 to 4. From the viewpoint of solubility, 1 to 2 is preferable, and from the viewpoint of raw material availability, 1 is more preferable.
- P is an integer of 0 to 3 independently. From the viewpoint of heat resistance, 1 to 2 is preferable, and from the viewpoint of raw material availability, 1 is more preferable.
- aromatic hydroxy compound those represented by any of the above formulas (A-4a) and (A-4b) can be used alone, or two or more kinds can be used together. can.
- the compound represented by the above formula (A-4a) it is preferable to use the compound represented by the above formula (A-4a) as the aromatic hydroxy compound.
- the compound represented by the above formula (A-4b) it is also preferable to use the compound represented by the above formula (A-4b) as the aromatic hydroxy compound.
- the compound (A) of the present embodiment is an oligomer (A-5) having an aralkyl structure represented by the following formula (A-5), which contains a predetermined amount of one or more selected from iodine, tellurium and fluorine. There may be.
- Ar 0 may independently contain the same group or a different group, and may contain a divalent group containing a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a pyrylene group, a fluorylene group, a biphenylene group, or a terphenylene group.
- R 0 may independently be the same group or a different group, may have a substituent, an alkyl group having 1 to 30 carbon atoms, or an aryl group, iodine, which may have a substituent.
- n represents an integer from 1 to 50;
- r 0 independently represents an integer from 0 to 3;
- p represents an integer of 0 or more independently.
- R 0 contains any one of iodine, tellurium and fluorine.
- Ar 0 represents a divalent group including a phenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a pyrylene group, a fluorylene group, a biphenylene group, or a terphenylene group, and represents a phenylene group and a naphthylene group.
- a divalent group containing a group, an anthrylene group, or a pyrylene group is preferable.
- Ar 0 may be the same group or different groups independently of each other.
- 1,4-phenylene group 1,3-phenylene group, 4,4'-biphenylene group, 2,4'-biphenylene group, 2,2'-biphenylene group, 2,3' -Biphenylene group, 3,3'-biphenylene group, 3,4'-biphenylene group, 2,6-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,8-naphthylene group, 1, Examples thereof include a 3-naphthylene group, a 1,4-naphthylene group, an anthrylene group, a phenanthylene group, a pyrylene group, a fluorylene group, a terphenylene group and the like.
- the Ar 0 is a divalent group in which a plurality of phenylene groups such as a divalent group containing a diphenylmethyl structure, a bisphenol structure, or a bis (hydroxyphenyl) diisopropylphenyl structure are linked by an alkylene group or the like. Is also included.
- R 0 is a substituent of Ar 0 , and each independently has an alkyl group having 1 to 30 carbon atoms, which may have the same group or a different group, and may have a substituent, or a substituent. Represents a good aryl group. Specific examples of R 0 include specific examples of R a and R b described later.
- n represents an integer of 1 to 50. From the viewpoint of film flattening performance, n is preferably 3 to 40, more preferably 3 to 30, and particularly preferably 3 to 20.
- r 0 independently represents an integer of 0 to 3. However, not all r 0s become 0 at the same time. r 0 is preferably 1 to 3 from the viewpoint of curability and improvement of solubility.
- p independently represents an integer of 0 or more. However, not all ps become 0 at the same time. p changes as appropriate depending on the type of Ar 0.
- the compound (A) is also preferably a compound (A-6) represented by the formula (A-6), which comprises a predetermined amount of one or more selected from iodine, tellurium and fluorine.
- R 1 represents a hydrogen atom or a methyl group or a halogen group.
- R 2 independently represents a hydrogen atom, a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, or a cyclic organic group having 3 to 20 carbon atoms.
- A represents an organic group having 1 to 30 carbon atoms.
- Q independently represents iodine, tellurium, fluorine, or an alkyl group or aryl group having at least iodine or tellurium or fluorine having 1 to 30 carbon atoms, and Q is preferably iodine.
- n 1 represents 0 or 1 and represents n 2 represents an integer from 1 to 20.
- R 1 can use a hydrogen atom or a methyl group or a halogen group.
- a known atom can be used as the halogen group, and F, Cl, Br, I and the like can be appropriately used.
- R 1 is preferably a methyl group or a halogen group from the viewpoint of exposure sensitivity when the compound of the present invention is used as a constituent unit of the resin for the resist and the stability of the material, and particularly from the viewpoint of exposure sensitivity. It is more preferably a halogen group, and even more preferably I.
- R 2 is two or more selected from the group consisting of a linear organic group having 1 to 20 carbon atoms, a branched organic group having 3 to 20 carbon atoms, and a cyclic organic group having 3 to 20 carbon atoms. It may be a combination.
- R 2 is preferably a hydrogen atom for the purpose of suppressing an increase in Tg of the resin and improving the effect of introducing an iodine element. Further, it is also preferable that the organic group has 1 or more carbon atoms for the purpose of improving the acid decomposability for the purpose of controlling the solubility in the developing solution. Further, it is also preferable that the hydrogen atom is used for the purpose of suppressing the acid decomposition property and particularly ensuring the solubility in an alkaline developer and suppressing the residue.
- R 2 may have a substituent.
- R 2 may have, for example, an alkyl group having 1 to 20 carbon atoms, 1 to 10 carbon atoms or 1 to 6 carbon atoms; and may have a substituent;
- R 2 include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, which may have a substituent.
- Icosyl group cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloicosyl group, adamantyl group, ethylene group, propylene group, butylene group, phenyl group, naphthyl group , Anthracene group, phenanthrene group, tetracene group, chrysen group, triphenylene group, pyrene group, benzopyrene group, azulene group, fluorene group and the like. These may include ether bonds, ketone bonds, and ester bonds.
- the illustrated group includes an isomer.
- the propyl group contains an n-propyl group and an isopropyl group
- the butyl group includes an n-butyl group, a sec-butyl group, an isobutyl group and a tert-butyl group.
- the substituent of R 2 is not particularly limited, but for example, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, a linear aliphatic hydrocarbon group, or a branched aliphatic hydrocarbon.
- Hydrogen group, cyclic aliphatic hydrocarbon group, aryl group, aralkyl group, alkoxy group, alkenyl group, acyl group, alkoxycarbonyl group, alkyloxy group, allyloyloxy group, alkylsilyl group and various crosslinkable groups Examples include acid dissociable groups.
- crosslinkable group is a group that is crosslinked by acid, alkali, light or heat, and is a group that is crosslinked in the presence of a catalyst or in the absence of a catalyst.
- the crosslinkable group is not particularly limited, and is, for example, a group having an allyl group, a group having a (meth) acryloyl group, a group having an epoxy (meth) acryloyl group, a group having a urethane (meth) acryloyl group, and a hydroxyl group.
- a group having a glycidyl group, a group having a vinylphenylmethyl group, a group having a styrene group, a group having an alkynyl group, a group having a carbon-carbon double bond, and a carbon-carbon triple bond examples thereof include a group having and a group containing these groups.
- the “acid dissociative group” is a group that cleaves in the presence of an acid to generate an alkali-soluble group (for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a hexafluoroisopropanol group) or the like.
- the acid dissociable group is not particularly limited, but is appropriately selected from those proposed in, for example, hydroxystyrene resins used in chemically amplified resist compositions for KrF and ArF, (meth) acrylic acid resins, and the like. Can be used.
- Specific examples of the acid dissociative group include those described in International Publication No. 2016/158168.
- A may have a substituent.
- Examples of the compound serving as the skeleton of A include alkanes having 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms or 1 to 6 carbon atoms, which may have a substituent; May have 2 to 30 carbon atoms, 2 to 20 carbon atoms, 2 to 10 carbon atoms or 2 to 6 carbon atoms; may have a substituent, 2 to 30 carbon atoms, carbon Alkin having 2 to 20 carbon atoms or 2 to 10 carbon atoms or 2 to 6 carbon atoms; may have a substituent, 3 to 30 carbon atoms, 3 to 20 carbon atoms, 3 to 10 carbon atoms or 3 carbon atoms.
- Cycloalkane of ⁇ 6 may have a substituent; cycloalkene having 3 to 30 carbon atoms, 3 to 20 carbon atoms, 3 to 10 carbon atoms or 3 to 6 carbon atoms; having a substituent. It may have 3 to 30 carbon atoms, 3 to 20 carbon atoms, 3 to 10 carbon atoms or 3 to 6 carbon atoms; it may have a substituent, 5 to 30 carbon atoms, 5 to 5 carbon atoms. 20, an array having 5 to 10 carbon atoms or 5 to 6 carbon atoms; combinations thereof and the like can be mentioned.
- Specific examples of the compound that forms the skeleton of A include, for example, methane, ethane, propane, butane, pentane, hexane, heptene, octane, nonane, decan, icosan, triacontane, and cyclo, which may have a substituent.
- the substituent of the compound that forms the skeleton of A is not particularly limited, but is, for example, a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a cyano group, a nitro group, an amino group, a thiol group, a heterocyclic group, or a linear group.
- Aliphatic hydrocarbon group branched aliphatic hydrocarbon group, cyclic aliphatic hydrocarbon group, aryl group, aralkyl group, alkoxy group, alkenyl group, acyl group, alkoxycarbonyl group, alkyloxy group, allyloyloxy group, Examples thereof include an alkylsilyl group, various crosslinkable groups, and an acid dissociable group.
- crosslinkable group and “acid dissociative group” are not particularly limited, but for example, those described in the description of R 2 can be used.
- n 1 represents 0 or 1 and is preferably 1.
- n 2 is an integer of 1 to 20, preferably an integer of 2 to 20, more preferably an integer of 2 to 10, and even more preferably an integer of 2 to 5.
- the compound (A) according to the present embodiment may be a compound (A-7) represented by the following formula (A-7) containing a predetermined amount of one or more selected from iodine, tellurium and fluorine. good.
- Compound (A-7) preferably contains a functional group whose solubility in an alkaline developer is improved by the action of an acid or base. It is preferable that any of the following Z, Y, and X contains a functional group whose solubility in an alkaline developer is improved by the action of an acid or a base.
- Each of X has 1 to 30 carbon atoms having a substituent of 1 to 5 selected from the group consisting of tellurium, I, F, Cl, Br, or tellurium, I, F, Cl, and Br, respectively. It is an organic group of. At least one of X is tellurium or I.
- L 1 is a single bond, an ether group, an ester group, a thioether group, an amino group, a thioester group, an acetal group, a phosphine group, a phosphon group, a urethane group, a urea group, an amide group, an imide group, or a phosphoric acid group.
- L 1 is preferably a single bond.
- M is an integer of 1 or more, preferably an integer of 1 or more and 5 or less, more preferably an integer of 2 or more and 4 or less, and further preferably 2 or 3.
- Y is independently a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, a phosphon group, a urethane group, A urea group, an amide group, an imide group, or a phosphoric acid group, which is an alkoxy group, an ester group, a carbonate ester group, an amino group, an ether group, a thioether group, a phosphine group, a phosphon group, a urethane group, or a urea group of Y.
- the amide group, imide group, and phosphate group may have a substituent.
- Y is preferably a group represented by the following formula (Y-1) independently of each other.
- L 2 is a group that is cleaved by the action of an acid.
- * 1 is a binding site with A
- * 2 is a binding site with R 2.
- L 2 is preferably an acetal group, a carbonic acid ester group or a carboxyalkoxy group.
- R 2 is a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and an aliphatic group containing a linear, branched or cyclic heteroatom having 1 to 30 carbon atoms.
- a group is an aromatic group containing a hetero atom having 1 to 30 carbon atoms
- the aliphatic group of R 2 , an aromatic group, an aliphatic group containing a hetero atom, and an aromatic group containing a hetero atom further contain a substituent. You may have. Examples of the substituent here include a linear, branched or cyclic aliphatic group having 1 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.
- R 2 is preferably an aliphatic group.
- the aliphatic group in R 2 is preferably a branched or cyclic aliphatic group.
- the number of carbon atoms of the aliphatic group is preferably 1 or more and 20 or less, more preferably 3 or more and 10 or less, and further preferably 4 or more and 8 or less.
- the aliphatic group is not particularly limited, and examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, and a methylcyclohexyl group. Among these, a tert-butyl group or a cyclohexyl group is preferable.
- a carboxylic acid group is formed and the dissociated portion and the non-dissociated portion in the developing process. Since the difference in solubility and the difference in dissolution rate are widened, the resolution is improved, and the residue at the bottom of the pattern in the fine line pattern is particularly suppressed, which is preferable.
- Y is preferably a group represented by any of the following formulas (Y-1-1) to (Y-1-7) independently of each other.
- n is an integer of 0 or more, preferably an integer of 1 or more, more preferably an integer of 1 or more and 5 or less, still more preferably an integer of 1 or more and 3 or less, and even more preferably 1 or 2. Is.
- R a , R b , and R c are each independently H, I, F, Cl, Br, or an organic group having 1 to 60 carbon atoms which may have a substituent.
- the substituent of the organic group having 1 to 60 carbon atoms is not particularly limited, and examples thereof include I, F, Cl, Br, and other substituents.
- the other substituent is not particularly limited, but for example, a hydroxyl group, an alkoxy group, an ester group, an acetal group, a carbonate ester group, a nitro group, an amino group, a carboxyl group, a thiol group, an ether group, a thioether group, a phosphine group, and the like.
- Examples thereof include a phosphon group, a urethane group, a urea group, an amide group, an imide group and a phosphoric acid group.
- the alkoxy group, ester group, carbonate ester group, amino group, ether group, thioether group, phosphine group, phosphon group, urethane group, urea group, amide group, imide group, and phosphoric acid group further have a substituent. You may be doing it.
- the substituent here include a linear, branched or cyclic aliphatic group having 1 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.
- the number of carbon atoms of the organic group which may have a substituent in R a , R b , and R c is preferably 1 to 30.
- the organic group having 1 to 60 carbon atoms which may have a substituent is not particularly limited, but is a linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms and having 4 to 60 carbon atoms. Examples thereof include an alicyclic hydrocarbon group and an aromatic group which may contain a heteroatom having 6 to 60 carbon atoms.
- the linear or branched aliphatic hydrocarbon group having 1 to 60 carbon atoms is not particularly limited, and for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and the like.
- Examples thereof include a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, a barrel group and a 2-ethylhexyl group.
- the alicyclic hydrocarbon group is not particularly limited, and examples thereof include a cyclohexyl group, a cyclododecyl group, a dicyclopentyl group, a tricyclodecyl group, and an adamantyl group.
- an aromatic group that may contain a hetero atom such as a benzodiazole group, a benzotriazole group, or a benzothiadiazole group can also be appropriately selected.
- the combination of these organic groups can be selected.
- the aromatic group that may contain a heteroatom having 6 to 60 carbon atoms is not particularly limited, and is, for example, a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, a benzodiazole group, and a benzotriazole group. , Benzotriazole group.
- a methyl group is preferable.
- A is an organic group having 1 to 30 carbon atoms.
- A may be a monocyclic organic group or a double ring organic group.
- A is preferably an aromatic ring.
- the carbon number of A is preferably 6 to 14, and more preferably 6 to 10.
- A is preferably a group represented by any of the following formulas (A-1) to (A-4), and more preferably a group represented by the following formula (A-1).
- P indicates the number of vinyl groups, and p is an integer of 1 or more, preferably an integer of 1 or more and 3 or less, more preferably an integer of 1 or more and 2 or less, and further preferably 1.
- Z is an alkoxy group, an ester group, an acetal group, or a carbonic acid ester group, respectively.
- r is an integer of 0 or more, preferably an integer of 0 or more and 2 or less, more preferably an integer of 0 or more and 1 or less, and further preferably 0.
- the resin having a structural unit derived from the compound (A) of the present embodiment may have a structural unit represented by the following formula (A-8).
- A-8 a structural unit represented by the following formula (A-8).
- R 1 , R 2 , A, n 1 , and n 2 are as defined in the above formula (A-6), and the symbol * represents the connection point with the adjacent repeating unit.
- the (meth) acrylate (co) polymer represented by the above formula (A-8) is obtained by polymerizing one or more (meth) acrylate compounds represented by the above formula (A-6), or one or more. It can be obtained by polymerizing the (meth) acrylate compound represented by the above formula (A-6) with other monomers.
- the (meth) acrylate (co) polymer can be used as a material for forming a film for lithography.
- the compound (A) of the present embodiment and the resin derived from the compound (A) are used as the underlayer film of the resist in the exposure process, the compound (A) is used as the underlayer film of the resist layer, and processing such as dry etching after pattern formation is performed.
- the pattern quality such as the rectangularness and roughness of the layer to be processed after processing is good.
- a resin having a condensed ring structure in which a plurality of ring structures are condensed is condensed.
- the ring structure preferably has an aromatic structure or a heteroaromatic structure.
- the compound (A) of the present embodiment and the resin derived from the compound (A) are used as the resist underlayer film, and one or more other spin-on carbon (SOC) layers or an inorganic hard mask layer are further used as the etching mask layer.
- the etching rate is faster than that of the resist from the viewpoint of the workability of the etching mask layer to which the pattern shape of the resist layer is transferred by etching and the shape of the resist immediately after development so that the pattern shape is not deteriorated by etching.
- etching mask layers are laminated on a substrate having a layer to be processed. Further, by laminating a layer made of the compound (A) of the present embodiment or a resin containing the compound (A) on the upper layer side of the etching mask layer, the quality of the pattern shape of the processed layer after processing is improved. It is also preferable.
- a resin having a small aromatic ring structure or a structure having no novolak structure is preferable, and a resin or an aliphatic having an aliphatic structure such as a polyacrylic resin, a polyethylene resin, or a polyalkylene ether resin as a main chain is preferable.
- a resin having a high content ratio of the carbon skeleton constituting the structure is preferable.
- compound (A) is not limited thereto.
- composition containing compound (A) and / and resin (A) The composition of this embodiment comprises compound (A) and / and resin (A).
- solvent As the solvent in this embodiment, a known solvent can be appropriately used as long as the above-mentioned compound (A) and / and the resin (A) are at least soluble.
- Specific examples of the solvent are not particularly limited, but for example, ethylene glycol mono such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate.
- Alkyl ether acetates ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, Propropylene glycol monoalkyl ether acetates such as propylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate , Lactic acid esters such as n-butyl lactic acid and n-amyl lactic acid; methyl acetate, ethyl acetate, n-propyl acetate, n-butyl a
- Aliphatic carboxylic acid esters methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxy Other esters such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate, etc.
- aromatic hydrocarbons such as toluene and xylene
- ketones such as acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclopentanone (CPN), cyclohexanone (CHN);
- N, N -Amids such as dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone
- lactones such as ⁇ -lactone and the like can be mentioned, but are not particularly limited.
- the solvent used in this embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate and ethyl lactate. Yes, more preferably at least one selected from PGMEA, PGME, CHN, CPN and ethyl lactate.
- the amount of the solid component and the amount of the solvent are not particularly limited, but are 1 to 80% by mass of the solid component and 20 to 99% by mass of the solvent with respect to the total mass of the amount of the solid component and the solvent. It is preferable, more preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, further preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent, and particularly preferably 2 to 10% by mass of the solid component. It is 90% by mass and 90 to 98% by mass of the solvent.
- composition of the present embodiment directly or indirectly by irradiation or heating with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray and ion beam. It is preferable to contain at least one acid generator that generates acid.
- the acid generator is not particularly limited, and either a nonionic type or an ionic type may be used.
- Nonionic acid generators include sulfonate esters (eg 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone, diazonaphthoquinone 4-sulfonate), sulfones (eg disulfone, etc.). Ketosulfone, sulfonyldiazomethane) and the like.
- an onium salt containing an onium cation for example, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt
- an onium salt containing an onium cation for example, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt
- Examples of the onium salt anion include a sulfonic acid anion, a sulfonylimide anion, and a sulfonylmethide anion.
- a sulfonic acid anion for example, International Publication WO 2013/024778, JP-A-2009-134808, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A. 63-163452, Japanese Patent Application Laid-Open No. 62-153853, Japanese Patent Application Laid-Open No. 63-146029, US Pat. No. 3,779,778, US Pat. No. 3,849,137, German Patent No. 3914407, Europe
- the acid-generating compounds described in Japanese Patent Nos. 126, 712 and the like can be used.
- the acid generator may be used alone or in combination of two or more.
- the amount of the acid generator used is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, further preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass, based on the total mass of the solid component.
- the method of generating the acid is not particularly limited.
- a compound capable of promoting or suppressing the diffusion of the generated acid can be included as an acid diffusion control agent.
- Preferred acid diffusion promoters have a pKa value as low as 2.0 or less and a molecular weight of 1000 or less or a clogP value of 30 or less or Tg for the purpose of allowing the acid to be released under necessary conditions while retaining the generated acid.
- the temperature is 250 ° C. or lower, the heat diffusibility in the resin matrix can be promoted, and a compound having heat resistance at at least 250 ° C. can be contained.
- a specific structure of the acid diffusion accelerator either a nonionic system or an ionic system may be used.
- Nonionic acid diffusion promoters include sulfonate esters (eg 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxyimide, sulfonyloxyketone), sulfones (eg disulfone, ketosulfone, sulfonyldiazomethane). And so on.
- an onium salt containing an onium cation for example, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt is typical.
- Examples of the onium salt anion include a sulfonic acid anion, a sulfonylimide anion, and a sulfonylmethide anion.
- the cation in the ionic compound can be used without particular limitation as long as it is a cation that satisfies the above molecular weight, clogP, Tg, and heat resistance in a state where a salt with the anion is formed.
- organic ammonium cations, organic iodonium cations, and organic sulfonium cations can be preferably used.
- the acid diffusion inhibitor is an acid generated from an acid generator or the like by exposure, which suppresses diffusion in the resist film or the underlayer film in each step of exposure, PEB, and development, and is present in a trace amount or diffusion in an unexposed area. It can be used for the purpose of suppressing the reaction of the resist resin or the underlayer film resin due to the influence of. Other effects include improving the stability of the resist resin composition or the underlayer resin composition over time, improving the resolution in lithography, and suppressing the time dependence of pattern quality from exposure to development. It is possible to provide a resist resin composition or an underlayer film resin composition which leads to improvement in process robustness and has excellent process stability.
- As the acid diffusion inhibitor a small molecule compound may be applied as a form incorporated as a part of a polymer, or both forms may be used in combination.
- the acid diffusion inhibitor a salt that forms an acid having a weak acid dissociation property as compared with the acid generated from the acid generator used can be used.
- Acidity as an index of acid dissociation is indicated by acid dissociation constant (pKa).
- the acid dissociation constant of the acid generated from the acid diffusion inhibitor is -3 ⁇ pKa. It is preferably -1 ⁇ pKa ⁇ 7, and more preferably 0 ⁇ pKa ⁇ 5.
- the acid diffusion inhibitor include a nitrogen atom-containing compound, a photobase generator that is exposed to light and generates a weak acid upon exposure, and the like.
- nitrogen atom-containing compound examples include amine compounds such as trypentylamine and trioctylamine, amide group-containing compounds such as formamide and N, N-dimethylacetamide, urea compounds such as urea and 1,1-dimethylurea, and pyridine.
- nitrogen-containing heterocyclic compounds such as N- (undecylcarbonyloxyethyl) morpholine and Nt-pentyloxycarbonyl-4-hydroxypiperidin.
- Examples of the photobase generator include compounds containing an onium cation and a weak acid anion that are decomposed by exposure.
- a weak acid is generated from a proton generated by decomposition of an onium cation and an anion of a weak acid in an exposed portion, so that the acid diffusion controllability is lowered.
- Examples of salts that generate an acid having a weaker acidity than the acid generated from an acid generator include a salt represented by the formula (D) described in JP-A-2015-147926, JP-A-2012-229206. Examples thereof include the salts described in JP-A-2012-6908, JP-A-2012-721109, JP-A-2011-39502 and JP-A-2011-191745.
- Examples of other preferred acid diffusion inhibitors include, but are not limited to:
- the lower limit of the content of the acid diffusion control agent is preferably 0.1 part by mass with respect to 100 parts by mass of the polymer component (or resin component). , 0.5 parts by mass is more preferable, and 1 part by mass is further preferable.
- the upper limit of the content is preferably 20 parts by mass, more preferably 10 parts by mass, and even more preferably 5 parts by mass.
- the lower limit of the content of the acid diffusion control agent is preferably 1 mol% and more preferably 5 mol% with respect to 100 mol% of the acid generator. 10 mol% is more preferred.
- the upper limit of the content is preferably 250 mol%, more preferably 150 mol%, still more preferably 100 mol%.
- the acid diffusion control body may contain one kind or two or more kinds.
- cross-linking agent means a compound capable of cross-linking at least either the compound (A) or the resin (A).
- the cross-linking agent is preferably an acid cross-linking agent capable of intramolecularly or intermolecularly cross-linking the compound (A) or the resin (A) in the presence of an acid generated from the acid generator.
- Examples of such an acid cross-linking agent include compounds having one or more groups (hereinafter, referred to as “cross-linking groups”) capable of cross-linking the compound (A) or the resin (A).
- crosslinkable group examples include (i) hydroxy (alkyl group having 1 to 6 carbon atoms), alkoxy having 1 to 6 carbon atoms (alkyl group having 1 to 6 carbon atoms), and acetoxy (alkyl group having 1 to 6 carbon atoms).
- a group derived from the aromatic group of (vi), a polymerizable multiple bond-containing group such as a vinyl group or an isopropenyl group, and the like can be mentioned.
- a crosslinkable group of the cross-linking agent in the present embodiment a hydroxyalkyl group, an alkoxyalkyl group and the like are preferable, and an alkoxymethyl group is particularly preferable.
- the cross-linking agent having a cross-linking group is not particularly limited, but for example, the acid cross-linking agent described in International Publication WO2013 / 024778 can be used.
- the cross-linking agent may be used alone or in combination of two or more.
- the amount of the cross-linking agent used is preferably 0.5 to 50% by mass, more preferably 0.5 to 40% by mass, further preferably 1 to 30% by mass, and 2 to 20% by mass of the total mass of the solid component. % Is particularly preferable.
- the compounding ratio of the cross-linking agent is 0.5% by mass or more, the solvent resistance tends to be improved and dissolution in the resist solvent applied after curing tends to be suppressed, while when it is 50% by mass or less. , There is a tendency that the decrease in heat resistance after curing can be suppressed.
- composition of the present embodiment As other components, various additions such as dissolution accelerator, dissolution control agent, sensitizer, surfactant and organic carboxylic acid or phosphorus oxo acid or a derivative thereof are added to the composition of the present embodiment, if necessary. One or more agents can be added.
- the dissolution accelerator is a component having an action of increasing the solubility of a solid component in a developing solution and appropriately increasing the dissolution rate of the compound during development.
- the dissolution accelerator is preferably one having a low molecular weight, and examples thereof include a low molecular weight phenolic compound. Examples of the low molecular weight phenolic compound include bisphenols and tris (hydroxyphenyl) methane. These dissolution accelerators can be used alone or in combination of two or more.
- the blending amount of the dissolution accelerator is appropriately adjusted according to the type of the solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total mass of the solid component. % Is more preferable, and 0% by mass is particularly preferable.
- the dissolution control agent is a component having an action of controlling the solubility of a solid component in a developing solution and appropriately reducing the dissolution rate during development.
- a dissolution control agent those that do not chemically change in the steps of firing the film, irradiating the film, applying the upper layer, and the like are preferable.
- the dissolution control agent is not particularly limited, and for example, aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthylketone; Sulfones and the like can be mentioned. These dissolution control agents may be used alone or in combination of two or more.
- the blending amount of the dissolution control agent is appropriately adjusted according to the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0-1% by mass of the total mass of the solid component. Is more preferable, and 0% by mass is particularly preferable.
- the sensitizer is a component that absorbs the energy of the irradiated radiation and transfers the energy to the acid generator, thereby having an action of increasing the amount of acid produced and improving the curability.
- Examples of such a sensitizer include benzophenones, biacetyls, pyrenes, phenothiazines, fluorenes, and the like, but are not particularly limited. These sensitizers can be used alone or in combination of two or more.
- the blending amount of the sensitizer is appropriately adjusted according to the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total mass of the solid component. More preferably, 0% by mass is particularly preferable.
- the surfactant is a component having an action of improving the coatability and striation of the composition of the present embodiment, the coatability of the upper layer film, and the like.
- the surfactant may be any of an anionic surfactant, a cationic surfactant, a nonionic surfactant or an amphoteric surfactant.
- Preferred surfactants include nonionic surfactants.
- the nonionic surfactant has a good affinity with the solvent used for producing the composition of the present embodiment, and can further enhance the effect of the composition of the present embodiment.
- nonionic surfactant examples include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the like, but are not particularly limited.
- Commercially available products of these surfactants are Ftop (manufactured by Gemco), Megafuck (manufactured by Dainippon Ink and Chemicals, Inc.), Florard (manufactured by Sumitomo 3M), and Asahigard under the following trade names.
- the blending amount of the surfactant is appropriately adjusted according to the type of the solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0 to 1% by mass of the total mass of the solid component. % Is more preferable, and 0% by mass is particularly preferable.
- the composition of the present embodiment may contain one or more additives other than the above-mentioned components, if necessary.
- additives include dyes, pigments, adhesive aids and the like.
- a dye or a pigment because the latent image of the exposed portion can be visualized and the influence of halation during exposure can be alleviated.
- an adhesive aid because the adhesiveness to the substrate and the layer in contact with the substrate can be improved.
- examples of other additives include anti-halation agents, storage stabilizers, antifoaming agents, shape improvers and the like, specifically 4-hydroxy-4'-methylchalcone and the like.
- the total amount of the arbitrary components can be 0 to 99% by mass, preferably 0 to 49% by mass, more preferably 0 to 10% by mass, and 0 to 0 to 99% by mass of the total mass of the solid components. 5% by mass is further preferable, 0 to 1% by mass is further preferable, and 0% by mass is particularly preferable.
- composition of the present embodiment is usually prepared by dissolving each component in a solvent at the time of use to obtain a uniform solution, and then, if necessary, filtering with a filter having a pore size of about 0.2 ⁇ m or the like. NS.
- composition of this embodiment is used for lithography applications. It is preferable that the composition is cured after forming a thin film to form a lower layer film or a film in contact with a resist layer (resist layer contact film).
- the composition of the present embodiment can form an amorphous film by spin coating. Moreover, the composition of this embodiment can be applied to a general semiconductor manufacturing process. After curing, the composition of the present embodiment generates protons by irradiation with extreme ultraviolet rays, and by supplying the protons to the adjacent layers, the sensitivity of the adjacent layers can be improved.
- the composition of the present embodiment is preferably cured before use. After curing, it is preferably solvent resistant so that it does not dissolve in the composition of the adjacent layer.
- a lower layer film forming step of forming a lower layer film using the composition on a substrate and a lower layer film formed by the lower layer film forming step are performed. It includes a photoresist film forming step of forming a one-layer photoresist film, and a step of irradiating a predetermined region of the photoresist film formed by the photoresist film forming step with radiation to develop the photoresist film.
- the lower layer film forming step of forming the lower layer film on the substrate and the lower layer film formed by the lower layer film forming step are carried out by using the composition.
- a pattern forming step of etching the resist layer contact film, or the resist layer contact film and the lower layer film to form a pattern, and etching the substrate using the pattern formed by the pattern forming step as a mask to form a pattern on the substrate. Includes a substrate pattern forming step to be formed.
- the storage stability of the composition containing the compound or resin is determined by allowing the composition containing the above-mentioned underlayer film composition to stand at 23 ° C. for 3 days to check for precipitation. It was evaluated by observing visually. Further, the composition was rotationally coated on a clean silicon wafer and then baked on a hot plate at 250 ° C. to form an amorphous film having a thickness of 100 nm. The prepared composition was evaluated as ⁇ when it was a uniform solution and the thin film formation was good, ⁇ when it was a uniform solution but the thin film had defects, and ⁇ when it had precipitation.
- Sensitivity evaluation EUV sensitivity-TMAH aqueous solution development
- a resist solution for sensitivity evaluation and pattern evaluation was prepared.
- the above underlayer film composition was applied onto a silicon wafer and baked at 240 ° C. for 60 seconds to form an underlayer film having a film thickness of 100 nm on the silicon wafer.
- a resist solution was applied onto the lower film of the present invention formed on a silicon wafer and baked at 110 ° C. for 60 seconds to form a photoresist layer having a film thickness of 100 nm.
- extreme ultraviolet (EUV) exposure apparatus "EUVES-7000" product name, Litho-made Tech Japan Co., Ltd.
- EUVES-7000 product name, Litho-made Tech Japan Co., Ltd.
- TMAH tetramethylammonium hydroxide
- etching test was carried out under the above conditions for a film formed on a silicon wafer using the underlayer film solution made of the material of the present invention prepared in each Example and Comparative Example, and the etching rate at that time was measured. Then, the etching resistance was evaluated according to the following evaluation criteria based on the etching rate of the underlayer film produced using Novolac (“PSM4357” manufactured by Gun Ei Chemical Industry Co., Ltd.). Evaluation Criteria A: The difference in etching rate is 10% or more smaller than the lower layer film of Novolac B: The difference in etching rate is less than ⁇ 10% of the lower layer film of Novolac C: The difference in etching rate compared to the underlayer of novolak is greater than 10% of the novolak ratio.
- Synthesis Example 1 Synthesis of BisB-1 In a container having an internal volume of 200 mL equipped with a stirrer, a cooling tube, and a burette, 25.0 g (204.7 mmol) of 2,6-dimethylphenol (reagent manufactured by Tokyo Kasei Co., Ltd.) was added. 25.0 g (107.7 mmol) of 4-iodobenzaldehyde (Tokyo Chemicals' reagent) and 20 mL of 1-methoxy-2-propanol were charged, and 5.3 g (53.9 mmol) of sulfuric acid was added to prepare a reaction solution. .. The reaction was carried out by stirring the reaction solution at 90 ° C. for 6 hours.
- Synthesis Example 2 Synthesis of BisB-2 42.8 g (230 mmol) of 4,4'-biphenol (reagent manufactured by Tokyo Kasei Co., Ltd.) and 3, 21.5 g (57.5 mmol) of 5-diiodosalicylaldehyde (Tokyo Kasei's reagent) and 428 mL of ⁇ -butyrolactone were charged, and 5.8 g (58 mmol) of sulfuric acid was added to prepare a reaction solution. The reaction was carried out by stirring the reaction solution at 90 ° C. for 56 hours.
- Synthesis Example 3 Synthesis of XbisN-1 7.0 g (40 mmol) of 2,6-naphthalenediol (a reagent manufactured by Sigma-Aldrich) and 3-iodobenzaldehyde in a container having an internal volume of 300 ml equipped with a stirrer, a cooling tube and a burette. (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.) 4.6 g (20 mmol) was charged into 100 ml of ⁇ -butyrolactone, 0.5 g of p-toluenesulfonic acid was added, and the reaction was carried out by stirring at 90 ° C. for 23 hours to carry out the reaction.
- the reaction solution was added to 1000 g of pure water, and then extracted and concentrated with ethyl acetate to obtain a solution.
- the obtained solution was separated by column chromatography and then washed with chloroform to obtain 4.2 g of the target compound (XbisN-1) represented by the following formula (XbisN-1).
- the molecular weight of the obtained compound (XbisN-1) was measured by the above method and found to be 516.
- the obtained compound (XbisN-1) was subjected to NMR measurement under the above measurement conditions, the following peaks were found, and it was confirmed that the compound (XbisN-1) had a chemical structure of the following formula (XbisN-1). ⁇ (ppm) 9.7 (2H, Oh), 7.0-8.5 (14H, Ph-H), 6.5 (1H, CH)
- Synthesis Example 4 Synthesis of BMI-1 Using a 200 mL glass flask as a reaction vessel, neopentyl glycol bis (4-aminophenyl) ether (product name: DANPG, manufactured by Wakayama Seika Kogyo Co., Ltd.) 5. After dissolving in 73 g (20 mmol) using butanol as a solvent, a 20 mass% iodine chloride aqueous solution (81.2 g, 100 mmol) was added dropwise at 50 ° C. over 60 minutes, and then the mixture was stirred at 50 ° C. for 2 hours. Was carried out, and salicyl alcohol was reacted with iodine chloride.
- the compound (X) obtained above was transferred to a container having an internal volume of 200 ml equipped with a stirrer, a cooling tube and a burette, and 2.54 g (26.0 mmol) of maleic anhydride (manufactured by Kanto Chemical Co., Ltd.). 50 ml of dimethylformamide and 50 ml of m-xylene were charged, and 0.5 g (2.9 mmol) of p-toluenesulfonic acid was added to prepare a reaction solution. This reaction solution was stirred at 130 ° C. for 4.0 hours to carry out a reaction, and the produced water was recovered by Dean-Stark trap by azeotropic dehydration. Next, the reaction solution was cooled to 40 ° C.
- Synthesis Example 5 Synthesis of XBisN-2 32.0 g (20 mmol) of 2,6-naphthalenediol (reagent manufactured by Sigma-Aldrich) and 3, Add 29.9 g (80 mmol) of 5-diiodosalicyylaldehyde (reagent manufactured by Tokyo Kasei Co., Ltd.) and 200 mL of 1,4-dioxane, add 10 mL of 95% sulfuric acid, and stir at 100 ° C. for 6 hours to react. went.
- Synthesis Example 5-1 Synthesis of RXBisN-2 2.6 g (7.0 mmol) of XBisN-2 and 1.0 g (monobutyl phthalate) of copper phthalate in a container having an internal volume of 100 mL equipped with a stirrer, a cooling tube and a burette. 2 mmol) was charged, 20 mL of 1-butanol was added as a solvent, and the reaction solution was stirred at 100 ° C. for 6 hours to carry out the reaction. After cooling, the precipitate was filtered and the resulting crude was dissolved in 20 mL of ethyl acetate.
- Synthesis Example 6 Synthesis of NAFP-AL Under nitrogen, 1,4-bis (chloromethyl) benzene (28.8 g, 0.148 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-naphthol (1-naphthol) in a 300 mL four-necked flask. 30.0 g, 0.1368 mol, manufactured by Tokyo Chemical Industry Co., Ltd., paratoluenesulfonic acid monohydrate (5.7 g, 0.029 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) is added, and propylene glycol monomethyl ether is further added.
- Synthesis Example 6-1 Synthesis of I-NAFP-AL After using a 200 mL glass flask as a reaction vessel and dissolving 8 g (20 mmol) of NAFP-AL obtained above with butanol as a solvent. , A 20 mass% iodine chloride aqueous solution (81.2 g, 100 mmol) was added dropwise at 50 ° C. over 60 minutes, and then stirring was performed at 50 ° C. for 2 hours to react salicyl alcohol with iodine chloride. An aqueous sodium thiosulfate solution was added to the reaction solution after the reaction, and the mixture was stirred for 1 hour, and then the liquid temperature was cooled to 10 ° C. The precipitate precipitated by cooling was filtered off, washed and dried to obtain 11.5 g of a brown solid.
- Synthesis Example 7 Synthesis of 2I-PHS A 200 mL glass flask was used as a reaction vessel, dissolved in 4.96 g (40 mmol) of salicyl alcohol using butanol as a solvent, and then 20% by mass at 50 ° C. An aqueous solution of iodine chloride (81.2 g, 100 mmol) was added dropwise over 60 minutes, and then stirring was performed at 50 ° C. for 2 hours to react salicyl alcohol with iodine chloride. An aqueous sodium thiosulfate solution was added to the reaction solution after the reaction, and the mixture was stirred for 1 hour, and then the liquid temperature was cooled to 10 ° C.
- the obtained organic phase is further washed with a 2 mol / L sodium carbonate aqueous solution, water, and saline solution in this order by a liquid separation operation, filtered, and the solvent is distilled off from the organic phase to obtain the following formula (2I-PHS). ), The compound 2I-PHS (4-hydroxy-3,5-diiodostyrene 8.1 g) was obtained.
- Synthesis Example 7-1 Synthesis of P-2I-PHS-MMA 3.0 g of compound 2I-PHS and 1.2 g of methyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was dissolved. Was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain a white powdery polymer P-2I-PHS-MMA represented by the following formula (P-2I-PHS-MMA). The weight average molecular weight (Mw) of this polymer was 8000, and the dispersity (Mw / Mn) was 1.50.
- Mw weight average molecular weight
- Mn dispersity
- the following formula (P-2I-PHS-MMA) is simply described to indicate the ratio of each structural unit, but the arrangement order of each structural unit is random, and each structural unit is independent. It is not a block copolymer forming the block.
- Synthesis Example 8 Synthesis of XBisN-3 100 g of a compound (XBisN-C1) represented by the following formula described in International Publication 2013/024779 in a container having an internal volume of 3 L equipped with a stirrer, a cooling tube and a burette. (0.214 mol) and 71.2 g (0.429 mol) of potassium iodide were charged, 1 L of methanol was added as a solvent, and 146 g (1.5 mol) of sulfuric acid was further added dropwise under ice-cooling, and the mixture was stirred at 10 ° C. for 4 hours. And reacted.
- XBisN-3 100 g of a compound (XBisN-C1) represented by the following formula described in International Publication 2013/024779 in a container having an internal volume of 3 L equipped with a stirrer, a cooling tube and a burette. (0.214 mol) and 71.2 g (0.429 mol) of potassium iodide were charged, 1
- Synthesis Example 9-1 Synthesis of MAC-ADI 16.8 g (0.1 mol) of 1,3-adamantandiol (manufactured by Mitsubishi Gas Chemical Company) was dissolved in 200 mL of toluene, and 89.8 g (0) of a 57% aqueous hydrogen iodide solution was dissolved. .4 mol) was added, and the mixture was stirred at 80 ° C. for 8 hours to react. After the reaction, water was added, the mixture was washed with sodium hydrogencarbonate, the organic layer was concentrated, and then separated and purified by column chromatography to obtain 12 g of 3-iodo-1-hydroxyadamantane represented by the following formula.
- Synthesis Example 10-1 Synthesis of MAC-ADI2 2.3 g (12.5 mmol) of 1,3,5-adamantane triol (manufactured by Mitsubishi Gas Chemical Company) was dissolved in 100 mL of toluene, and 28.1 g of a 57% aqueous hydrogen iodide solution was dissolved. (125 mmol) was added, and the mixture was stirred and reacted at 80 ° C. for 13 hours. After the reaction, water is added, the mixture is washed with sodium hydrogencarbonate, the organic layer is concentrated, and then separated and purified by column chromatography to obtain 0.9 g of 3,5-diiodo-1-hydroxyadamantane represented by the following formula. Obtained.
- Synthesis Example 9 Synthesis of P-MAC-ADI resin MAC-ADI (4.2 g), 2-methyl-2-adamantyl methacrylate 1.5 g, ⁇ -butyrolactone methacrylic acid ester 2.0 g, and hydroxyadamantyl methacrylate 1.5 g of the ester was dissolved in 45 mL of tetrahydrofuran and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 liters of n-heptane. The precipitated resin was separated by filtration and dried under reduced pressure to obtain a white powdery resin represented by the following chemical formula (P-MAC-ADI).
- the molecular weight (Mw) of this resin was 9300, and the dispersity (Mw / Mn) was 1.9.
- the following chemical formula (P-MAC-ADI) is simply described to indicate the ratio of each structural unit, but in P-MAC-ADI, each structural unit forms an independent block. It is not a block copolymer.
- Synthesis Example 10 Synthesis of P-MAC-ADI2 resin MAC-ADI2 (5.6 g), 2-methyl-2-adamantyl methacrylate 1.5 g, ⁇ -butyrolactone methacrylic acid ester 2.0 g, and hydroxyadamantyl methacrylic acid. 1.5 g of the ester was dissolved in 45 mL of tetrahydrofuran and 0.20 g of azobisisobutyronitrile was added. After refluxing for 12 hours, the reaction solution was added dropwise to 2 liters of n-heptane. The precipitated resin was separated by filtration and dried under reduced pressure to obtain a white powdery resin represented by the following chemical formula (P-MAC-ADI2).
- the molecular weight (Mw) of this resin was 8350, and the dispersity (Mw / Mn) was 2.0.
- the following chemical formula (P-MAC-ADI2) is simply described to indicate the ratio of each structural unit, but in P-MAC-ADI2, each structural unit forms an independent block. It is not a block copolymer.
- Synthesis Comparative Example AR1 Synthesis of P-PHS-MMA 1.0 g of the compound p-hydroxystyrene and 1.2 g of methyl methacrylate were dissolved in 45 mL of tetrahydrofuran, and 0.20 g of azobisisobutyronitrile was added. .. After refluxing for 12 hours, the reaction solution was added dropwise to 2 L of n-heptane. The precipitated polymer was separated by filtration and dried under reduced pressure to obtain a white powdery polymer P-PHS-MMA represented by the following formula (P-PHS-MMA). The weight average molecular weight (Mw) of this polymer was 9100, and the dispersity (Mw / Mn) was 1.60.
- Mw weight average molecular weight
- P-PHS-MMA The following equation (P-PHS-MMA) is simply described to indicate the ratio of each structural unit, but the arrangement order of each structural unit is random, and each structural unit is an independent block. It is not a block copolymer forming.
- the precipitated polymer was separated by filtration and dried under reduced pressure to obtain a white powdery polymer MAR1 represented by the following formula (MAR1).
- the weight average molecular weight (Mw) of this polymer was 1,2000, and the dispersity (Mw / Mn) was 1.90.
- the following equation (MAR1) is simply described to indicate the ratio of each structural unit, but the arrangement order of each structural unit is random, and each structural unit forms an independent block. It is not a block copolymer.
- the polystyrene-based monomer (p-hydroxystyrene) is the carbon at the base of the benzene ring, and the methacrylate-based monomer (2-methyl-2-adamantyl methacrylate, ⁇ -butyrolactone methacrylic acid ester, and hydroxyadamantyl methacrylic acid ester) is an ester bond.
- the molar ratio of carbonyl carbon was determined based on the respective integration ratios.
- the precipitated polymer was separated by filtration and dried under reduced pressure to obtain a white powdery polymer MAR2 represented by the following formula (MAR2).
- the weight average molecular weight (Mw) of this polymer was 1,2000, and the dispersity (Mw / Mn) was 1.90.
- the following equation (MAR2) is simply described to indicate the ratio of each structural unit, but the arrangement order of each structural unit is random, and each structural unit forms an independent block. It is not a block copolymer.
- the polystyrene-based monomer (p-hydroxystyrene) is the carbon at the base of the benzene ring, and the methacrylate-based monomer (2-methyl-2-adamantyl methacrylate, ⁇ -butyrolactone methacrylic acid ester, and hydroxyadamantyl methacrylic acid ester) is an ester bond.
- the molar ratio of carbonyl carbon was determined based on the respective integration ratios.
- the components used in the preparation of the underlayer membrane composition solution are as follows.
- ⁇ Acid diffusion control agent> The following were used as acid diffusion promoters.
- ⁇ WPAG199 (Bis (4-methylphenylsulfonyl) diazomehtane) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
- WPAG367 (Diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
- WPAG336 Diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
- Sensitivity evaluation (EUV sensitivity-n-butyl acetate development) 5 parts by mass, 1 part by mass of triphenylsulfonium nonafluoromethanesulfonate, 0.2 part by mass of tributylamine, 80 parts by mass of PGMEA, and 12 parts by mass of PGME are blended with the polymer MAR2 obtained in the above-mentioned example of polymer synthesis for resist.
- a resist solution 2 for sensitivity evaluation and pattern evaluation was prepared.
- the prepared underlayer film composition was applied onto a silicon wafer and baked at 240 ° C. for 60 seconds to form an underlayer film having a film thickness of 100 nm on the silicon wafer.
- the resist solution 2 was applied onto the lower film of the present invention formed on a silicon wafer and baked at 110 ° C. for 60 seconds to form a photoresist layer having a film thickness of 100 nm.
- extreme ultraviolet (EUV) exposure apparatus "EUVES-7000" product name, Litho-made Tech Japan Co., Ltd.
- EUVES-7000 product name, Litho-made Tech Japan Co., Ltd.
- the wafer was baked (PEB) at 110 ° C. for 90 seconds, developed with n-butyl acetate for 30 seconds, and 80 shots of shot exposure was performed on the wafer to obtain a wafer.
- the film thickness was measured with an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.), profile data of the film thickness with respect to the exposure amount was acquired, and the film thickness with respect to the exposure amount was obtained.
- the exposure amount at which the gradient of the film thickness fluctuation amount was the largest was calculated as a sensitivity value (mJ / cm 2 ) and used as an index of the EUV sensitivity of the resist.
- the prepared underlayer film composition was applied onto a silicon wafer and baked at 240 ° C. for 60 seconds to form an underlayer film having a film thickness of 100 nm on the silicon wafer. Further, a resist solution was applied onto the lower film of the present invention formed on a silicon wafer and baked at 110 ° C. for 60 seconds to form a photoresist layer having a film thickness of 100 nm.
- EUV extreme ultraviolet
- EUVES-7000 product name, manufactured by Litho Tech Japan Corporation
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Abstract
Description
この中でも、特に極端紫外線によるリソグラフィーは、近年の技術進展により導入例が増加している。
従来においては、これらレジスト材料の溶液を基板上に塗布することによって作製したレジスト薄膜に、紫外線、遠紫外線、電子線、極端紫外線などを照射することで、10~100nm程度のラインパターンを形成している。
上述のような問題を改善するレジスト材料としては、チタン、スズ、ハフニウムやジルコニウム等の金属元素を有する無機レジスト材料が提案されている(例えば、特許文献1参照)。
すなわち、本発明は次のとおりである。
ヨウ素、テルル及びフッ素からなる群から選択される少なくとも1種の元素を有する化合物、又は前記化合物に由来する構成単位を有する樹脂を含む、リソグラフィー用組成物であって、
前記化合物中における前記原子の合計質量が、15質量%以上75質量%以下である、前記リソグラフィー用組成物。
[2]
前記少なくとも1種の元素が、ヨウ素及びテルルからなる群から選択される少なくとも1種の元素である、[1]に記載のリソグラフィー用組成物。
[3]
前記少なくとも1種の元素がヨウ素であり、前記化合物中における前記ヨウ素の質量が、15質量%以上75質量%以下である、[1]又は[2]に記載のリソグラフィー用組成物。
[4]
前記化合物が、式(A-4a)で表される、[1]~[3]のいずれかに記載のリソグラフィー用組成物。
Xは酸素原子、硫黄原子、単結合又は無架橋であることを示し、
Yは炭素数1~60の2n価の基又は単結合であり、
ここで、Xが無架橋であるとき、Yは前記2n価の基であり、
R0は各々独立して、置換基を有していてもよい炭素数1~40のアルキル基、置換基を有していてもよい炭素数6~40のアリール基、置換基を有していてもよい炭素数2~40のアルケニル基、置換基を有していてもよい炭素数2~40のアルキニル基、置換基を有していてもよい炭素数1~40のアルコキシ基、ハロゲン原子、チオール基又は水酸基であり、
ここで、R0の少なくとも1つは水酸基であり、
mは各々独立して1~9の整数であり、
Qはヨウ素、テルル、フッ素、又はヨウ素若しくはテルル若しくはフッ素を少なくとも含む炭素数1~30のアルキル基、又はヨウ素若しくはテルル若しくはフッ素を少なくとも含む炭素数6~40のアリール基を表し、
nは1~4の整数であり、
pは各々独立して0~3の整数であり、
Q、R0、Yの少なくとも一つは、ヨウ素、テルル、フッ素の少なくとも1つの元素を含み、
qは各々独立して0~(4+2×p-m)の整数である。)
[4-1]
Xが、酸素原子又は無架橋である、[4]に記載のリソグラフィー用組成物。
[4-2]
Qが、ヨウ素である、[4]又は[4-1]に記載のリソグラフィー用組成物。
[4-3]
Q、R0、Yの少なくとも一つが、ヨウ素を含む、[4]~[4-2]のいずれかに記載のリソグラフィー用組成物。
[4-4]
qが、各々独立して1~(4+2×p-m)の整数である、[4]~[4-3]のいずれかに記載のリソグラフィー用組成物。
[5]
Yが、置換基を有していてもよい炭素数6~60のアリール基を有する2n価の炭化水素基である、[4]~[4-4]のいずれかに記載のリソグラフィー用組成物。
[5-1]
前記2n価の炭化水素基が、メチレン基である、[5]に記載のリソグラフィー用組成物。
[5-2]
前記炭素数6~60のアリール基が、フェニル基又はビフェニル基である、[5]又は[5-1]に記載のリソグラフィー用組成物。
[5-3]
前記置換基が、ヨウ素である、[5]~[5-2]のいずれかに記載のリソグラフィー用組成物。
[6]
前記化合物が、式(A-4c)で表される、[1]~[3]のいずれかに記載のリソグラフィー用組成物。
Xは酸素原子、硫黄原子、単結合又は無架橋であることを示し、
Yは炭素数1~60の2n価の基又は単結合であり、
ここで、Xが無架橋であるとき、Yは前記2n価の基であり、
R0は各々独立して、置換基を有していてもよい炭素数1~40のアルキル基、置換基を有していてもよい炭素数6~40のアリール基、置換基を有していてもよい炭素数2~40のアルケニル基、置換基を有していてもよい炭素数2~40のアルキニル基、置換基を有していてもよい炭素数1~40のアルコキシ基、ハロゲン原子、チオール基又は水酸基であり、
ここで、R0の少なくとも1つは水酸基であり、
R0の少なくとも1つはヨウ素、又はヨウ素を含有する基であり、
mは各々独立して1~9の整数であり、
nは1~4の整数であり、
pは各々独立して0~3の整数である。)
[6-1]
Xが、酸素原子又は無架橋である、[6]に記載のリソグラフィー用組成物。
[7]
Yが、置換基を有していてもよい炭素数6~60のアリール基を有する2n価の炭化水素基である、[6]又は[6-1]のいずれかに記載のリソグラフィー用組成物。
[7-1]
前記2n価の炭化水素基が、メチレン基である、[7]に記載のリソグラフィー用組成物。
[7-2]
前記炭素数6~60のアリール基が、フェニル基又はビフェニル基である、[7]又は[7-1]に記載のリソグラフィー用組成物。
[7-3]
前記置換基が、ヨウ素である、[7]~[7-2]のいずれかに記載のリソグラフィー用組成物。
[8]
前記化合物が一般式(AM1)で表される、[1]~[3]のいずれかに記載のリソグラフィー用組成物。
R1は、水素原子、メチル、又はハロゲン基を表し、
R2は、それぞれ独立して、水素原子、炭素数1~20の直鎖状の有機基、炭素数3~20の分岐状の有機基、又は炭素数3~20の環状の有機基を表し、
Aは、炭素数1~30の有機基を表し、
n1は0又は1を表し、
n2は1~20の整数を表す。)
[8-1]
R1が、メチルである、[8]に記載のリソグラフィー用組成物。
[8-2]
n1が0である、[8]又は[8-1]に記載のリソグラフィー用組成物。
[8-3]
Aが、脂環式炭化水素基である、[8]~[8-2]のいずれかに記載のリソグラフィー用組成物。
[8-4]
Aが、アダマンチル基である、[8]~[8-3]のいずれかに記載のリソグラフィー用組成物。
[9]
前記化合物が一般式(A-7)で表される、[1]~[3]のいずれかに記載のリソグラフィー用組成物。
Xは、それぞれ独立して、テルル、I、F、又は、テルル、I、及びFからなる群から選ばれる1以上5以下の置換基を有する炭素数1~30の有機基を表し、かつXの少なくとも1つはテルル又はIであり、
L1は、単結合、エーテル基、エステル基、チオエーテル基、アミノ基、チオエステル基、アセタール基、ホスフィン基、ホスフォン基、ウレタン基、ウレア基、アミド基、イミド基、又はリン酸基を表し、
mは1以上の整数であり、
Yは、それぞれ独立して、水酸基、アルコキシ基、エステル基、アセタール基、炭酸エステル基、ニトロ基、アミノ基、カルボキシル基、チオール基、エーテル基、チオエーテル基、ホスフィン基、ホスフォン基、ウレタン基、ウレア基、アミド基、イミド基、又はリン酸基を表し、
nは、0以上の整数であり、
Zは、それぞれ独立して、アルコキシ基、エステル基、アセタール基、又は炭酸エステル基であり、
rは、0以上の整数であり、
Aは、炭素数1~30の有機基であり、
Ra、Rb、及びRcは、それぞれ独立して、H、I、F、Cl、Br、又は、置換基を有していてもよい炭素数1~60の有機基であり
pは、1以上の整数である。)
[9-1]
Xが、ヨウ素である、[9]に記載のリソグラフィー用組成物。
[9-2]
L1が、単結合である、[9]又は[9-1]に記載のリソグラフィー用組成物。
[9-3]
Yが、水酸基であり、nが、1以上の整数である、[9]~[9-2]のいずれかに記載のリソグラフィー用組成物。
[9-4]
rが、0である、[9]~[9-3]のいずれかに記載のリソグラフィー用組成物。
[9-5]
Aが、炭素数6~14の芳香環である、[9]~[9-4]のいずれかに記載のリソグラフィー用組成物。
[9-6]
Ra、Rb、及びRcが、水素である、[9]~[9-5]のいずれかに記載のリソグラフィー用組成物。
[10]
溶媒をさらに含有する、[1]~[9-6]のいずれかに記載のリソグラフィー用組成物。
[11]
酸発生剤をさらに含有する、[1]~[10]のいずれかに記載のリソグラフィー用組成物。
[12]
酸拡散促進剤をさらに含有する、[1]~[11]のいずれかに記載のリソグラフィー用組成物。
[13]
酸拡散抑制剤をさらに含有する、[1]~[12]のいずれかに記載のリソグラフィー用組成物。
[14]
架橋剤をさらに含有する、[1]~[13]のいずれかに記載のリソグラフィー用組成物。
[15]
薄膜形成後に硬化される、[1]~[14]のいずれかに記載のリソグラフィー用組成物。
[16]
レジスト層接触膜を形成するための、[1]~[15]のいずれかに記載のリソグラフィー用組成物。
[17]
下層膜を形成するための、[1]~[15]のいずれかに記載のリソグラフィー用組成物。
[18]
基板上に、[17]に記載のリソグラフィー用組成物を用いて下層膜を形成する下層膜形成工程と、
該下層膜形成工程により形成した下層膜上に、少なくとも1層のフォトレジスト膜を形成するフォトレジスト膜形成工程と、
該フォトレジスト膜形成工程により形成したフォトレジスト膜の所定の領域に放射性を照射し、現像を行う工程と、
を含む、レジストパターン形成方法。
[19]
基板上に、下層膜を形成する下層膜形成工程と、
該下層膜形成工程により形成した下層膜上に、[16]に記載のリソグラフィー用組成物を用いて、レジスト層接触膜を形成する、レジスト層接触膜形成工程と、
該レジスト層接触膜形成工程により形成したレジスト層接触膜上に、少なくとも1層のフォトレジスト膜を形成するフォトレジスト膜形成工程と、
該フォトレジスト膜形成工程により形成したフォトレジスト膜の所定の領域に放射線を照射し、現像してレジストパターンを形成するレジストパターン形成工程と、
該レジストパターン形成工程により形成したレジストパターンをマスクとして、前記レジスト層接触膜、または前記レジスト層接触膜及び前記下層膜をエッチングしてパターンを形成するパターン形成工程と、
該パターン形成工程により形成したパターンをマスクとして前記基板をエッチングして基板にパターンを形成する基板パターン形成工程と、
を含む、回路パターン形成方法。
[20]
式(A-4a)で表される化合物。
Xは酸素原子、硫黄原子、単結合又は無架橋であることを示し、
Yは炭素数1~60の2n価の基又は単結合であり、
ここで、Xが無架橋であるとき、Yは前記2n価の基であり、
R0は各々独立して、置換基を有していてもよい炭素数1~40のアルキル基、置換基を有していてもよい炭素数6~40のアリール基、置換基を有していてもよい炭素数2~40のアルケニル基、置換基を有していてもよい炭素数2~40のアルキニル基、置換基を有していてもよい炭素数1~40のアルコキシ基、ハロゲン原子、チオール基又は水酸基であり、
ここで、R0の少なくとも1つは水酸基であり、
mは各々独立して1~9の整数であり、
Qはヨウ素、テルル、フッ素、又はヨウ素若しくはテルル若しくはフッ素を少なくとも含む炭素数1~30のアルキル基、又はヨウ素若しくはテルル若しくはフッ素を少なくとも含む炭素数6~40のアリール基を表し、
nは1~4の整数であり、
pは各々独立して0~3の整数であり、
Q、R0、Yの少なくとも一つは、ヨウ素、テルル、フッ素の少なくとも1つの元素を含み、
qは各々独立して0~(4+2×p-m)の整数である。)
[20-1]
Xが、酸素原子又は無架橋である、[20]に記載の化合物。
[20-2]
Qが、ヨウ素である、[20]又は[20-1]に記載の化合物。
[20-3]
Q、R0、Yの少なくとも一つが、ヨウ素を含む、[20]~[20-2]のいずれかに記載の化合物。
[20-4]
qが、各々独立して1~(4+2×p-m)の整数である、[20]~[20-3]のいずれかに記載の化合物。
[21]
Yが、置換基を有していてもよい炭素数6~60のアリール基を有する2n価の炭化水素基である、[20]~[20-4]のいずれかに記載の化合物。
[21-1]
前記2n価の炭化水素基が、メチレン基である、[21]に記載の化合物。
[21-2]
前記炭素数6~60のアリール基が、フェニル基又はビフェニル基である、[21]又は[21-1]に記載の化合物。
[21-3]
前記置換基が、ヨウ素である、[21]~[21-2]のいずれかに記載の化合物。
[22]
式(A-4c)で表される化合物。
Xは酸素原子、硫黄原子、単結合又は無架橋であることを示し、
Yは炭素数1~60の2n価の基又は単結合であり、
ここで、Xが無架橋であるとき、Yは前記2n価の基であり、
R0は各々独立して、置換基を有していてもよい炭素数1~40のアルキル基、置換基を有していてもよい炭素数6~40のアリール基、置換基を有していてもよい炭素数2~40のアルケニル基、置換基を有していてもよい炭素数2~40のアルキニル基、置換基を有していてもよい炭素数1~40のアルコキシ基、ハロゲン原子、チオール基又は水酸基であり、
ここで、R0の少なくとも1つは水酸基であり、
R0の少なくとも1つはヨウ素、又はヨウ素を含有する基であり、
mは各々独立して1~9の整数であり、
nは1~4の整数であり、
pは各々独立して0~3の整数である。)
[22-1]
Xが、酸素原子又は無架橋である、[22]に記載の化合物。
[23]
Yが、置換基を有していてもよい炭素数6~60のアリール基を有する2n価の炭化水素基である、[22]又は[22-1]に記載の化合物。
[23-1]
前記2n価の炭化水素基が、メチレン基である、[23]に記載の化合物。
[23-2]
前記炭素数6~60のアリール基が、フェニル基又はビフェニル基である、[23]又は[23-1]に記載の化合物。
[23-3]
前記置換基が、ヨウ素である、[23]~[23-2]のいずれかに記載の化合物。
本実施形態に係る化合物(以下、「化合物(A)」ともいう。)、及び前記化合物に由来する構成単位を有する樹脂(以下、「樹脂(A)」ともいう。)は、ヨウ素、テルル及びフッ素からなる群(好ましくは、ヨウ素及びテルルからなる群)から選択される少なくとも1種の元素を有する。ヨウ素及びテルルは極端紫外線の吸収能力が高いため、極端紫外線を吸収して化合物(A)をイオン化し、効率よくプロトンを生成することができる。
ヨウ素及びテルルの合計含有量が15質量%以下であると極端紫外線の吸収能力が低くなるため、プロトンの生成効率が低くなる。また、ヨウ素及びテルルの合計含有量が75質量%以上であると、化合物の安定性が低くなり、分解しやすくなる。
また、化合物(A)は基板やレジスト層との密着性の観点から、水酸基などの親水性基を含有していることも好ましい。
また、「重合性基」とは、触媒存在下、又は無触媒下で重合する基をいう。重合性基としては、特に限定されないが、例えば、(メタ)アクリル基を有する基、ビニル基など不飽和二重結合を有する基、プロパギル基などの不飽和三重結合を有する基が挙げられる。
「解離性基」とは、触媒存在下、又は無触媒下で解離する基をいう。解離性基の中でも、酸解離性基とは、酸の存在下で開裂して、アルカリ可溶性基等に変化する特性基をいう。酸解離性基の具体例としては、国際公開第2016/158168号に記載のものを挙げることができる。酸解離性基の好ましい例としては、酸により解離する性質を有する、1-置換エチル基、1-置換-n-プロピル基、1-分岐アルキル基、シリル基、アシル基、1-置換アルコキシメチル基、環状エーテル基、アルコキシカルボニル基及びアルコキシカルボニルアルキル基からなる群より選ばれる基が挙げられる。
本実施形態における多環ポリフェノール樹脂は、以下に限定されないが、典型的には、下記(1)~(5)の特性を有する。
(1)本実施形態における多環ポリフェノール樹脂は、有機溶媒(特に安全溶媒)に対する優れた溶解性を有する。このため、例えば、本実施形態における多環ポリフェノール樹脂をリソグラフィー用膜形成材料として用いると、スピンコート法やスクリーン印刷等の湿式プロセスによりリソグラフィー用膜を形成できる。
(2)本実施形態における多環ポリフェノール樹脂では、炭素濃度が比較的高く、酸素濃度が比較的低い。また、分子中にフェノール性水酸基を有するため、硬化剤との反応による硬化物の形成に有用であるが、単独でも高温ベーク時にフェノール性水酸基が架橋反応することにより硬化物を形成できる。これらに起因して、本実施形態における多環ポリフェノール樹脂は、高い耐熱性を発現でき、リソグラフィー用膜形成材料として用いると、高温ベーク時の膜の劣化が抑制され、酸素プラズマエッチング等に対するエッチング耐性に優れたリソグラフィー用膜を形成できる。
(3)本実施形態における多環ポリフェノール樹脂は、上記のように、高い耐熱性及びエッチング耐性を発現できるとともに、レジスト層やレジスト中間層膜材料との密着性に優れる。このため、リソグラフィー用膜形成材料として用いると、レジストパターン形成性に優れたリソグラフィー用膜を形成できる。なお、ここでいう「レジストパターン形成性」とは、レジストパターン形状に大きな欠陥が見られず、解像性及び感度ともに優れる性質をいう。
(4)本実施形態における多環ポリフェノール樹脂は、芳香環密度が高いため高屈折率であり、また低温から高温までの広範囲の熱処理によっても着色が抑制され、透明性に優れることから、各種光学部品形成材料としても有用である。
(5)本実施形態における多環ポリフェノール樹脂は、官能基としてQを有することで、EUV露光光源に対する吸収率を向上することができ、リソグラフィー用の下層膜として使用した場合における、感度向上、およびパターン倒れ等のパターン欠陥の抑制により生産性の向上に繋げることができる。
式(A-4a)中、Xは酸素原子、硫黄原子、単結合又は無架橋であることを示す。Xとしては、耐熱性の観点から、酸素原子が好ましい。
炭素数1~60の2n価の基とは、例えば、2n価の炭化水素基であり、当該炭化水素基は、置換基として、後述する種々の官能基を有するものであってもよい。また、2n価の炭化水素基は、n=1のときには、炭素数1~60のアルキレン基、n=2のときには、炭素数1~60のアルカンテトライル基、n=3のときには、炭素数2~60のアルカンヘキサイル基、n=4のときには、炭素数3~60のアルカンオクタイル基のことを示す。該2n価の炭化水素基としては、例えば、2n+1価の炭化水素基と、直鎖状炭化水素基、分岐状炭化水素基又は脂環式炭化水素基とが結合した基等が挙げられる。ここで、脂環式炭化水素基については、有橋脂環式炭化水素基も含まれる。
2n+1価の炭化水素基としては、以下に限定されないが、例えば、3価のメチン基、エチン基等が挙げられる。
また、前記2n価の炭化水素基は、二重結合、ヘテロ原子及び/又は炭素数6~59のアリール基を有していてもよい。なお、Yはフルオレンやベンゾフルオレン等のフルオレン骨格を有する化合物に由来する基を含んでいてもよいが、本明細書中、「アリール基」との用語は、フルオレンやベンゾフルオレン等のフルオレン骨格を有する化合物に由来する基を含まないものとして用いる。
2n価の基に含まれ得る置換基であって、脂環式炭化水素基および炭素数6~60の芳香族基としては、特に限定されないが、例えば、無置換のフェニル基、ナフタレン基、ビフェニル基、アントラシル基、ピレニル基、シクロヘキシル基、シクロドデシル基、ジシクロペンチル基、トリシクロデシル基、アダマンチル基、フェニレン基、ナフタレンジイル基、ビフェニルジイル基、アントラセンジイル基、ピレンジイル基、シクロヘキサンジイル基、シクロドデカンジイル基、ジシクロペンタンジイル基、トリシクロデカンジイル基、アダマンタンジイル基、ベンゼントリイル基、ナフタレントリイル基、ビフェニルトリイル基、アントラセントリイル基、ピレントリイル基、シクロヘキサントリイル基、シクロドデカントリイル基、ジシクロペンタントリイル基、トリシクロデカントリイル基、アダマンタントリイル基、ベンゼンテトライル基、ナフタレンテトライル基、ビフェニルテトライル基、アントラセンテトライル基、ピレンテトライル基、シクロヘキサンテトライル基、シクロドデカンテトライル基、ジシクロペンタンテトライル基、トリシクロデカンテトライル基、アダマンタンテトライル基等が挙げられる。
ここで、R0の少なくとも1つは水酸基である。
炭素数6~40のアリール基としては、以下に限定されないが、例えば、フェニル基、ナフタレン基、ビフェニル基、アントラシル基、ピレニル基、ペリレン基等が挙げられる。
炭素数2~40のアルケニル基としては、以下に限定されないが、例えば、エチニル基、プロペニル基、ブチニル基、ペンチニル基等が挙げられる。
炭素数2~40のアルキニル基としては、以下に限定されないが、例えば、アセチレン基、エチニル基等が挙げられる。
炭素数1~40のアルコキシ基としては、以下に限定されないが、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペントキシ等が挙げられる。
Ar0は、各々独立に、同一の基でも異なる基でもよく、フェニレン基、ナフチレン基、アントリレン基、フェナンスリレン基、ピリレン基、フルオリレン基、ビフェニレン基、又はターフェニレン基、を含む2価の基を表し;
R0は、各々独立に、同一の基でも異なる基でもよく、置換基を有していてもよい炭素数1~30のアルキル基、又は置換基を有していてもよいアリール基、ヨウ素、テルル、フッ素、またはヨウ素またはテルルまたはフッ素を少なくとも含む炭素数1~30のアルキル基、アリール基を表し;
nは1~50の整数を表し;
r0は、各々独立に、0~3の整数を表し;
pは、各々独立に、0以上の整数を表す。但し、全てのr0が同時に0になることはない。また、全てのpが同時に0になることはない。またR0のうち少なくとも一つはヨウ素、テルル、フッ素のいずれかを含む。)
Ar0として具体的には、1,4-フェニレン基、1,3-フェニレン基、4,4’-ビフェニレン基、2,4’-ビフェニレン基、2,2’-ビフェニレン基、2,3’-ビフェニレン基、3,3’-ビフェニレン基、3,4’-ビフェニレン基、2,6-ナフチレン基、1,5-ナフチレン基、1,6-ナフチレン基、1,8-ナフチレン基、1,3-ナフチレン基、1,4-ナフチレン基、アントリレン基、フェナントリレン基、又はピリレン基、フルオリレン基、ターフェニレン基等が挙げられる。また、前記Ar0としては、ジフェニルメチル構造、ビスフェノール構造、又は、ビス(ヒドロキシフェニル)ジイソプロピルフェニル構造、を含む二価の基など複数のフェニレン基等がアルキレン基等で連結された二価の基も含まれる。
R0はAr0の置換基であり、各々独立に、同一の基でも異なる基でもよく、置換基を有していてもよい炭素数1~30のアルキル基、又は置換基を有していてもよいアリール基を表す。R0の具体例としては、後述するRa及びRbの具体例が挙げられる。
R1は、水素原子又はメチル基またはハロゲン基を表し、
R2は、それぞれ独立して、水素原子、炭素数1~20の直鎖状の有機基、炭素数3~20の分岐状の有機基、又は炭素数3~20の環状の有機基を表し、
Aは、炭素数1~30の有機基を表し、
Qは、各々独立して、ヨウ素、テルル、フッ素、またはヨウ素またはテルルまたはフッ素を少なくとも含む炭素数1~30のアルキル基、アリール基を表し、好ましくは、Qはヨウ素であり、
n1は0又は1を表し、
n2は1~20の整数を表す。
Xは、それぞれ独立して、テルル、I、F、Cl、Br、又は、テルル、I、F、Cl、及びBrからなる群から選ばれる1以上5以下の置換基を有する炭素数1~30の有機基である。Xの少なくとも1つはテルル又はIである。
L2は、酸の作用により開裂する基である。酸の作用により開裂する基としては、例えば、エステル基[*1-O-(C=O)-*2又は*1-(C=O)-O-*2]、アセタール基[*1-O-(C(R21)2)-O-*2(R21は、それぞれ独立にH、又は、炭素数1~10の炭化水素基である。)]、カルボキシアルコキシ基[*1-O-R22-(C=O)-O-*2(R22は、炭素数1~10の2価の炭化水素基である。)]、及び炭酸エステル基[*1-O-(C=O)-O-*2]からなる群より選ばれる少なくとも1種の2価の連結基が挙げられる。なお、式中、*1は、Aとの結合部位、*2は、R2との結合部位である。これらの中でも、L2は、アセタール基、炭酸エステル基又はカルボキシアルコキシ基が好ましい。
炭素数1~60の直鎖状又は分岐状の脂肪族炭化水素基としては、特に限定されないが、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-ブチル基、n-ペンチル基、n-ヘキシル基、n-ドデシル基、バレル基、2-エチルヘキシル基が挙げられる。
Aは、下記式(A-1)~(A-4)のいずれかで表される基であることが好ましく、下記式(A-1)で表される基であることがより好ましい。
尚、本実施形態の化合物(A)および化合物(A)に由来する樹脂を露光プロセスにおけるレジスト下層膜として用いる際に、レジスト層の下層膜として使用し、且つパターン形成後のドライエッチング等の加工工程において加工対象となる被加工層上に積層して下層膜層を形成し被加工層を加工するプロセスを用いる場合には、被加工層の加工後の矩形性やラフネスなどのパターン品質を良好にするためのエッチングマスク性能の観点から、エッチングレートを抑制できるように、高炭素含率、低水素含率、高い環構造導入率であることが好ましく、化合物構造として単環や2個以上の複数の環構造が縮合した縮環構造を有する樹脂を用いることが好ましい。この際、環構造は芳香族構造やヘテロ芳香族構造を有することが好ましい。
また、本実施形態の化合物(A)および化合物(A)に由来する樹脂をレジスト下層膜として用い、更にエッチングマスク層として1層以上の別のスピンオンカーボン(SOC)層や無機のハードマスク層を用いる場合には、レジスト層のパターン形状をエッチングにより転写する対象となるエッチングマスク層の加工性、および現像直後のレジストの形状からエッチングによりパターン形状を劣化させない観点から、レジストよりもエッチングレートが速く易エッチング性を示す本実施形態の化合物(A)または化合物(A)に由来する樹脂からなるレジスト下層膜を使用し、被加工層を有する基板上に少なくとも一つ以上のエッチングマスク層を積層し、更に該エッチングマスク層よりも上層側に本実施形態の化合物(A)または化合物(A)を含む樹脂からなる層を積層することで、加工後の被加工層のパターン形状の品質向上を図ることも好ましい。これらの観点からは、芳香環構造が少ない樹脂、またはノボラック構造を有しない構造の方が好ましく、ポリアクリル樹脂やポリエチレン樹脂、ポリアルキレンエーテル樹脂等の脂肪族構造を主鎖に有する樹脂や脂肪族構造を構成する炭素骨格の含有比率が高い樹脂の方が好ましい。
本実施形態の組成物は化合物(A)又は/及び樹脂(A)を含む。
本実施形態における溶媒は、上述した化合物(A)又は/及び樹脂(A)が少なくとも溶解するものであれば、公知のものを適宜用いることができる。溶媒の具体例としては、特に限定されないが、例えば、エチ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、エチレングリコールモノ-n-プロピルエーテルアセテート、エチレングリコールモノ-n-ブチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテルなどのエチレングリコールモノアルキルエーテル類;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)、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノ-n-プロピルエーテルアセテート、プロピレングリコールモノ-n-ブチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類;プロピレングリコールモノメチルエーテル(PGME)、プロピレングリコールモノエチルエーテルなどのプロピレングリコールモノアルキルエーテル類;乳酸メチル、乳酸エチル、乳酸n-プロピル、乳酸n-ブチル、乳酸n-アミル等の乳酸エステル類;酢酸メチル、酢酸エチル、酢酸n-プロピル、酢酸n-ブチル、酢酸n-アミル、酢酸n-ヘキシル、プロピオン酸メチル、プロピオン酸エチル等の脂肪族カルボン酸エステル類;3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、3-メトキシ-2-メチルプロピオン酸メチル、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、3-メトキシ-3-メチルプロピオン酸ブチル、3-メトキシ-3-メチル酪酸ブチル、アセト酢酸メチル、ピルビン酸メチル、ピルビン酸エチル等の他のエステル類;トルエン、キシレン等の芳香族炭化水素類;アセトン、2-ブタノン、2-ヘプタノン、3-ヘプタノン、4-ヘプタノン、シクロペンタノン(CPN)、シクロヘキサノン(CHN)等のケトン類;N,N-ジメチルホルムアミド、N-メチルアセトアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等のアミド類;γ-ラクトン等のラクトン類等を挙げることができるが、特に限定はされない。本実施形態で使用される溶媒は、安全溶媒であることが好ましく、より好ましくは、PGMEA、PGME、CHN、CPN、2-ヘプタノン、アニソ-ル、酢酸ブチル及び乳酸エチルから選ばれる少なくとも1種であり、さらに好ましくはPGMEA、PGME、CHN、CPN及び乳酸エチルから選ばれる少なくとも一種である。
本実施形態の組成物において、可視光線、紫外線、エキシマレーザー、電子線、極端紫外線(EUV)、X線及びイオンビ-ムから選ばれるいずれかの放射線の照射、又は加熱により直接的又は間接的に酸を発生する酸発生剤を一種以上含むことが好ましい。酸発生剤は、特に限定されないが、非イオン系又はイオン系のいずれを用いてもよい。非イオン系酸発生剤としては、スルホネートエステル類(例えば2-ニトロベンジルエステル、芳香族スルホネート、オキシムスルホネート、N-スルホニルオキシイミド、スルホニルオキシケトン、ジアゾナフトキノン 4-スルホネート)、スルホン類(例えばジスルホン、ケトスルホン、スルホニルジアゾメタン)等が挙げられる。イオン系酸発生剤としては、オニウムカチオンを含むオニウム塩(例えばジアゾニウム塩、ホスホニウム塩、スルホニウム塩、ヨードニウム塩)が代表的である。オニウム塩のアニオンとしては、スルホン酸アニオン、スルホニルイミドアニオン、スルホニルメチドアニオン等が挙げられる。例えば、国際公開WO2013/024778号、特開2009-134088号、特開昭63-26653号、特開昭55-164824号、特開昭62-69263号、特開昭63-146038号、特開昭63-163452号、特開昭62-153853号、特開昭63-146029号、米国特許第3,779,778号、米国特許第3,849,137号、独国特許第3914407号、欧州特許第126,712号等に記載の酸を発生する化合物を用いることができる。酸発生剤は、単独で又は2種以上を使用することができる。
また、併用することができるその他の化合物として、発生した酸の拡散を促進または抑制することができる化合物を酸拡散制御剤として含むことができる。
<酸拡散促進剤>
好ましい酸拡散促進剤としては、発生酸を保持しつつ必要な状況では酸を放出可能とする目的でpKa値が2.0以下と低く、かつ、分子量が1000以下またはclogP値が30以下またはTgが250℃以下となることで樹脂マトリックス中での熱拡散性を促進でき、かつ少なくとも250℃における耐熱性を有する化合物を含むこともできる。具体的な酸拡散促進剤の構造としては非イオン系又はイオン系のいずれを用いてもよい。非イオン系酸拡散促進剤としては、スルホネートエステル類(例えば2-ニトロベンジルエステル、芳香族スルホネート、オキシムスルホネート、N-スルホニルオキシイミド、スルホニルオキシケトン)、スルホン類(例えばジスルホン、ケトスルホン、スルホニルジアゾメタン)等が挙げられる。イオン系酸拡散促進剤としては、オニウムカチオンを含むオニウム塩(例えばジアゾニウム塩、ホスホニウム塩、スルホニウム塩、ヨードニウム塩)が代表的である。オニウム塩のアニオンとしては、スルホン酸アニオン、スルホニルイミドアニオン、スルホニルメチドアニオン等が挙げられる。
イオン系化合物におけるカチオンとしては、アニオンとの塩を形成した状態で上記の分子量、clogP、Tgのいずれか、および耐熱性を満たすカチオンであれば特に限定せずに使用することができる。具体的なカチオンの例としては有機アンモニウムカチオン、有機ヨードニウムカチオン、有機スルホニウムカチオン、を好ましく用いることができる。
酸拡散抑制剤は、露光により酸発生剤等から生じる酸が、露光、PEB、現像の各工程におけるレジスト膜や下層膜中の拡散を抑制し、未露光部に微量発生または拡散により存在する酸の影響によるレジスト樹脂または下層膜樹脂の反応を抑制する目的で使用することができる。また、その他の効果として、レジスト樹脂組成物または下層膜樹脂組成物の経時安定性の向上や、リソグラフィーにおける解像性の向上、パターン品質についての露光後から現像までに要する時間依存性の抑制による工程ロバストネスの向上につながり、プロセス安定性に優れたレジスト樹脂組成物または下層膜樹脂組成物を提供することができる。酸拡散抑制剤としては、低分子化合物でも、重合体の一部として組み込まれた形態として適用してもよいし、これらの両方の形態を併用してもよい。
酸拡散抑制剤としては、例えば窒素原子含有化合物、露光により感光し弱酸を発生する光塩基発生剤等が挙げられる。
酸発生剤から発生する酸よりも酸性度の弱い酸を発生する塩の例としては、特開2015-147926号公報記載の式(D)で表される塩、特開2012-229206号公報 、特開2012-6908号公報、特開2012-72109号公報、特開2011-39502号公報及び特開2011-191745号公報記載の塩を挙げることができる。
その他の好ましい酸拡散抑制剤の例として以下を上げることができるが、これらに限定されない。
本実施形態において、組成物中に、架橋剤を一種以上含めることができる。架橋剤は少なくとも化合物(A)又は樹脂(A)のいずれかを架橋し得る化合物を意味する。前記架橋剤としては、酸発生剤から発生した酸の存在下で、化合物(A)又は樹脂(A)を分子内又は分子間架橋し得る酸架橋剤であることが好ましい。このような酸架橋剤としては、例えば化合物(A)又は樹脂(A)を架橋し得る1種以上の基(以下、「架橋性基」という。)を有する化合物を挙げることができる。
本実施形態の組成物には、その他の成分として、必要に応じて、溶解促進剤、溶解制御剤、増感剤、界面活性剤及び有機カルボン酸又はリンのオキソ酸若しくはその誘導体等の各種添加剤を1種又は2種以上添加することができる。
溶解促進剤は、固形成分の現像液に対する溶解性が低すぎる場合に、その溶解性を高めて、現像時の前記化合物の溶解速度を適度に増大させる作用を有する成分である。前記溶解促進剤としては、低分子量のものが好ましく、例えば、低分子量のフェノール性化合物を挙げることができる。低分子量のフェノール性化合物としては、例えば、ビスフェノール類、トリス(ヒドロキシフェニル)メタン等を挙げることができる。これらの溶解促進剤は、単独で又は2種以上を混合して使用することができる。
溶解制御剤は、固形成分の現像液に対する溶解性が高すぎる場合に、その溶解性を制御して現像時の溶解速度を適度に減少させる作用を有する成分である。このような溶解制御剤としては、膜の焼成、放射線照射、上層の塗布等の工程において化学変化しないものが好ましい。
溶解制御剤の配合量は、使用する前記化合物の種類に応じて適宜調節されるが、固形成分全質量の0~49質量%が好ましく、0~5質量%がより好ましく、0~1質量%がさらに好ましく、0質量%が特に好ましい。
増感剤は、照射された放射線のエネルギーを吸収して、そのエネルギーを酸発生剤に伝達し、それにより酸の生成量を増加する作用を有し、硬化性を向上させる成分である。このような増感剤としては、例えば、ベンゾフェノン類、ビアセチル類、ピレン類、フェノチアジン類、フルオレン類等を挙げることができるが、特に限定はされない。これらの増感剤は、単独で又は2種以上を使用することができる。
界面活性剤は、本実施形態の組成物の塗布性やストリエーション、上層膜の塗布性等を改良する作用を有する成分である。界面活性剤は、アニオン系界面活性剤、カチオン系界面活性剤、ノニオン系界面活性剤又は両性界面活性剤のいずれでもよい。好ましい界面活性剤としては、ノニオン系界面活性剤が挙げられる。ノニオン系界面活性剤は、本実施形態の組成物の製造に用いる溶媒との親和性がよく、本実施形態の組成物の効果をより高めることができる。ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリエチレングリコールの高級脂肪酸ジエステル類等が挙げられるが、特に限定されない。これら界面活性剤の市販品としては、以下商品名で、エフトップ(ジェムコ社製)、メガファック(大日本インキ化学工業社製)、フロラ-ド(住友スリ-エム社製)、アサヒガ-ド、サ-フロン(以上、旭硝子社製)、ペポ-ル(東邦化学工業社製)、KP(信越化学工業社製)、ポリフロ-(共栄社油脂化学工業社製)等を挙げることができる。
さらに、本実施形態の組成物には、必要に応じて、上述した成分以外の添加剤を1種又は2種以上配合することができる。このような添加剤としては、例えば、染料、顔料、及び接着助剤等が挙げられる。例えば、染料又は顔料を配合すると、露光部の潜像を可視化させて、露光時のハレ-ションの影響を緩和できるので好ましい。また、接着助剤を配合すると、基板、及び接している層との接着性を改善することができるので好ましい。さらに、他の添加剤としては、ハレーション防止剤、保存安定剤、消泡剤、形状改良剤等、具体的には4-ヒドロキシ-4’-メチルカルコン等を挙げることができる。
本実施形態の組成物は、スピンコートによってアモルファス膜を形成することができる。また、本実施形態の組成物は、一般的な半導体製造プロセスに適用することができる。本実施形態の組成物は硬化後、極端紫外線の照射によりプロトンを生成し、隣接する層にプロトンを供給することにより、隣接する層の感度を向上させることができる。本実施形態の組成物は、硬化して用いることが好ましい。硬化後は、隣接する層の組成物に溶解しないために、耐溶剤性があることが好ましい。
本実施形態の組成物を用いて、基板上にアモルファス膜を形成することが可能である。
本実施形態の組成物を用いたレジストパターン形成方法は、基板上に、前記組成物を用いて下層膜を形成する下層膜形成工程と、該下層膜形成工程により形成した下層膜上に、少なくとも1層のフォトレジスト膜を形成するフォトレジスト膜形成工程と、該フォトレジスト膜形成工程により形成したフォトレジスト膜の所定の領域に放射性を照射し、現像を行う工程と、を含む。
本実施形態の組成物を用いた回路パターン形成方法は、基板上に、下層膜を形成する下層膜形成工程と、該下層膜形成工程により形成した下層膜上に、前記組成物を用いて、レジスト層接触膜を形成する、レジスト層接触膜形成工程と、該レジスト層接触膜形成工程により形成したレジスト層接触膜上に、少なくとも1層のフォトレジスト膜を形成するフォトレジスト膜形成工程と、該フォトレジスト膜形成工程により形成したフォトレジスト膜の所定の領域に放射線を照射し、現像してレジストパターンを形成するレジストパターン形成工程と、該レジストパターン形成工程により形成したレジストパターンをマスクとして、前記レジスト層接触膜、または前記レジスト層接触膜及び前記下層膜をエッチングしてパターンを形成するパターン形成工程と、該パターン形成工程により形成したパターンをマスクとして前記基板をエッチングして基板にパターンを形成する基板パターン形成工程と、を含む。
(1)化合物の構造
化合物の構造は、Bruker社製AdvanceIII 500 を用いて、以下の条件で、1H-NMR測定を行い、確認した。
周波数:500MHz
溶媒:d6-DMSO
内部標準:TMS
測定温度:23℃
(下層膜組成物の調整)
下記合成実施例で得られた化合物又は重合体を10質量部、熱酸発生剤 TAG-2689(キングインダストリーズ社製、トリフルオロメタンスルホン酸の第4級アンモニウム塩)0.2質量部、TMOM-BP(本州化学社製)1質量部、PGMEA76.8質量部、及びPGME12質量部を配合し、本発明の化合物を含む下層膜組成物溶液を調製した。
なお、実施例4の化合物については、TAG-2689の代わりにWPBG300(0.2質量部)、またTMOM-BPの代わりにBPN01S(1質量部)を添加した。
化合物のPGMEAへの溶解性は、各溶媒への溶解量を用いて以下の基準で評価した。なお、溶解量の測定は23℃にて、化合物を試験管に精秤し、対象となる溶媒を所定の濃度となるよう加え、超音波洗浄機にて30分間超音波をかけ、その後の液の状態を目視にて観察することにより測定した。
A:5.0質量% ≦ 溶解量
B:2.0質量%≦ 溶解量 <5.0質量%
C:溶解量 <2.0質量%
化合物や樹脂を含む組成物の保存安定性は、上記の下層膜組成物を作成後、23℃にて3日間静置し、析出の有無を目視にて観察することにより評価した。また、組成物を清浄なシリコンウェハー上に回転塗布した後、250℃のホットプレート上でベークして、厚さ100nmのアモルファス膜を形成した。作成した組成物について、均一溶液であり薄膜形成が良好な場合には○、均一溶液だが薄膜に欠陥がある場合には△、析出がある場合は×と評価した。
(EUV感度-TMAH水溶液現像)
下記レジスト用重合体合成実施例で得られた重合体MAR1を5質量部、トリフェニルスルホニウムノナフルオロメタンスルホナート1質量部、トリブチルアミン0.2質量部、PGMEA80質量部、及びPGME12質量部を配合し感度評価用およびパターン評価用のレジスト溶液を調製した。
上記の下層膜組成物をシリコンウエハ上に塗布し、240℃で60秒間ベーク処理を行い、膜厚100nmの下層膜をシリコンウエハ上に形成した。
更に、シリコンウエハ上に形成した本発明の下層膜上にレジスト溶液を塗布し、110℃で60秒間ベークして膜厚100nmのフォトレジスト層を形成した。
次いで、極端紫外線(EUV)露光装置「EUVES―7000」(製品名、リソテックジャパン株式会社製)で1mJ/cm2から1mJ/cm2ずつ80mJ/cm2まで露光量を増加させたマスクレスでのショット露光をした後、110℃で90秒間ベーク(PEB)し、2.38質量%テトラメチルアンモニウムヒドロキシド(TMAH)水溶液で60秒間現像し、ウェハ上に80ショット分のショット露光を行ったウェハを得た。得られた各ショット露光エリアについて、光干渉膜厚計「VM3200」(製品名、株式会社SCREENセミコンダクターソリューションズ製)により膜厚を測定し、露光量に対する膜厚のプロファイルデータを取得し、露光量に対する膜厚変動量の傾きが一番大きくなる露光量を感度値(mJ/cm2)として算出し、レジストのEUV感度の指標とした。
エッチング装置:サムコインターナショナル社製 RIE-10NR
出力:50W
圧力:20Pa
時間:2min
エッチングガス
Arガス流量:CF4ガス流量:O2ガス流量=50:5:5(sccm)
評価基準
A:ノボラックの下層膜に比べてエッチングレートの差が、対ノボラック比で10%以上小さい
B:ノボラックの下層膜に比べてエッチングレートの差が、対ノボラック比で±10%以内
C:ノボラックの下層膜に比べてエッチングレートの差が、対ノボラック比で10%より大きい
攪拌機、冷却管、及びビュレットを備えた内容積200mLの容器に、2,6-ジメチルフェノール(東京化成社製試薬)25.0g(204.7mmol)と、4-ヨードベンズアルデヒド(東京化成製試薬)25.0g(107.7mmol)と、1-メトキシ-2-プロパノール20mLとを仕込み、硫酸5.3g(53.9mmol)を加えて、反応液を調製した。この反応液を90℃で6時間攪拌して反応を行った。反応終了後、反応液に純水1Lを加え、氷冷しながら重曹を加えて、pH7~8に調整し、酢酸エチルにより抽出、濃縮し溶液を得た。得られた溶液を、カラムクロマトによる分離精製を行うことにより、下記式で表される目的化合物(BisB-1)24.9gを得た。得られた化合物(BisB-1)について、前記測定条件でNMR測定を行ったところ、以下のピークが見いだされ、下記式(BisB-1)の化学構造を有することを確認した。
δ(ppm)8.1(2H、-O-H)、6.5~7.7(8H、Ph-H)、5.2(1H、C-H)、2.1(12H、CH3)
攪拌機、冷却管、及びビュレットを備えた内容積500mLの容器に、4,4’-ビフェノール(東京化成社製試薬)42.8g(230mmol)と、3,5-ジヨードサリチルアルデヒド(東京化成製試薬)21.5g(57.5mmol)と、γ-ブチロラクトン428mLとを仕込み、硫酸5.8g(58mmol)を加えて、反応液を調製した。この反応液を90℃で56時間攪拌して反応を行った。反応終了後、反応液に純水1Lを加え、水酸化ナトリウムで中和し、酢酸エチルにより抽出、濃縮し溶液を得た。得られた溶液を、カラムクロマトによる分離精製を行うことにより、下記式で表される目的化合物(BisB-2)10gを得た。得られた化合物(BisB-2)について、前記測定条件でNMR測定を行ったところ、以下のピークが見いだされ、下記式(BisB-2)の化学構造を有することを確認した。
δ(ppm)9.4(4H、-O-H)、8.9(1H、-O-H)、6.2~7.8(16H、Ph-H)、6.3(1H、C-H)
攪拌機、冷却管及びビュレットを備えた内容積300mlの容器に2,6-ナフタレンジオール(シグマ-アルドリッチ社製試薬)7.0g(40mmol)と3-ヨードベンズアルデヒド(東京化成工業社製試薬)4.6g(20mmol)とを100mlのγ―ブチロラクトンに仕込み、p-トルエンスルホン酸0.5gを加えて、90℃で23時間撹拌して反応を行って反応液を得た。次に反応液を純水1000gに加えたあと、酢酸エチルにより抽出、濃縮を行って溶液を得た。
得られた溶液を、カラムクロマトによる分離後、クロロホルム洗浄を行い、下記式(XbisN-1)で表される目的化合物(XbisN-1)が4.2g得られた。得られた化合物(XbisN-1)について、前記方法により分子量を測定した結果、516であった。
得られた化合物(XbisN-1)について、前記測定条件で、NMR測定を行ったところ、以下のピークが見出され、下記式(XbisN-1)の化学構造を有することを確認した。
δ(ppm)9.7(2H,O-H)、7.0~8.5(14H,Ph-H)、6.5(1H,C-H)
200mLのガラス製フラスコを反応容器として使用し、ネオペンチルグリコール ビス(4-アミノフェニル)エーテル(製品名:DANPG、和歌山精化工業(株)製)5.73g(20mmol)に対し、溶媒としてブタノールを用いて溶解した後、50℃にて20質量%塩化ヨウ素水溶液(81.2g、100mmol)を60分かけて滴下したのち、50℃、2時間の撹拌を行い、サリチルアルコールと塩化ヨウ素とを反応させた。反応後の反応溶液に対して、チオ硫酸ナトリウム水溶液を加えて1時間撹拌したのち、液温を10℃まで冷却した。冷却により析出した沈殿物を濾別、洗浄、乾燥を行い、褐色固体9.5gを得た。褐色固体のサンプルを液体クロマトグラフィー―質量分析(LC-MS)で分析した結果、下記式(X)で表される化合物(X)を確認した。
1H-NMR:(d-DMSO、内部標準TMS)
δ(ppm)7.0~7.5(4H,Ph-H)、3.2(4H,-CH=CH)、2.4(4H,-CH2-)、1.6~1.7(6H,CH3-C-CH3)
攪拌機、冷却管及びビュレットを備えた内容積500mLの容器に、2,6-ナフタレンジオール(シグマ-アルドリッチ社製試薬)32.0g(20mmol)と、3,5-ジヨードサリチルアルデヒド(東京化成社製試薬)29.9g(80mmol)と、1,4-ジオキサン200mLとを仕込み、95%の硫酸10mLを加えて、100℃で6時間撹拌して反応を行った。次に、24%水酸化ナトリウム水溶液にて反応液を中和し、純水100gを加えて反応生成物を析出させ、室温まで冷却した後、濾過を行って分離した。得られた固形物を乾燥させた後、カラムクロマトによる分離精製を行うことにより、下記式で表される目的化合物(XBisN-2)2.6gを得た。
なお、500MHz-1H-NMRにより以下のピークが見出され、下記式の化学構造を有することを確認した。
1H-NMR:(d-DMSO、内部標準TMS)
δ(ppm)9.6~9.7(3H,O-H)、6.7~8.5(12H,Ph-H)、6.2(1H,C-H)
攪拌機、冷却管及びビュレットを備えた内容積100mLの容器に、XBisN-2を2.6g(7.0mmol)とフタル酸モノブチル銅を1.0g(2mmol)仕込み、溶媒として1-ブタノールを20mL加えて、反応液を100℃で6時間撹拌して反応を行った。冷却後に析出物を濾過し、得られた粗体を酢酸エチル20mLに溶解させた。次に塩酸1mLを加え、室温で攪拌後、炭酸水素ナトリウムで中和処理を行った。酢酸エチル溶液を濃縮し、メタノール40mLを加えて反応生成物を析出させ、室温まで冷却した後、濾過を行って分離した。得られた固形物を乾燥させることにより、下記式で表される構造を有する目的樹脂(RXBisN-2)1.0gを得た。
得られた樹脂について、前記方法によりポリスチレン換算分子量を測定した結果、Mn:4300、Mw:5500、Mw/Mn:1.28であった。
得られた樹脂について、前記測定条件でNMR測定を行ったところ、以下のピークが見出され、下記式の化学構造を有することを確認した。
δ(ppm)9.5~9.7(3H,O-H)、6.7~8.5(12H,Ph-H)、6.0~6.3(1H,C-H)
窒素下、300mL四口フラスコに1,4-ビス(クロロメチル)ベンゼン(28.8g、0.148mol、東京化成工業(株)製)、1-ナフトール(30.0g、0.1368mol、東京化成工業(株)製)、パラトルエンスルホン酸一水和物(5.7g、0.029mol、東京化成工業(株)製)を加え、さらにプロピレングリコールモノメチルエーテルアセテート(以下PGMEAという略称で示す。)150.4gを仕込み、撹拌し、リフラックスが確認されるまで昇温し溶解させ、重合を開始した。16時間後60℃まで放冷後、メタノール1600gへ再沈殿させた。
得られた沈殿物をろ過し、減圧乾燥機で60℃、16時間乾燥させ、下記式(NAFP-AL)で表される構造単位を有する目的とするオリゴマー38.6gを得た。得られたオリゴマーのGPCによるポリスチレン換算で測定される重量平均分子量は2020、分散度は1.86であった。
200mLのガラス製フラスコを反応容器として使用し、上記で得られたNAFP-AL 8g(20mmol)に対し、溶媒としてブタノールを用いて溶解した後、50℃にて20質量%塩化ヨウ素水溶液(81.2g、100mmol)を60分かけて滴下したのち、50℃、2時間の撹拌を行い、サリチルアルコールと塩化ヨウ素とを反応させた。反応後の反応溶液に対して、チオ硫酸ナトリウム水溶液を加えて1時間撹拌したのち、液温を10℃まで冷却した。冷却により析出した沈殿物を濾別、洗浄、乾燥を行い、褐色固体11.5gを得た。
200mLのガラス製フラスコを反応容器として使用し、サリチルアルコール 4.96g(40mmol)に対し、溶媒としてブタノールを用いて溶解した後、50℃にて20質量%塩化ヨウ素水溶液(81.2g、100mmol)を60分かけて滴下したのち、50℃ 2時間の撹拌を行い、サリチルアルコールと塩化ヨウ素とを反応させた。反応後の反応溶液に対して、チオ硫酸ナトリウム水溶液を加えて1時間撹拌したのち、液温を10℃まで冷却した。冷却により析出した沈殿物を濾別、洗浄、乾燥を行い、白色個体12.1gを得た。白色個体のサンプルを液体クロマトグラフィー―質量分析(LC-MS)で分析した結果、4-ヒドロキシ-3,5-ジヨウドベンジルアルコールを確認した。
3.0gの化合物2I-PHSと、メチルメタクリル酸1.2gとを45mLのテトラヒドロフランに溶解し、アゾビスイソブチロニトリル0.20gを加えた。12時間還流した後、反応溶液を2Lのn-ヘプタンに滴下した。析出した重合体を濾別、減圧乾燥を行い、白色な粉体状の下記式(P-2I-PHS-MMA)で表される重合体P-2I-PHS-MMAを得た。この重合体の重量平均分子量(Mw)は8000、分散度(Mw/Mn)は1.50であった。また、13C-NMRを測定した結果、下記式(P-2I-PHS-MMA)中の組成比(モル比)はa:b=1:1であった。なお、下記式(P-2I-PHS-MMA)は、各構成単位の比率を示すために簡略的に記載されているが、各構成単位の配列順序はランダムであり、各構成単位がそれぞれ独立したブロックを形成しているブロック共重合体ではない。
攪拌機、冷却管及びビュレットを備えた内容積3Lの容器に、国際公開2013/024779に記載されている下記式で表される化合物(XBisN-C1)を100g(0.214mol)とヨウ化カリウム71.2g(0.429mol)を仕込み、溶媒としてメタノール1Lを加えて、さらに氷冷下で硫酸146g(1.5mol)を滴下し、10℃で4時間攪拌して反応を行った。反応終了後に酢酸ブチルで抽出し、水洗洗浄、中和後に、ろ過乾燥して下記式(XBisN-3)で表される目的化合物(RBisN-3)87.8gを得た。
得られた化合物について、前記測定条件でNMR測定を行ったところ、以下のピークが見出され、下記式の化学構造を有することを確認した。
δ(ppm)10.6(2H,O-H)、7.2~8.6(17H,Ph-H)、6.7(1H,C-H)
1,3-アダマンタンジオール(三菱ガス化学製)16.8g(0.1mol)をトルエン200mLに溶解し、57%ヨウ化水素水溶液89.8g(0.4mol)を加え、80℃で8時間攪拌し反応した。反応後、水を加えて、炭酸水素ナトリウムで洗浄し、有機層を濃縮後にカラムクロマトで分離精製を行うことにより、下記式で表される3-ヨード-1-ヒドロキシアダマンタン12gを得た。
δ(ppm)(d-DMSO):6.4~6.5(2H、=CH2)、1.3~3.2(17H、Ad-H、-C(CH3)=C)
1,3,5-アダマンタントリオール(三菱ガス化学製)2.3g(12.5mmol)をトルエン100mLに溶解し、57%ヨウ化水素水溶液28.1g(125mmol)を加え、80℃で13時間攪拌し反応した。反応後、水を加えて、炭酸水素ナトリウムで洗浄し、有機層を濃縮後にカラムクロマトで分離精製を行うことにより、下記式で表される3,5-ジヨード-1-ヒドロキシアダマンタン0.9gを得た。
δ(ppm)(d-DMSO):6.4~6.5(2H、=CH2)、1.5~3.9(16H、Ad-H、-C(CH3)=C)
MAC-ADI(4.2g)と、2-メチル-2-アダマンチルメタクリレート1.5g、γ-ブチロラクトンメタクリル酸エステル2.0gと、ヒドロキシアダマンチルメタクリル酸エステル1.5gとを45mLのテトラヒドロフランに溶解し、アゾビスイソブチロニトリル0.20gを加えた。12時間還流した後、反応溶液を2lのn-ヘプタンに滴下した。析出した樹脂を濾別、減圧乾燥を行い、白色な粉体状の下記化学式(P-MAC-ADI)で示される樹脂を得た。この樹脂の分子量(Mw)は9300、分散度(Mw/Mn)は1.9であった。また、13C-NMRを測定した結果、下記化学式(P-MAC-ADI)中の組成比(モル比)はa:b:c:d=20:30:15:35であった。なお、下記化学式(P-MAC-ADI)は、各構成単位の比率を示すために簡略的に記載されているが、P-MAC-ADIは、各構成単位がそれぞれ独立したブロックを形成しているブロック共重合体ではない。
MAC-ADI2(5.6g)と、2-メチル-2-アダマンチルメタクリレート1.5g、γ-ブチロラクトンメタクリル酸エステル2.0gと、ヒドロキシアダマンチルメタクリル酸エステル1.5gとを45mLのテトラヒドロフランに溶解し、アゾビスイソブチロニトリル0.20gを加えた。12時間還流した後、反応溶液を2lのn-ヘプタンに滴下した。析出した樹脂を濾別、減圧乾燥を行い、白色な粉体状の下記化学式(P-MAC-ADI2)で示される樹脂を得た。この樹脂の分子量(Mw)は8350、分散度(Mw/Mn)は2.0であった。また、13C-NMRを測定した結果、下記化学式(MAC-ADI2)中の組成比(モル比)はa:b:c:d=20:30:15:35であった。なお、下記化学式(P-MAC-ADI2)は、各構成単位の比率を示すために簡略的に記載されているが、P-MAC-ADI2は、各構成単位がそれぞれ独立したブロックを形成しているブロック共重合体ではない。
1.0gの化合物p-ヒドロキシスチレンと、メチルメタクリル酸1.2gとを45mLのテトラヒドロフランに溶解し、アゾビスイソブチロニトリル0.20gを加えた。12時間還流した後、反応溶液を2Lのn-ヘプタンに滴下した。析出した重合体を濾別、減圧乾燥を行い、白色な粉体状の下記式(P-PHS-MMA)で表される重合体P-PHS-MMAを得た。この重合体の重量平均分子量(Mw)は9100、分散度(Mw/Mn)は1.60であった。また、13C-NMRを測定した結果、下記式(P-PHS-MMA)中の組成比(モル比)はa:b=1:1であった。なお、下記式(P-PHS-MMA)は、各構成単位の比率を示すために簡略的に記載されているが、各構成単位の配列順序はランダムであり、各構成単位がそれぞれ独立したブロックを形成しているブロック共重合体ではない。
p-ヒドロキシスチレン(東邦化学工業株式会社製)0.5gと、2-メチル-2-アダマンチルメタクリレート3.0gと、γ-ブチロラクトンメタクリル酸エステル2.0gと、ヒドロキシアダマンチルメタクリル酸エステル1.5gとを45mLのテトラヒドロフランに溶解し、アゾビスイソブチロニトリル0.20gを加えた。12時間還流した後、反応溶液を2Lのn-ヘプタンに滴下した。析出した重合体を濾別、減圧乾燥を行い、白色な粉体状の下記式(MAR1)で表される重合体MAR1を得た。この重合体の重量平均分子量(Mw)は1,2000、分散度(Mw/Mn)は1.90であった。また、13C-NMRを測定した結果、下記式(MAR1)中の組成比(モル比)はa:b:c:d=40:30:15:15であった。なお、下記式(MAR1)は、各構成単位の比率を示すために簡略的に記載されているが、各構成単位の配列順序はランダムであり、各構成単位がそれぞれ独立したブロックを形成しているブロック共重合体ではない。ポリスチレン系モノマー(p-ヒドロキシスチレン)はベンゼン環の根元の炭素、メタアクリレート系のモノマー(2-メチル-2-アダマンチルメタクリレート、γ-ブチロラクトンメタクリル酸エステル、及び、ヒドロキシアダマンチルメタクリル酸エステル)はエステル結合のカルボニル炭素について、それぞれの積分比を基準にモル比を求めた。
p-ヒドロキシスチレン(東邦化学工業株式会社製)1.0gと、2-メチル-2-アダマンチルメタクリレート3.8gと、γ-ブチロラクトンメタクリル酸エステル0.7gと、ヒドロキシアダマンチルメタクリル酸エステル1.0gとを45mLのテトラヒドロフランに溶解し、アゾビスイソブチロニトリル0.20gを加えた。12時間還流した後、反応溶液を2Lのn-ヘプタンに滴下した。析出した重合体を濾別、減圧乾燥を行い、白色な粉体状の下記式(MAR2)で表される重合体MAR2を得た。この重合体の重量平均分子量(Mw)は1,2000、分散度(Mw/Mn)は1.90であった。また、13C-NMRを測定した結果、下記式(MAR2)中の組成比(モル比)はa:b:c:d=50:10:10:30であった。なお、下記式(MAR2)は、各構成単位の比率を示すために簡略的に記載されているが、各構成単位の配列順序はランダムであり、各構成単位がそれぞれ独立したブロックを形成しているブロック共重合体ではない。ポリスチレン系モノマー(p-ヒドロキシスチレン)はベンゼン環の根元の炭素、メタアクリレート系のモノマー(2-メチル-2-アダマンチルメタクリレート、γ-ブチロラクトンメタクリル酸エステル、及び、ヒドロキシアダマンチルメタクリル酸エステル)はエステル結合のカルボニル炭素について、それぞれの積分比を基準にモル比を求めた。
合成実施例1~10、および合成比較例AR1で得られた化合物又は樹脂の安全溶媒溶解度、保存安定性、薄膜形成性、感度、エッチング耐性を、上述のとおりに評価した。結果を表1に示す。
合成実施例1~10で得られた化合物又は樹脂に換えて、国際公開2013/024779に記載されている下記式で表される化合物(XBisN-C1)を用いる以外は実施例1~10と同様にして評価を行った。結果を表1に示す。
<酸拡散制御剤>
以下を酸拡散促進剤として使用した。
・WPAG199(Bis(4-methylphenylsulfonyl)diazomehtane) (富士フイルム和光純薬製)
(EUV感度- n-酢酸ブチル現像)
上記レジスト用重合体合成実施例で得られた重合体MAR2を5質量部、トリフェニルスルホニウムノナフルオロメタンスルホナート1質量部、トリブチルアミン0.2質量部、PGMEA80質量部、及びPGME12質量部を配合し感度評価用およびパターン評価用のレジスト溶液2を調製した。
作製した下層膜組成物をシリコンウエハ上に塗布し、240℃で60秒間ベーク処理を行い、膜厚100nmの下層膜をシリコンウエハ上に形成した。
更に、シリコンウエハ上に形成した本発明の下層膜上にレジスト溶液2を塗布し、110℃で60秒間ベークして膜厚100nmのフォトレジスト層を形成した。
次いで、極端紫外線(EUV)露光装置「EUVES―7000」(製品名、リソテックジャパン株式会社製)で1mJ/cm2から1mJ/cm2ずつ80mJ/cm2まで露光量を増加させたマスクレスでのショット露光をした後、110℃で90秒間ベーク(PEB)し、n-酢酸ブチルで30秒間現像し、ウェハ上に80ショット分のショット露光を行ったウェハを得た。得られた各ショット露光エリアについて、光干渉膜厚計「VM3200」(製品名、株式会社SCREENセミコンダクターソリューションズ製)により膜厚を測定し、露光量に対する膜厚のプロファイルデータを取得し、露光量に対する膜厚変動量の傾きが一番大きくなる露光量を感度値(mJ/cm2)として算出し、レジストのEUV感度の指標とした。
作製した下層膜組成物をシリコンウエハ上に塗布し、240℃で60秒間ベーク処理を行い、膜厚100nmの下層膜をシリコンウエハ上に形成した。
更に、シリコンウエハ上に形成した本発明の下層膜上にレジスト溶液を塗布し、110℃で60秒間ベークして膜厚100nmのフォトレジスト層を形成した。
次いで、極端紫外線(EUV)露光装置「EUVES―7000」(製品名、リソテックジャパン株式会社製)で、上記のTMAH現像におけるEUV感度評価にて取得したEUV感度値より3%大きい露光量にて、ウェハ全面にショット露光を施し、さらに110℃で90秒間ベーク(PEB)、2.38質量%テトラメチルアンモニウムヒドロキシド(TMAH)水溶液で60秒間現像を行い、ウェハ全面に80ショット分のショット露光を行ったウェハを得た。
作成した露光済ウェハに対し、エッチング装置「Telius SCCM」(製品名、東京エレクトロン株式会社製)にて、CF4/Arガスを用いて酸化膜を60nmエッチングするまでエッチング処理を行った。エッチングで作成したウェハについて、欠陥検査装置「Surfscan SP5」(製品名、KLA社製)で欠陥評価を行い、19nm以上のコーン欠陥の数をエッチング欠陥の指標として求めた。
(評価基準)
A: コーン欠陥の数 ≦ 20個未満
B: 20個 < コーン欠陥の数 ≦ 200個
C: 200個 < コーン欠陥の数 ≦ 1000個
D: 1000個 < コーン欠陥の数
得られた評価結果を、表3に示す。
上述のエッチング評価-TMAHの方法において、レジスト溶液としてレジスト溶液2を使用し、露光量としてn-酢酸ブチル現像におけるEUV感度より3%少ない露光量にて露光し、かつ現像液としてTMAH水溶液の代わりにn-酢酸ブチルを用いて現像時間を30秒とする以外は同様の方法により、エッチング欠陥評価を行った。
得られた評価結果を、表3に示す。
Claims (23)
- ヨウ素、テルル及びフッ素からなる群から選択される少なくとも1種の元素を有する化合物、又は前記化合物に由来する構成単位を有する樹脂を含む、リソグラフィー用組成物であって、
前記化合物中における前記原子の合計質量が、15質量%以上75質量%以下である、前記リソグラフィー用組成物。 - 前記少なくとも1種の元素が、ヨウ素及びテルルからなる群から選択される少なくとも1種の元素である、請求項1に記載のリソグラフィー用組成物。
- 前記少なくとも1種の元素がヨウ素であり、前記化合物中における前記ヨウ素の質量が、15質量%以上75質量%以下である、請求項1又は2に記載のリソグラフィー用組成物。
- 前記化合物が、式(A-4a)で表される、請求項1~3のいずれかに記載のリソグラフィー用組成物。
Xは酸素原子、硫黄原子、単結合又は無架橋であることを示し、
Yは炭素数1~60の2n価の基又は単結合であり、
ここで、Xが無架橋であるとき、Yは前記2n価の基であり、
R0は各々独立して、置換基を有していてもよい炭素数1~40のアルキル基、置換基を有していてもよい炭素数6~40のアリール基、置換基を有していてもよい炭素数2~40のアルケニル基、置換基を有していてもよい炭素数2~40のアルキニル基、置換基を有していてもよい炭素数1~40のアルコキシ基、ハロゲン原子、チオール基又は水酸基であり、
ここで、R0の少なくとも1つは水酸基であり、
mは各々独立して1~9の整数であり、
Qはヨウ素、テルル、フッ素、又はヨウ素若しくはテルル若しくはフッ素を少なくとも含む炭素数1~30のアルキル基、又はヨウ素若しくはテルル若しくはフッ素を少なくとも含む炭素数6~40のアリール基を表し、
nは1~4の整数であり、
pは各々独立して0~3の整数であり、
Q、R0、Yの少なくとも一つは、ヨウ素、テルル、フッ素の少なくとも1つの元素を含み、
qは各々独立して0~(4+2×p-m)の整数である。) - Yが、置換基を有していてもよい炭素数6~60のアリール基を有する2n価の炭化水素基である、請求項4に記載のリソグラフィー用組成物。
- 前記化合物が、式(A-4c)で表される、請求項1~3のいずれかに記載のリソグラフィー用組成物。
Xは酸素原子、硫黄原子、単結合又は無架橋であることを示し、
Yは炭素数1~60の2n価の基又は単結合であり、
ここで、Xが無架橋であるとき、Yは前記2n価の基であり、
R0は各々独立して、置換基を有していてもよい炭素数1~40のアルキル基、置換基を有していてもよい炭素数6~40のアリール基、置換基を有していてもよい炭素数2~40のアルケニル基、置換基を有していてもよい炭素数2~40のアルキニル基、置換基を有していてもよい炭素数1~40のアルコキシ基、ハロゲン原子、チオール基又は水酸基であり、
ここで、R0の少なくとも1つは水酸基であり、
R0の少なくとも1つはヨウ素、又はヨウ素を含有する基であり、
mは各々独立して1~9の整数であり、
nは1~4の整数であり、
pは各々独立して0~3の整数である。) - Yが、置換基を有していてもよい炭素数6~60のアリール基を有する2n価の炭化水素基である、請求項6に記載のリソグラフィー用組成物。
- 前記化合物が一般式(A-7)で表される、請求項1~3のいずれかに記載のリソグラフィー用組成物。
Xは、それぞれ独立して、テルル、I、F、又は、テルル、I、及びFからなる群から選ばれる1以上5以下の置換基を有する炭素数1~30の有機基を表し、かつXの少なくとも1つはテルル又はIであり、
L1は、単結合、エーテル基、エステル基、チオエーテル基、アミノ基、チオエステル基、アセタール基、ホスフィン基、ホスフォン基、ウレタン基、ウレア基、アミド基、イミド基、又はリン酸基を表し、
mは1以上の整数であり、
Yは、それぞれ独立して、水酸基、アルコキシ基、エステル基、アセタール基、炭酸エステル基、ニトロ基、アミノ基、カルボキシル基、チオール基、エーテル基、チオエーテル基、ホスフィン基、ホスフォン基、ウレタン基、ウレア基、アミド基、イミド基、又はリン酸基を表し、
nは、0以上の整数であり、
Zは、それぞれ独立して、アルコキシ基、エステル基、アセタール基、又は炭酸エステル基であり、
rは、0以上の整数であり、
Aは、炭素数1~30の有機基であり、
Ra、Rb、及びRcは、それぞれ独立して、H、I、F、Cl、Br、又は、置換基を有していてもよい炭素数1~60の有機基であり
pは、1以上の整数である。) - 溶媒をさらに含有する、請求項1~9のいずれかに記載のリソグラフィー用組成物。
- 酸発生剤をさらに含有する、請求項1~10のいずれかに記載のリソグラフィー用組成物。
- 酸拡散促進剤をさらに含有する、請求項1~11のいずれかに記載のリソグラフィー用組成物。
- 酸拡散抑制剤をさらに含有する、請求項1~12のいずれかに記載のリソグラフィー用組成物。
- 架橋剤をさらに含有する、請求項1~13のいずれかに記載のリソグラフィー用組成物。
- 薄膜形成後に硬化される、請求項1~14のいずれかに記載のリソグラフィー用組成物。
- レジスト層接触膜を形成するための、請求項1~15のいずれかに記載のリソグラフィー用組成物。
- 下層膜を形成するための、請求項1~15のいずれかに記載のリソグラフィー用組成物。
- 基板上に、請求項17に記載のリソグラフィー用組成物を用いて下層膜を形成する下層膜形成工程と、
該下層膜形成工程により形成した下層膜上に、少なくとも1層のフォトレジスト膜を形成するフォトレジスト膜形成工程と、
該フォトレジスト膜形成工程により形成したフォトレジスト膜の所定の領域に放射性を照射し、現像を行う工程と、
を含む、レジストパターン形成方法。 - 基板上に、下層膜を形成する下層膜形成工程と、
該下層膜形成工程により形成した下層膜上に、請求項16に記載のリソグラフィー用組成物を用いて、レジスト層接触膜を形成する、レジスト層接触膜形成工程と、
該レジスト層接触膜形成工程により形成したレジスト層接触膜上に、少なくとも1層のフォトレジスト膜を形成するフォトレジスト膜形成工程と、
該フォトレジスト膜形成工程により形成したフォトレジスト膜の所定の領域に放射線を照射し、現像してレジストパターンを形成するレジストパターン形成工程と、
該レジストパターン形成工程により形成したレジストパターンをマスクとして、前記レジスト層接触膜、または前記レジスト層接触膜及び前記下層膜をエッチングしてパターンを形成するパターン形成工程と、
該パターン形成工程により形成したパターンをマスクとして前記基板をエッチングして基板にパターンを形成する基板パターン形成工程と、
を含む、回路パターン形成方法。 - 式(A-4a)で表される化合物。
Xは酸素原子、硫黄原子、単結合又は無架橋であることを示し、
Yは炭素数1~60の2n価の基又は単結合であり、
ここで、Xが無架橋であるとき、Yは前記2n価の基であり、
R0は各々独立して、置換基を有していてもよい炭素数1~40のアルキル基、置換基を有していてもよい炭素数6~40のアリール基、置換基を有していてもよい炭素数2~40のアルケニル基、置換基を有していてもよい炭素数2~40のアルキニル基、置換基を有していてもよい炭素数1~40のアルコキシ基、ハロゲン原子、チオール基又は水酸基であり、
ここで、R0の少なくとも1つは水酸基であり、
mは各々独立して1~9の整数であり、
Qはヨウ素、テルル、フッ素、又はヨウ素若しくはテルル若しくはフッ素を少なくとも含む炭素数1~30のアルキル基、又はヨウ素若しくはテルル若しくはフッ素を少なくとも含む炭素数6~40のアリール基を表し、
nは1~4の整数であり、
pは各々独立して0~3の整数であり、
Q、R0、Yの少なくとも一つは、ヨウ素、テルル、フッ素の少なくとも1つの元素を含み、
qは各々独立して0~(4+2×p-m)の整数である。) - Yが、置換基を有していてもよい炭素数6~60のアリール基を有する2n価の炭化水素基である、請求項20に記載の化合物。
- 式(A-4c)で表される化合物。
Xは酸素原子、硫黄原子、単結合又は無架橋であることを示し、
Yは炭素数1~60の2n価の基又は単結合であり、
ここで、Xが無架橋であるとき、Yは前記2n価の基であり、
R0は各々独立して、置換基を有していてもよい炭素数1~40のアルキル基、置換基を有していてもよい炭素数6~40のアリール基、置換基を有していてもよい炭素数2~40のアルケニル基、置換基を有していてもよい炭素数2~40のアルキニル基、置換基を有していてもよい炭素数1~40のアルコキシ基、ハロゲン原子、チオール基又は水酸基であり、
ここで、R0の少なくとも1つは水酸基であり、
R0の少なくとも1つはヨウ素、又はヨウ素を含有する基であり、
mは各々独立して1~9の整数であり、
nは1~4の整数であり、
pは各々独立して0~3の整数である。) - Yが、置換基を有していてもよい炭素数6~60のアリール基を有する2n価の炭化水素基である、請求項22に記載の化合物。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20230286890A1 (en) * | 2020-09-08 | 2023-09-14 | Innoverda | Method for synthesizing 3,5-diiodo-4-hydroxy benzyl alcohol |
WO2023158848A3 (en) * | 2022-02-18 | 2023-09-21 | The Research Foundation For The State University Of New York | Lithography compositions and methods for forming resist patterns and/or making semiconductor devices |
WO2023195546A1 (ja) * | 2022-04-08 | 2023-10-12 | 三菱瓦斯化学株式会社 | ヨウ素原子を有する環状化合物 |
EP4290309A1 (en) * | 2022-06-10 | 2023-12-13 | Shin-Etsu Chemical Co., Ltd. | Resist underlayer film material, patterning process, and method for forming resist underlayer film |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015161823A (ja) * | 2014-02-27 | 2015-09-07 | 富士フイルム株式会社 | パターン形成方法、電子デバイスの製造方法、及び、電子デバイス、並びに、感活性光線性又は感放射線性樹脂組成物、及び、レジスト膜 |
WO2017043561A1 (ja) * | 2015-09-10 | 2017-03-16 | 三菱瓦斯化学株式会社 | 化合物、樹脂、レジスト組成物又は感放射線性組成物、レジストパターン形成方法、アモルファス膜の製造方法、リソグラフィー用下層膜形成材料、リソグラフィー用下層膜形成用組成物、回路パターンの形成方法、及び、精製方法 |
JP2018172640A (ja) * | 2017-03-31 | 2018-11-08 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | 酸開裂性モノマー及びこれを含むポリマー |
JP2019061217A (ja) * | 2017-09-25 | 2019-04-18 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
JP2019101417A (ja) * | 2017-11-29 | 2019-06-24 | 信越化学工業株式会社 | パターン形成方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6196897B2 (ja) | 2013-12-05 | 2017-09-13 | 東京応化工業株式会社 | ネガ型レジスト組成物、レジストパターン形成方法及び錯体 |
-
2021
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015161823A (ja) * | 2014-02-27 | 2015-09-07 | 富士フイルム株式会社 | パターン形成方法、電子デバイスの製造方法、及び、電子デバイス、並びに、感活性光線性又は感放射線性樹脂組成物、及び、レジスト膜 |
WO2017043561A1 (ja) * | 2015-09-10 | 2017-03-16 | 三菱瓦斯化学株式会社 | 化合物、樹脂、レジスト組成物又は感放射線性組成物、レジストパターン形成方法、アモルファス膜の製造方法、リソグラフィー用下層膜形成材料、リソグラフィー用下層膜形成用組成物、回路パターンの形成方法、及び、精製方法 |
JP2018172640A (ja) * | 2017-03-31 | 2018-11-08 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | 酸開裂性モノマー及びこれを含むポリマー |
JP2019061217A (ja) * | 2017-09-25 | 2019-04-18 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
JP2019101417A (ja) * | 2017-11-29 | 2019-06-24 | 信越化学工業株式会社 | パターン形成方法 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20230286890A1 (en) * | 2020-09-08 | 2023-09-14 | Innoverda | Method for synthesizing 3,5-diiodo-4-hydroxy benzyl alcohol |
US11834396B2 (en) * | 2020-09-08 | 2023-12-05 | Innoverda | Method for synthesizing 3,5-diiodo-4-hydroxy benzyl alcohol |
WO2023158848A3 (en) * | 2022-02-18 | 2023-09-21 | The Research Foundation For The State University Of New York | Lithography compositions and methods for forming resist patterns and/or making semiconductor devices |
WO2023195546A1 (ja) * | 2022-04-08 | 2023-10-12 | 三菱瓦斯化学株式会社 | ヨウ素原子を有する環状化合物 |
EP4290309A1 (en) * | 2022-06-10 | 2023-12-13 | Shin-Etsu Chemical Co., Ltd. | Resist underlayer film material, patterning process, and method for forming resist underlayer film |
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JPWO2021157551A1 (ja) | 2021-08-12 |
KR20220137951A (ko) | 2022-10-12 |
US20230096137A1 (en) | 2023-03-30 |
CN115053183A (zh) | 2022-09-13 |
TW202142957A (zh) | 2021-11-16 |
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