WO2022131277A1 - 樹脂組成物、硬化膜、硬化膜の製造方法、多層膜付き基板、パターン付き基板の製造方法、感光性樹脂組成物、パターン硬化膜の製造方法、重合体の製造方法及び樹脂組成物の製造方法 - Google Patents

樹脂組成物、硬化膜、硬化膜の製造方法、多層膜付き基板、パターン付き基板の製造方法、感光性樹脂組成物、パターン硬化膜の製造方法、重合体の製造方法及び樹脂組成物の製造方法 Download PDF

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Publication number
WO2022131277A1
WO2022131277A1 PCT/JP2021/046165 JP2021046165W WO2022131277A1 WO 2022131277 A1 WO2022131277 A1 WO 2022131277A1 JP 2021046165 W JP2021046165 W JP 2021046165W WO 2022131277 A1 WO2022131277 A1 WO 2022131277A1
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Prior art keywords
group
less
general formula
resin composition
carbon atoms
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Ceased
Application number
PCT/JP2021/046165
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English (en)
French (fr)
Japanese (ja)
Inventor
毅 増渕
祐梨 及川
一広 山中
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Central Glass Co Ltd
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Central Glass Co Ltd
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Publication date
Application filed by Central Glass Co Ltd filed Critical Central Glass Co Ltd
Priority to JP2022570027A priority Critical patent/JPWO2022131277A1/ja
Priority to KR1020237022904A priority patent/KR20230118902A/ko
Priority to CN202180081688.9A priority patent/CN116601210A/zh
Publication of WO2022131277A1 publication Critical patent/WO2022131277A1/ja
Priority to US18/334,125 priority patent/US20230333468A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58—Metal-containing linkages
    • 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
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • 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
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G03F7/2006—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light using coherent light; using polarised light
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/201—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by an oblique exposure; characterised by the use of plural sources; characterised by the rotation of the optical device; characterised by a relative movement of the optical device, the light source, the sensitive system or the mask

Definitions

  • the present disclosure discloses a resin composition, a cured film, a method for producing a cured film, a substrate with a multilayer film, a method for producing a patterned substrate, a photosensitive resin composition, a method for producing a patterned cured film, a method for producing a polymer, and a resin composition. Regarding the manufacturing method of goods.
  • LSI Large Scale Integration
  • LSI manufacturing a pattern forming substrate is transferred by dry etching the substrate with a chlorine-based gas or a fluorine-based gas via a resist pattern formed by exposure development on the substrate according to lithography. Is manufactured. At this time, a resin having a chemical structure having etching resistance against these gases is used as the resist.
  • Such resists include a positive type resist in which the exposed part is solubilized by irradiation with light and a negative type resist in which the exposed part is insoluble, and either of them is used.
  • g-line (wavelength 463 nm) and i-line (wavelength 365 nm) emitted by a high-pressure mercury lamp, ultraviolet rays having a wavelength of 248 nm oscillated by a KrF excimer laser or a wavelength of 193 nm oscillated by an ArF excimer laser, or extreme ultraviolet light (hereinafter referred to as EUV). May be called) etc. are used.
  • a multilayer resist method is known in order to disintegrate the pattern when forming the resist pattern and to improve the etching resistance of the resist.
  • the absorbance of EUV light is low in the conventional resist layer made of hydrocarbons. Therefore, for example, in Patent Document 1 and Non-Patent Document 1, EUV absorbance is applied to the underlying film of the resist. It is described that by using a high material (using MoSi pairs as a multi-layer stack), secondary electrons from EUV photons are returned from the underlayer film to the resist side, and EUV light sensitivity (utilization efficiency of EUV light) is enhanced. There is.
  • the present disclosure provides a resin composition which is a uniform liquid containing the obtained polymer, which is hydrolyzed and polycondensed without precipitating during the sol-gel reaction even if a metal species having high EUV absorbance is introduced. That is one of the issues.
  • the polymer may be a copolymer obtained by hydrolyzing and polycondensing a monomer of a metal species having a high EUUV absorbance and a monomer of a sol-gel raw material other than the above. Further, it may be a copolymer obtained by hydrolyzing and polycondensing the monomer of the metal species having high EUV absorbance in advance to form an oligomer, and then hydrolyzing and polycondensing the monomer of the other sol-gel raw material.
  • it may be a copolymer obtained by hydrolyzing and polycondensing a monomer of the other sol-gel raw material in advance to form an oligomer, and then hydrolyzing and polycondensing the monomer of a metal species having high EUV absorbance.
  • the above-mentioned monomer of a metal species having high EUV absorptivity is preliminarily hydrolyzed and polycondensed to form an oligomer
  • the other monomers of the sol-gel raw material are preliminarily hydrolyzed and polycondensed to form an oligomer.
  • the above-mentioned monomer of a metal species having high EUV absorptivity is polymerized by hydrolyzing and polycondensing in advance, and the other monomers of the sol-gel raw material are polymerized by pre-hydrolyzing and polycondensing. May be a mixture obtained by mixing (hereinafter, may also be referred to as “blend”).
  • one of the problems is to provide a cured film obtained by curing a resin composition or a method for producing the same.
  • Another object of the present invention is to provide a substrate with a multilayer film having a lower layer film of a resist which is a cured product of a resin composition, or a method for manufacturing a patterned substrate using a substrate with a multilayer film.
  • Another object of the present disclosure is to provide a photosensitive resin composition containing a resin composition or a method for producing a pattern cured film formed by applying a photosensitive resin composition on a substrate. ..
  • Another object of the present disclosure is to provide a method for producing a polymer obtained by hydrolysis and polycondensation without precipitation during a sol-gel reaction even if a metal species having high EUV absorbance is introduced. ..
  • one of the problems is to provide a method for producing a resin composition for treating the obtained polymer.
  • Each of R 1 independently has a hydrogen atom, a hydroxy group, a halogen group, an alkoxy group having 1 or more and 5 or less carbon atoms, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 10 or less carbon atoms.
  • Is. b is a number of 0 or more and less than 4
  • c is a number of more than 0 and 4 or less
  • b + c 3 or 4.
  • R 2 is a group represented by the following general formula (1a).
  • X is a hydrogen atom or an acid instability group.
  • a is a number from 1 to 5, and the broken line represents a bond.
  • R 3 is an independent hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 10 or less carbon atoms
  • R 4 is an independent hydrogen atom or carbon number. It is an alkyl group of 1 or more and 5 or less.
  • d is a number of 1 or more and 3 or less
  • e is a number of 0 or more and 2 or less
  • f is a number of 0 or more and less than 3
  • g is a number of more than 0 and 3 or less
  • d + e + f + g 4.
  • Each of R 1 independently has a hydrogen atom, a hydroxy group, a halogen group, an alkoxy group having 1 or more and 5 or less carbon atoms, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 10 or less carbon atoms.
  • Is. b is a number of 0 or more and less than 4
  • c is a number of more than 0 and 4 or less
  • b + c 3 or 4.
  • R 2 is a group represented by the following general formula (1a).
  • X is a hydrogen atom or an acid unstable group.
  • a is a number from 1 to 5, and the broken line represents a bond.
  • R 3 is an independent hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 10 or less carbon atoms
  • R 4 is an independent hydrogen atom or carbon number. It is an alkyl group of 1 or more and 5 or less.
  • d is a number of 1 or more and 3 or less
  • e is a number of 0 or more and 2 or less
  • f is a number of 0 or more and less than 3
  • g is a number of more than 0 and 3 or less
  • d + e + f + g 4.
  • the group represented by the general formula (1a) may be any of the groups represented by the following general formulas (1aa) to (1ad).
  • X and the broken line are the same as the definitions in the general formula (1a).
  • the above polymer or At least one of the above (a) a polysiloxane compound having a structural unit represented by the general formula (1) and (b) a metalloxane compound having a structural unit represented by the general formula (1-A) is It may further include a structural unit represented by the following general formula (2) and / or the following general formula (3).
  • R5 is a substitution selected from monovalent organic groups having 1 or more and 30 or less carbon atoms substituted with any of an epoxy group, an oxetane group, an acryloyl group, a methacryloyl group or a lactone group. It is a group.
  • R 6 is selected from the group consisting of a hydrogen atom, a halogen group, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, a hydroxy group, an alkoxy group having 1 or more and 3 or less carbon atoms, and a fluoroalkyl group having 1 or more and 10 or less carbon atoms. It is a substituent to be used.
  • h is a number of 1 or more and 3 or less
  • i is a number of 0 or more and less than 3
  • j is a number of more than 0 and 3 or less
  • h + i + j 4.
  • R 5 and R 6 When there are a plurality of R 5 and R 6 , each of them is independently selected from any of the above-mentioned substituents.
  • R 7 is a substituent selected from the group consisting of a halogen group, an alkoxy group and a hydroxy group.
  • k is a number of 0 or more and less than 4
  • l is a number of more than 0 and 4 or less
  • k + l 4.
  • the monovalent organic group R 5 may be any of the groups represented by the following general formulas (2a), (2b), (2c), (3a) or (4a).
  • R g , R h and R i each independently represent a divalent linking group, and the broken line represents a bond.
  • R j and R k each independently represent a divalent linking group, and the broken line represents a bond.
  • M may be at least one selected from the group consisting of Ge, ⁇ o and W.
  • the resin composition is (C) A solvent may be further contained.
  • the solvent is propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, ⁇ -butyrolactone, diacetone alcohol, jigglime, methyl isobutyl ketone, 3-methoxybutyl acetate, 2-heptanone, N, N-. It may contain at least one compound selected from the group consisting of dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, glycols, glycol ethers and glycol ether esters.
  • a cured film obtained by curing the above resin composition is provided.
  • a method for producing a cured film which comprises a step of applying the above resin composition on a substrate and then heating it at a temperature of 80 ° C. or higher and 350 ° C. or lower.
  • a substrate with a multilayer film which has an organic layer on a substrate, a lower layer film of a resist which is a cured product of the resin composition on the organic layer, and a resist layer on the lower layer film. ..
  • a method for manufacturing a patterned substrate is provided, which comprises a step 3 and a fourth step of performing dry etching of a substrate through a pattern of an organic layer to obtain a pattern on the substrate.
  • the underlayer film is dry-etched with a fluorine-based gas
  • the organic layer is dry-etched with an oxygen-based gas
  • the fluorine-based gas or chlorine-based gas is used. Dry etching of the base material may be performed.
  • the wavelength of the light beam used for exposure may be 1 nm or more and 600 nm or less.
  • the wavelength of the light beam used for exposure may be 6 nm or more and 27 nm or less.
  • the above resin composition and (D) A photosensitive resin composition containing a photoinduced compound is provided.
  • the photoinduced compound may be at least one selected from the group consisting of naphthoquinone diazide, a photoacid generator, a photobase generator and a photoradical generator.
  • the photosensitive resin composition is applied onto a substrate to form a photosensitive coating film, the photosensitive coating film is exposed via a photomask, and the exposed photosensitive coating film is obtained.
  • a method for producing a pattern cured film which comprises developing, forming a pattern film, and heating the pattern film to cure the pattern film to form a pattern cured film.
  • the photosensitive coating film may be exposed via a photomask by irradiating a light beam having a wavelength of 1 nm or more and 600 nm or less.
  • the produced polymer has a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (1-A).
  • R 3 is an independent hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 10 or less carbon atoms, and R 4 is independent of each other.
  • X is a hydrogen atom or an acid instability group.
  • M is at least one selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ga, Ge, ⁇ o, Pd, Ag, Sn, Cs, Ba, W and Hf. be.
  • R 8 is independently a hydrogen atom, a hydroxy group, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 10 or less carbon atoms
  • R 9 is an alkoxy having 1 to 5 carbon atoms. It is a group or a halogen.
  • m is a number of 0 or more and 3 or less
  • n is a number of 1 or more and 4 or less
  • m + n 3 or 4.
  • M is at least one selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ga, Ge, ⁇ o, Pd, Ag, Sn, Cs, Ba, W and Hf.
  • R 1 is independently a hydrogen atom, a hydroxy group, a halogen group, an alkoxy group having 1 or more and 5 or less carbon atoms, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoro group having 1 or more and 10 or less carbon atoms. It is an alkyl group.
  • b is a number of 0 or more and less than 4
  • c is a number of more than 0 and 4 or less
  • b + c 3 or 4.
  • R 2 is a group represented by the following general formula (1a).
  • X is a hydrogen atom or an acid instability group.
  • a is a number from 1 to 5, and the broken line represents a bond.
  • R 3 is an independent hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 10 or less carbon atoms
  • R 4 is an independent hydrogen atom or carbon number. It is an alkyl group of 1 or more and 5 or less.
  • d is a number of 1 or more and 3 or less
  • e is a number of 0 or more and 2 or less
  • f is a number of 0 or more and less than 3
  • g is a number of more than 0 and 3 or less
  • d + e + f + g 4.
  • a chelating agent may be added to the metal compound represented by the general formula (1-2) at or before hydrolysis polycondensation.
  • the polymer obtained by the above production method is subjected to at least one operation selected from the group consisting of dilution with a solvent, concentration, extraction, washing with water, ion exchange resin purification and filtration. Manufacturing method is provided.
  • a homogeneous liquid containing the obtained polymer is hydrolyzed and polycondensed without precipitating components derived from the raw materials during the sol-gel reaction.
  • a cured product of the resin composition or a method for producing the same is provided.
  • a substrate with a multilayer film having a lower layer film of a resist which is a cured product of a resin composition, or a method for manufacturing a patterned substrate using a substrate with a multilayer film is provided.
  • a method for producing a patterned cured film formed by applying a photosensitive resin composition containing a resin composition or a photosensitive resin composition onto a substrate is provided.
  • the resin composition, the cured film, the method for producing the cured film, the substrate with the multilayer film, the method for producing the patterned substrate, the photosensitive resin composition, the method for producing the patterned cured film, and the polymer according to the embodiment of the present invention The production method and the production method of the resin composition will be described. However, the embodiments of the present invention are not construed as being limited to the contents described in the embodiments and examples shown below. In the present specification, the notation "Xa to Ya" in the description of the numerical range shall indicate Xa or more and Ya or less unless otherwise specified.
  • the present inventors have made a raw material of a specific structural unit containing a hexafluoroisopropanol (HFIP) group represented by the general formula (1) described later, and a high EUV absorbance.
  • HFIP hexafluoroisopropanol
  • a raw material of a specific structural unit represented by the general formula (1-A) described later which contains a metal species, hydrolysis / polycondensation is performed while suppressing the precipitation of the raw material-derived component in the sol-gel reaction.
  • a resin composition which is a uniform liquid containing a polymer can be obtained.
  • the present inventors have obtained a polysiloxane compound obtained by polymerizing a raw material of a specific structural unit containing a hexafluoroisopropanol (HFIP) group represented by the general formula (1), and a metal species having high EUV absorbance.
  • HFIP hexafluoroisopropanol
  • a metal species having high EUV absorbance When combined with a metalloxane compound obtained by polymerizing a raw material of a specific structural unit represented by the general formula (1-A), precipitation can be suppressed in the blend of both, and as a result, a mixture is contained. It has been found that a resin composition which is a uniform liquid can be obtained.
  • a cured film containing a metal species having a high EUV absorbance uniformly can be obtained. Therefore, in a substrate with a multilayer film using the cured film as an underlayer film of a resist. , It has been found that excellent etching selectivity can be obtained.
  • sedimentation in the present specification means a state in which a precipitate derived from a raw material and / or a precipitate cannot be visually confirmed in the resin composition or the photosensitive resin composition. Further, in the present specification, the state in which sedimentation is suppressed may be described as "dispersion”.
  • the term "dispersion” means, for example, that the structural unit represented by the general formula (1-A) (B) interacts with other components contained in the resin composition or the photosensitive resin composition. For example, it may refer to a state of being incorporated into the network through a copolymerization reaction or the like).
  • the resin composition or the photosensitive resin composition contains a precipitate, there is a concern that the smoothness of the film surface at the time of film formation may be impaired. In addition, there is a concern that the precipitates contained in the resin composition and the photosensitive resin composition may cause film cracking. Further, fine particles larger than the EUV wavelength may adversely affect EUV exposure.
  • these problems in the prior art are solved by the fact that the resin composition and the photosensitive resin composition according to the present invention are uniform liquids.
  • the resin composition of the present invention has a structural unit represented by the general formula (1) (A) and a structural unit represented by the general formula (1-A) (B). Includes polymers with.
  • the resin composition of the present invention is a polysiloxane compound having a structural unit represented by the general formula (1), and a configuration represented by the general formula (1-A). It contains a metalloxane compound (b) having a unit and a polymer having the unit.
  • (A) is a structural unit represented by the following general formula (1) (hereinafter, also referred to as “first structural unit”). Further, (a) is a polysiloxane compound having a structural unit represented by the following general formula (1). [(R 2 ) d (R 3 ) e (OR 4 ) f SiO g / 2 ] (1)
  • R 2 is a group represented by the following general formula (1a).
  • X is a hydrogen atom or an acid instability group.
  • a is a number from 1 to 5, and the broken line represents a bond.
  • R 3 is an independent hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 10 or less carbon atoms
  • R 4 is an independent hydrogen atom or carbon number. It is an alkyl group of 1 or more and 5 or less.
  • d is a number of 1 or more and 3 or less
  • e is a number of 0 or more and 2 or less
  • f is a number of 0 or more and less than 3
  • g is a number of more than 0 and 3 or less
  • d + e + f + g 4.
  • g may be a decimal number that is rounded to 0 or more and 3 or less (where g ⁇ 0).
  • g is an integer of 0 to 3
  • g is a decimal number that is rounded to 0 or more and 3 or less (however, g ⁇ 0). It means that a monomer can be taken as a constituent unit of, but it shows that not all of them are a monomer.
  • a is an integer of 1 or more and 5 or less as a theoretical value.
  • the value obtained by the 29 Si NMR measurement may be a decimal number in which a is rounded to 1 or more and 5 or less.
  • the group represented by the general formula (1a) may be any of the groups represented by the following general formulas (1aa) to (1ad).
  • X and the broken line are the same as the definitions in the general formula (1a).
  • the polymer in the resin composition of the present invention or a polysiloxane compound having a structural unit represented by the general formula (1) is represented by (a) and the general formula (1-A).
  • At least one of (b), which is a metalloxane compound having a structural unit is a structural unit represented by the following general formula (2) (hereinafter, also referred to as “second structural unit”) and / or the following general formula (hereinafter, also referred to as “second structural unit”).
  • the structural unit represented by 3) (hereinafter, also referred to as “third structural unit”) may be further included.
  • R5 is a substitution selected from monovalent organic groups having 1 or more and 30 or less carbon atoms substituted with any of an epoxy group, an oxetane group, an acryloyl group, a methacryloyl group or a lactone group. It is a group.
  • R 6 is selected from the group consisting of a hydrogen atom, a halogen group, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, a hydroxy group, an alkoxy group having 1 or more and 3 or less carbon atoms, and a fluoroalkyl group having 1 or more and 10 or less carbon atoms. It is a substituent to be used.
  • h is a number of 1 or more and 3 or less
  • i is a number of 0 or more and less than 3
  • j is a number of more than 0 and 3 or less
  • h + i + j 4.
  • R 7 is a substituent selected from the group consisting of a halogen group, an alkoxy group and a hydroxy group.
  • k is a number of 0 or more and less than 4
  • l is a number of more than 0 and less than 4
  • k + l 4.
  • the presence of the HFIP group in (A) means that Fe, Co, Ni, Cu, Zn, Ga, Ge, ⁇ o, Pd, Ag, Sn, Cs, Ba, W, It is considered that the precipitation of the component derived from the raw material (B) containing a metal species having high EUV absorbance such as Hf and Hf can be suppressed, and as a result, the resin composition and the photosensitive resin composition of the present invention can be obtained. ..
  • Og / 2 in the general formula (1) is generally used as a notation of a compound having a siloxane bond, and in the following formula (1-1), g is 1, and the formula (1-) is used. 2) represents the case where g is 2, and the formula (1-3) represents the case where g is 3. When g is 1, it is located at the end of the siloxane chain in the compound having a siloxane bond.
  • R x is synonymous with R 2 in the general formula (1), and R a and R b are independently R in the general formula (1). It is synonymous with 2 , R 3 , and OR 4 .
  • the broken line represents a bond with another Si atom.
  • j is 1 in the following general formula (2-1), j is 2 in the general formula (2-2), and the general formula (2-3) is the same as above.
  • j is 3.
  • j is 1, it is located at the end of the siloxane chain in the compound having a siloxane bond.
  • R y is synonymous with R 5 in the general formula (2), and R a and R b are independently R in the general formula (2). It is synonymous with 5 and R6 .
  • the broken line represents a bond with another Si atom.
  • the broken line represents a bond with another Si atom.
  • O 4/2 in the above general formula (3) is generally called a Q4 unit, and shows a structure in which all four bonds of Si atoms form a siloxane bond.
  • the general formula (3) may include a hydrolyzable / condensable group in the bond, such as the Q0, Q1, Q2, and Q3 units shown below. Further, the general formula (3) may have at least one selected from the group consisting of Q1 to Q4 units.
  • Q0 unit A structure in which all four bonds of the Si atom are groups capable of hydrolyzing and polycondensing (groups capable of forming a siloxane bond, such as a halogen group, an alkoxy group, or a hydroxy group).
  • Q1 unit A structure in which one of the four bonds of the Si atom forms a siloxane bond and the remaining three are all hydrolyzable / polycondensable groups.
  • Q2 unit Of the four bonds of Si atoms, two form a siloxane bond and the remaining two are all hydrolyzable / polycondensable groups.
  • Q3 unit A structure in which three of the four bonds of the Si atom form a siloxane bond, and the remaining one is a group capable of hydrolyzing and polycondensing.
  • R 2 is a group represented by the following general formula (1a).
  • X is a hydrogen atom or an acid instability group.
  • a is a number from 1 to 5, and the broken line represents a bond.
  • the acid instability group is a group desorbed by the action of a so-called acid, and may contain an oxygen atom, a carbonyl bond, and a fluorine atom as a part thereof.
  • the acid instability group can be used without particular limitation as long as it is a photo-induced compound containing a photoacid generator or a group that undergoes desorption due to the effect of hydrolysis, etc., but if a specific example is given, it can be used.
  • Examples thereof include an alkyl group, an alkyloxycarbonyl group, an acetal group, a silyl group, an acyl group and the like.
  • alkyl group tert-butyl group, tert-amyl group, 1,1-dimethylpropyl group, 1-ethyl-1-methylpropyl group, 1,1-dimethylbutyl group, allyl group, 1-pyrenylmethyl group, 5 -Dibenzosveryl group, triphenylmethyl group, 1-ethyl-1-methylbutyl group, 1,1-diethylpropyl group, 1,1-dimethyl-1-phenylmethyl group, 1-methyl-1-ethyl-1- Phenylmethyl group, 1,1-diethyl-1-phenylmethyl group, 1-methylcyclohexyl group, 1-ethylcyclohexyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-isobornyl group, 1-methyladamantyl group , 1-Ethyl adamantyl group, 1-isopropyl adamantyl group, 1-iso
  • the alkyl group is preferably a tertiary alkyl group, more preferably a group represented by —CR p R q R r (R p , R q and R r are independently linear or branched alkyl, respectively). It is a group, a monocyclic or polycyclic cycloalkyl group, an aryl group or an aralkyl group, and two of R p , R q and R r may be bonded to form a ring structure).
  • alkoxycarbonyl group examples include a tert-butoxycarbonyl group, a tert-amyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group and the like.
  • examples of the acetal group include methoxymethyl group, ethoxyethyl group, butoxyethyl group, cyclohexyloxyethyl group, benzyloxyethyl group, phenethyloxyethyl group, ethoxypropyl group, benzyloxypropyl group, phenethyloxypropyl group and ethoxybutyl group. Examples thereof include an ethoxyisobutyl group.
  • silyl group examples include a trimethylsilyl group, an ethyldimethylsilyl group, a methyldiethylsilyl group, a triethylsilyl group, an i-propyldimethylsilyl group, a methyldi-i-propylsilyl group, a tri-i-propylsilyl group and t-butyl.
  • Examples thereof include a dimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, a triphenylsilyl group and the like.
  • acyl group examples include an acetyl group, a propionyl group, a butyryl group, a heptanoyle group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a lauroyl group, a myritoyl group, a palmitoyl group, a stearoyl group, an oxalyl group, a malonyl group and a succinyl group.
  • Glutaryl group adipoil group, pimeroyl group, subberoyl group, azella oil group, sebacoil group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoil group, fumaroyl group, mesaconoyl group, canhoroyl group, benzoyl group, phthaloyl group.
  • Examples thereof include a group, an isophthaloyl group, a terephthaloyl group, a naphthoyl group, a toluoil group, a hydroatropoil group, an atropoyl group, a cinnamoyl group, a floyl group, a tenoyl group, a nicotinoyle group, an isonicotinoyl group and the like.
  • a tert-butoxycarbonyl group, a methoxymethyl group, an ethoxyethyl group and a trimethylsilyl group are generally preferable.
  • those in which some or all of the hydrogen atoms of these acid instability groups are replaced with fluorine atoms can also be used.
  • a single type of these acid instability groups may be used, or a plurality of types may be used.
  • Particularly preferable structures of the acid instability group include a structure represented by the following general formula (ALG-1) and a structure represented by the following general formula (ALG-2).
  • R 11 is a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms.
  • R 12 is a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms or 7 to 7 carbon atoms.
  • R 13 , R 14 and R 15 are each independently a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 3 to 10 carbon atoms, and 6 to 20 carbon atoms. It is an aryl group or an aralkyl group having 7 to 21 carbon atoms. Two of R 13 , R 14 and R 15 may combine with each other to form a ring structure. * Represents the binding site with the oxygen atom.
  • Each of R 3 is independently a hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 10 or less carbon atoms.
  • Each of R4 is independently a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms.
  • d is a number of 1 or more and 3 or less
  • e is a number of 0 or more and 2 or less
  • f is a number of 0 or more and less than 3
  • g is a number of more than 0 and 3 or less
  • d + e + f + g 4.
  • R3 a hydrogen atom, a methyl group, an ethyl group, a 3,3,3-trifluoropropyl group and a phenyl group can be specifically exemplified.
  • R4 specifically, a hydrogen atom, a methyl group, and an ethyl group can be exemplified.
  • d is preferably an integer of 1 or 2.
  • e is preferably an integer of 0 or more and 2 or less, and more preferably an integer of 0 or 1.
  • f is preferably an integer of 0 or more and 2 or less, and more preferably an integer of 0 or 1.
  • g is preferably an integer of 1 or more and 3 or less, and more preferably an integer of 2 or 3.
  • a is preferably 1 or 2.
  • d is a number of 1 or more and 2 or less.
  • e is preferably a number of 0 or more and 2 or less, and more preferably 0 or more and 1 or less.
  • f is preferably a number of 0 or more and 2 or less, and more preferably 0 or more and 1 or less.
  • g is preferably a number of 1 or more and 3 or less, and more preferably 2 or more and 3 or less.
  • the number of HFIP group-containing aryl groups represented by the general formula (1a) in the general formula (1) is preferably one. That is, the structural unit in which d is 1 is an example of a particularly preferable structural unit of the general formula (1).
  • any of the groups represented by the general formulas (1aa) to (1ad) is particularly preferable.
  • the first structural unit represented by the general formula (1) preferably consists of a single structural unit.
  • “consisting of a single structural unit” means the number of a, the number of d, the number of substituents of R 3 and the number of e, and the substitution of OR 4 in the general formula (1). It means that it is composed of a structural unit in which the number of the basic species (excluding the hydroxy group and the alkoxy group) and the number f (however, excluding the number of the hydroxy group and the alkoxy group in f) are equal.
  • R5 is selected from monovalent organic groups having 1 to 30 carbon atoms substituted with any of an epoxy group, an oxetane group, an acryloyl group, a methacryloyl group, or a lactone group. It is a substituent.
  • R 6 is selected from the group consisting of a hydrogen atom, a halogen group, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, a hydroxy group, an alkoxy group having 1 or more and 3 or less carbon atoms, and a fluoroalkyl group having 1 or more and 10 or less carbon atoms. It is a substituent to be used.
  • h is a number of 1 or more and 3 or less
  • i is a number of 0 or more and less than 3
  • j is a number of more than 0 and 3 or less
  • h + i + j 4.
  • i is preferably an integer of 0 or more and 2 or less, and more preferably an integer of 0 or 1.
  • j is preferably an integer of 1 or more and 3 or less, and more preferably an integer of 2 or 3.
  • the value of h is particularly preferably 1.
  • the structural unit in which h is 1, i is 0, and j is 3, is an example of a particularly preferable structural unit of the general formula (2).
  • R 6 include a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a methoxy group, an ethoxy group, and a propoxy group.
  • h is preferably a number of 1 or more and 2 or less, and more preferably 1.
  • i is preferably a number of 0 or more and 2 or less, and more preferably 0 or more and 1 or less.
  • j is preferably a number of 1 or more and 3 or less, and more preferably 2 or more and 3 or less.
  • the R5 group of the second structural unit represented by the general formula (2) contains an epoxy group, an oxetane group, or a lactone group, from the resin composition or the photosensitive resin composition which is one embodiment. Good adhesion to various base materials having silicon, glass, resin or the like on the contact surface can be imparted to the obtained cured film or pattern cured film.
  • the R5 group contains an acryloyl group or a methacryloyl group, a highly curable film can be obtained and good solvent resistance can be obtained.
  • the R5 group contains an epoxy group and an oxetane group
  • the R5 group is preferably a group represented by the following general formulas ( 2a), (2b) and (2c).
  • R g , R h and R i each independently represent a divalent linking group.
  • the dashed line represents the bond.
  • examples of the divalent linking group include alkylene groups having 1 to 20 carbon atoms, forming an ether bond. It may contain one or more sites. When the number of carbon atoms is 3 or more, the alkylene group may be branched, or distant carbons may be connected to form a ring. When the number of alkylene groups is two or more, oxygen may be inserted between carbons to form one or more sites forming an ether bond, and as divalent linking groups, these may be contained. This is a preferred example.
  • a particularly preferable one is represented by alkoxysilane as a raw material, 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.).
  • R5 group contains an acryloyl group or a methacryloyl group, it is preferably a group selected from the following general formula (3a) or (4a).
  • R j and R k each independently represent a divalent linking group.
  • the dashed line represents the bond.
  • R j and R k are divalent linking groups, those mentioned as preferable groups in R g , R h and Ri can be mentioned again.
  • R5 group contains a lactone group
  • the following formulas (5-1) to (5-20) and formulas (6-1) to (6-7) are used.
  • R 7 is a substituent selected from the group consisting of a halogen group, an alkoxy group, and a hydroxy group.
  • k is a number of 0 or more and less than 4
  • l is a number of more than 0 and less than 4
  • k + l 4.
  • k is a number of 0 or more and 3 or less.
  • l is preferably a number of 1 or more and 4 or less.
  • Ol / 2 in the general formula (3) may have at least one selected from the group consisting of Q1 to Q4 units. It may also include a Q0 unit.
  • Q0 unit A structure in which all four bonds of the Si atom are groups capable of hydrolyzing and polycondensing (groups capable of forming a siloxane bond, such as a halogen group, an alkoxy group, or a hydroxy group).
  • Q1 unit A structure in which one of the four bonds of the Si atom forms a siloxane bond and the remaining three are all hydrolyzable / polycondensable groups.
  • Q2 unit Of the four bonds of Si atoms, two form a siloxane bond and the remaining two are all hydrolyzable / polycondensable groups.
  • Q3 unit A structure in which three of the four bonds of the Si atom form a siloxane bond, and the remaining one is a group capable of hydrolyzing and polycondensing.
  • Q4 unit A structure in which all four bonds of Si atoms form a siloxane bond.
  • the third structural unit represented by the general formula (3) has a structure similar to SiO 2 in which organic components are eliminated as much as possible, a cured film or a pattern cured film obtained from a resin composition or a photosensitive resin composition Can be imparted with heat resistance, transparency, and chemical resistance.
  • the third structural unit represented by the general formula (3) is tetraalkoxysilane, tetrahalosilane (for example, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, etc.).
  • tetraalkoxysilane for example, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, etc.
  • it is a polymer by using those oligomers as a raw material and hydrolyzing and polycondensing them, or a polysiloxane compound having a structural unit represented by the general formula (1) (a) and the general formula (1-). It can be incorporated into at least one of (b), which is a metalloxane
  • silicate 40 (average pentamer, manufactured by Tama Chemical Industry Co., Ltd.), ethyl silicate 40 (average pentamer, manufactured by Corcote Co., Ltd.), silicate 45 (average heptameric, manufactured by Tama Chemical Industry Co., Ltd.).
  • M silicate 51 (average tetramer, manufactured by Tama Chemical Industry Co., Ltd.), methyl silicate 51 (average tetramer, manufactured by Corcote Co., Ltd.), methyl silicate 53A (average heptameric, manufactured by Corcote Co., Ltd.), ethyl silicate
  • examples thereof include silicate compounds such as 48 (average tetramer, manufactured by Corcote Co., Ltd.) and EMS-485 (mixture of ethyl silicate and methyl silicate, manufactured by Corcote Co., Ltd.). From the viewpoint of ease of handling, silicate compounds are preferably used.
  • the structural unit (first structural unit) represented by the general formula (1) is contained in an amount of 5 mol% to 100 mol%. Is preferable. It is more preferably contained in an amount of 8 mol% to 100 mol%.
  • the ratio of each structural unit in at least one of the compound (a) and the metalloxane compound (b) having a structural unit represented by the general formula (1-A) in Si atom is the second, respectively. It is preferable that the constituent unit of the above is 0 to 80 mol% and the third constituent unit is 0 to 90 mol% (however, the second constituent unit and the third constituent unit are 1 to 95 mol% in total).
  • the second constituent unit may be more preferably 2 to 70 mol%, still more preferably 5 to 40 mol%.
  • the third structural unit may be more preferably in the range of less than 5 mol% or more than 50 mol%, and further preferably in the range of less than 5 mol% or more than 60 mol%.
  • the lower limit is not limited, but for example, it is preferably 0 mol% or more, and more preferably more than 0 mol%.
  • the upper limit is not limited, but may be, for example, 95 mol% or less.
  • the mol% of Si atoms can be determined, for example, from the peak area ratio in 29 Si-NMR.
  • at least one of (b) includes adjustment of solubility in a solvent (C) described later, heat resistance when a cured film or a pattern cured film is used, transparency, and the like.
  • other structural units containing Si atoms hereinafter, may be simply referred to as “arbitrary components” may be contained.
  • the optional component include chlorosilane and alkoxysilane. Chlorosilane and alkoxysilane may be referred to as "other Si monomers”.
  • chlorosilane examples include dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, diphenyldichlorosilane, bis (3,3,3-trifluoropropyl) dichlorosilane, and methyl (3,3,3-tri).
  • alkoxysilane examples include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldiphenoxysilane, and dipropyl.
  • phenyltrimethoxysilane, phenyltriethoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane are preferable for the purpose of enhancing the heat resistance and transparency of the obtained pattern cured film, and the flexibility of the obtained pattern cured film is preferable.
  • Dimethyldimethoxysilane and dimethyldiethoxysilane are preferable for the purpose of increasing the amount of dimethyldimethoxysilane and preventing cracks and the like.
  • the ratio of Si atoms contained as an optional component when the total amount of Si atoms contained in at least one of (b) is 100 mol% is not particularly limited, but is, for example, 0 to 99 mol%. It may be preferably 0 to 95 mol%, more preferably 10 to 85 mol%.
  • (b) is a metalloxane compound having a structural unit represented by the following general formula (1-A). [(R 1 ) b MO c / 2 ] (1-A)
  • M is at least one selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ga, Ge, ⁇ o, Pd, Ag, Sn, Cs, Ba, W and Hf.
  • R 1 is independently a hydrogen atom, a hydroxy group, a halogen group, an alkoxy group having 1 or more and 5 or less carbon atoms, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoro group having 1 or more and 10 or less carbon atoms. It is an alkyl group.
  • b is a number of 0 or more and less than 4
  • c is a number of more than 0 and 4 or less
  • b + c 3 or 4.
  • c 0 indicates that the constituent unit is a monomer, and the average value c ⁇ 0 indicates that all of the compounds are not monomers. Therefore, as a theoretical value, c is an integer of 0 to 4, and as a value obtained by the multinuclear NMR measurement, c is a decimal number that is rounded to 0 or more and 4 or less (however, c ⁇ 0).
  • a monomer may be contained in a compound containing a structural unit represented by the general formula (1-A), but it is shown that not all of the compounds are monomers.
  • the structural unit represented by the general formula (1-A) is selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ga, Ge, ⁇ o, Pd, Ag, Sn, Cs, Ba, W and Hf.
  • An alkoxy compound containing a metal, a halogen compound, or an oligomer thereof is used as a raw material, and the raw material is hydrolyzed and polycondensed to form a polymer or a metalloxane compound having a structural unit represented by the general formula (1-A).
  • an alkoxy compound having 1 or more and 5 or less carbon atoms and a halogen compound in which the halogen species is chlorine are preferable.
  • the metal species Ge, ⁇ o, or W, which can be easily removed with a fluorine-based etching gas, is preferable.
  • R 1 is preferably a hydroxy group, a halogen group, an alkoxy group having 1 or more and 5 or less carbon atoms, an alkyl group having 1 or more and 5 or less carbon atoms, or a phenyl group.
  • the monomer giving the structural unit represented by the general formula (1-A) is exemplified by an alkoxy compound, germanium tetramethoxyde, germanium tetraethoxydo, germanium tetrapropoxide, germanium tetrabutoxide, germanium tetraamyloxide, germanium Tetrahexyloxide, germanium tetracyclopentoxide, germanium tetracyclohexyloxide, germanium tetraaryroxide, germanium tetraphenoxide, germanium (mono, di, or tri) methoxy (mono, di, or tri) ethoxydo, germanium (mono) , Di, or tri) ethoxy (mono, di, or tri) propoxide, molybdenum tetraethoxydo, tungsten tetraethoxydo, tungsten tetraphenoxide, and the like can be exemplified.
  • the monomer giving the structural unit represented by the general formula (1-A) is exemplified by a halogen compound, tetrachlorogermanium, tetrabromogermanium, methyltrichlorogermanium, phenyltrichlorogermanium and the like can be exemplified.
  • the content of (B) in the polymer can be appropriately selected.
  • the desired EUV light is used as a cured film or a pattern cured film. It is preferable because it is easy to adjust the sensitivity. Further, it may be more preferably 10% by mass to 80% by mass.
  • the content of (b) with respect to the total amount of (a) and (b) can be appropriately selected.
  • the total of (a) and (b) is 100% by mass and (b) is 1% by mass to 90% by mass
  • the desired EUV light sensitivity is obtained when a cured film or a pattern cured film is used. It is preferable because it is easy to adjust. Further, it may be more preferably 10% by mass to 80% by mass.
  • the content of (B) contained in the resin composition is the M atom in the general formula (1-A) when the cured film obtained by curing the resin composition is measured by X-ray photoelectric spectroscopy. It is preferable that the total content of the above is 0.3 atm% or more and less than 20 atm% from the viewpoint of improving the EUV light sensitivity and the etching selectivity.
  • the content of (b) contained in the resin composition is M in the general formula (1-A) when the cured film obtained by curing the resin composition is measured by X-ray photoelectric spectroscopy. It is preferable that the total content of the atoms is 0.3 atm% or more and less than 20 atm% from the viewpoint of improving the EUV light sensitivity and the etching selectivity.
  • the content of each element is measured by X-ray photoelectric spectroscopy as the abundance ratio of the detected element excluding hydrogen atom.
  • the content of each element is determined by using a photoelectron spectroscope (XPS) of JEOL Ltd. (JEOL), for example, JPS-9000MC, and MgK ⁇ (1253.6eV) as an X-ray source.
  • XPS photoelectron spectroscope
  • JPS-9000MC JPS-9000MC
  • MgK ⁇ 1253.6eV
  • the resin composition is (C) A solvent can be further contained.
  • the solvent is propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, ⁇ -butyrolactone, diacetone alcohol, jigglime, methyl isobutyl ketone, 3-methoxybutyl acetate, 2-heptanone, N, N-. It can contain at least one compound selected from the group consisting of dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, glycols, glycol ethers and glycol ether esters.
  • glycols, glycol ethers, and glycol ether esters include Celtor (registered trademark) manufactured by Daicel Co., Ltd. and Highsolve (registered trademark) manufactured by Toho Kagaku Kogyo Co., Ltd. Specifically, cyclohexanol acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene.
  • the amount of the solvent (C) contained in the resin composition or the photosensitive resin composition is from 50 parts by mass or more to 500 parts by mass.
  • the amount is preferably 40 parts by mass or less, and more preferably 80 parts by mass or more and 400 parts by mass or less.
  • the resin composition may contain the following components as additives as long as the excellent properties of the resin composition are not significantly impaired.
  • an additive such as a surfactant may be contained for the purpose of improving coating property, leveling property, film forming property, storage stability, defoaming property and the like.
  • a commercially available surfactant product name Megafuck manufactured by DIC Co., Ltd., product number F142D, F172, F173 or F183, product name Florard manufactured by Sumitomo 3M Co., Ltd., product number FC-135, FC-170C, FC-430 or FC-431, trade name Surflon manufactured by AGC Seimi Chemical Co., Ltd., product numbers S-112, S-113, S-131, S-141 or S-145, or Toray Dow Corning Silicone. Examples thereof include product names manufactured by SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 manufactured by Japan Ltd.
  • the blending amount thereof is preferably 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of (A) or (a).
  • Megafuck is the trade name of the fluorine-based additive (surfactant / surface modifier) of DIC Co., Ltd.
  • Florard is the trade name of the fluorine-based surfactant manufactured by Sumitomo 3M Co., Ltd.
  • Surflon is AGC Seimi Chemical. It is a trade name of fluorine-based surfactants of Co., Ltd., and each is registered as a trademark.
  • a curing agent can be added for the purpose of improving the chemical resistance of the obtained cured film or pattern cured film.
  • the curing agent include a melamine curing agent, a urea resin curing agent, a polybasic acid curing agent, an isocyanate curing agent, and an epoxy curing agent. It is considered that the curing agent mainly reacts with the hydroxy group or the alkoxy group contained in (A) or (B) or (a) or (b) to form a crosslinked structure.
  • isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate or diphenylmethane diisocyanate, and melamine resins or ureas such as isocyanurate, blocked isocyanate or biuret, alkylated melamine, methylol melamine, imino melamine and the like.
  • An example can be exemplified of an epoxy curing agent having two or more epoxy groups obtained by reacting an amino compound such as a resin or a polyvalent phenol such as bisphenol A with epichlorohydrin.
  • a curing agent having a structure represented by the formula (11) is more preferable, and specifically, a melamine derivative or a urea derivative represented by the formulas (11a) to (11d) (trade name, Sanwa Chemical Co., Ltd.). (Made by a company) can be mentioned (in addition, in the formula (11), the broken line means the combiner).
  • the blending amount thereof is preferably 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of (A) or (a).
  • the resin composition may be produced by carrying out (may be described).
  • X x is a halogen atom
  • R 21 is an alkyl group
  • a is 1 to 5
  • d is 1 to 3
  • e is 0 to 2
  • the resin composition may be produced by performing a series of operations described later on the polymer.
  • R 3 is independently a hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 10 or less carbon atoms.
  • Each of R4 is independently a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms.
  • a is a number from 1 to 5.
  • d is a number of 1 or more and 3 or less.
  • e is a number of 0 or more and 2 or less.
  • cc is a number of 1 or more and 3 or less.
  • d + e + cc 4.
  • X is a hydrogen atom or an acid instability group.
  • M is at least one selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ga, Ge, ⁇ o, Pd, Ag, Sn, Cs, Ba, W and Hf. be.
  • Each of R 8 is independently a hydrogen atom, a hydroxy group, an alkyl group having 1 or more and 5 or less carbon atoms, a phenyl group, or a fluoroalkyl group having 1 or more and 10 or less carbon atoms.
  • R 9 is an alkoxy group or a halogen having 1 to 5 carbon atoms.
  • m is a number of 0 or more and 3 or less
  • n is a number of 1 or more and 4 or less
  • m + n 3 or 4.
  • M is at least one selected from the group consisting of Ge, ⁇ o and W.
  • R 8 is a halogen group and an alkoxy group having 1 or more and 5 or less carbon atoms.
  • the metal compound represented by the general formula (1-2) described later which is the raw material of the constituent unit represented by the general formula (1-A)
  • a polymer having the above (A) and the above (B) may be produced and used as a resin composition.
  • the resin composition may be produced by performing a series of operations described later on the polymer.
  • the halosilanes represented by the general formula (9), the alkoxysilane represented by the general formula (10), and the silicon compound represented by the general formula (1y), which are the raw materials of the first structural unit are used.
  • the above-mentioned oligomer is preferably a dimer to a pentamer.
  • a monomer for obtaining the above-mentioned second structural unit and the above-mentioned third structural unit, which are optional components, can be obtained.
  • a monomer or other Si monomer described above may be added.
  • the optional component may be added in advance as an oligomer.
  • This hydrolysis polycondensation reaction can be carried out by a general method in the hydrolysis and condensation reaction of halosilanes (preferably chlorosilane) and alkoxysilane.
  • the halosilanes and alkoxysilanes which are the raw materials of the above (A) and (B) are brought to room temperature (referred to as an ambient temperature that is not particularly heated or cooled, and is usually about 15 ° C. or higher and about 30 ° C. or lower. The same applies hereinafter).
  • room temperature referred to as an ambient temperature that is not particularly heated or cooled, and is usually about 15 ° C. or higher and about 30 ° C. or lower. The same applies hereinafter.
  • water for hydrolyzing halosilanes and alkoxysilanes, a catalyst for advancing the polycondensation reaction, and if desired, a reaction solvent are added into the reaction vessel to prepare a reaction solution. do.
  • reaction materials can be charged in any order to prepare a reaction solution.
  • any component may be added to the reaction vessel in the same manner as the halosilanes and alkoxysilanes.
  • the hydrolysis and condensation reaction are allowed to proceed at a predetermined temperature for a predetermined time to obtain a resin composition containing the polymer having the above (A) and the above (B). can.
  • the time required for hydrolysis condensation depends on the type of catalyst, but is usually 3 hours or more and 24 hours or less, and the reaction temperature is room temperature (for example, 25 ° C.) or more and 200 ° C. or less.
  • the reaction vessel should be closed or reflux such as a condenser to prevent unreacted raw materials, water, reaction solvent and / or catalyst in the reaction system from being distilled off from the reaction system. It is preferable to attach a device to reflux the reaction system.
  • the reaction from the viewpoint of handling the resin composition, it is preferable to remove the water remaining in the reaction system, the alcohol produced, and the catalyst.
  • Water, alcohol, and the catalyst may be removed by an extraction operation, or a solvent such as toluene that does not adversely affect the reaction may be added to the reaction system and azeotropically removed with a Dean-Stark tube.
  • the amount of water used in the hydrolysis and condensation reactions is not particularly limited. From the viewpoint of reaction efficiency, it is 0 with respect to the total number of moles of hydrolyzable groups (alkoxy groups and halogen atomic groups, if both are included, alkoxy groups and halogen atomic groups) contained in the raw materials alkoxysilane and halosilanes. It is preferably 0.01 times or more and 15 times or less.
  • the catalyst for advancing the polycondensation reaction is not particularly limited, but an acid catalyst and a base catalyst are preferably used.
  • the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, arsenic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, tosilic acid, formic acid, Examples thereof include polyvalent carboxylic acids such as maleic acid, malonic acid, and succinic acid, or anhydrides thereof.
  • the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, and carbonic acid. Examples thereof include sodium and tetramethylammonium hydroxide.
  • the amount of the catalyst used is based on the total number of moles of the hydrolyzable groups (alkoxy groups and halogen atomic groups, if both are contained, the alkoxy groups and halogen atomic groups) contained in the raw materials such as alkoxysilane and halosilanes. It is preferably 0.001 times or more and 0.5 times or less.
  • the reaction solvent In the hydrolysis and condensation reaction, it is not always necessary to use a reaction solvent, and the raw material compound, water and the catalyst can be mixed and hydrolyzed and condensed.
  • the type thereof is not particularly limited. Among them, a polar solvent is preferable, and an alcohol solvent is more preferable, from the viewpoint of solubility in a raw material compound, water, and a catalyst. Specific examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, diacetone alcohol, propylene glycol monomethyl ether and the like.
  • the amount to be used when the reaction solvent an arbitrary amount necessary for advancing the hydrolysis / condensation reaction in a uniform system can be used. Further, the solvent (C) may be used as the reaction solvent.
  • Blend of (a) and (b) obtained by prepolymerization Further, at least the above (a) obtained by prepolymerization and the above (b) are mixed by a known method to obtain the above (1).
  • a mixture containing a) and the above (b) may be produced and used as a resin composition.
  • the resin composition may be produced by performing a series of operations described later on the mixture.
  • the solvent (C) may be further contained.
  • the HFIP group in the first structural unit represented by the general formula (1) of (a) is Fe, Co, Ni, Cu, Zn, Ga, Ge, ⁇ o, Pd, Ag, Sn, Cs, Ba.
  • a resin composition and a photosensitive resin composition that enhances compatibility with (b) containing a metal species having high EUV absorbance such as W and Hf, and suppresses precipitation of components derived from raw materials, particularly precipitation of (b). Can be realized.
  • Alkoxysilanes represented by the formula (10) and the general formula (1y) and halosilanes represented by the formula (9), which are polymerization raw materials for providing the first structural unit of the general formula (1), are , A publicly known compound described in International Publication 2019/1677770, and may be synthesized according to the description in the publicly known document.
  • the ratio of the raw material of the first structural unit to the raw material of the structural unit represented by the general formula (1-A) is the same as that of the first structural unit.
  • the ratio of the structural units represented by the general formula (1-A) is 1% by mass to 90% by mass. Is preferable.
  • the molecular weight of the polymer obtained in the above ⁇ 1> and ⁇ 2> may be 500 to 50,000 in weight average molecular weight, preferably 800 to 40,000, and more preferably 1000 to 30,000.
  • the molecular weight can be set within a desired range by adjusting the amount of the catalyst and the temperature of the polymerization reaction.
  • the molecular weight of (a) and (b) after blending described in ⁇ 3> may be 500 to 50,000 in weight average molecular weight, preferably 800 to 40,000, and more preferably 1000 to 30,000. ..
  • the molecular weight can be set within a desired range by adjusting the mixing ratio of (a) and (b) and the respective molecular weights of (a) and (b).
  • a chelating agent is added to the metal compound represented by the general formula (1-2) at the time of hydrolysis polycondensation according to the above ⁇ 1> and ⁇ 2>, or before that, the water is added. This is preferable because the reaction uniformity of the decomposition polycondensation is improved.
  • a chelating agent is added to the metal compound represented by the general formula (1-2) at the time of hydrolysis polycondensation at the time of obtaining the polymerized (b) in advance in ⁇ 3>, or before that, the chelating agent is added. This is preferable because the reaction uniformity of the hydrolysis polycondensation is improved.
  • the chelating agent examples include ⁇ -diketones such as acetylacetone, benzoylacetone and dibenzoylmethane, and ⁇ -keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.
  • the solvent used for dilution one or more solvents selected from the above-mentioned solvent (C) can be used, so detailed description thereof will be omitted.
  • the concentration when diluting or concentrating the polymer with a solvent may be a concentration required for the resin composition, and is not particularly limited.
  • the polymer may be 0.5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the resin composition.
  • a general method such as an evaporator may be adopted.
  • a general method such as using a separating funnel may be adopted.
  • water remaining in the system after the hydrolysis polycondensation reaction, the alcohol produced, and the catalyst may be removed by extraction.
  • the above-mentioned polymer when the above-mentioned polymer is separated from water, it may be washed with water, or the above-mentioned polymer may be dissolved in a solvent for separating with water to make an organic solution and washed with water.
  • the ion exchange resin purification may be to reduce the metal content in the system by contacting with a commercially available ion exchange resin.
  • the filtration may be to reduce insoluble matter such as particles in the system by a general method.
  • the atom represented by M in the general formula (1-A) and the Si atom in the general formula (1) can easily form a bond via an oxygen atom, and a more uniform resin composition can be obtained.
  • ⁇ 1> and ⁇ 2> are preferable, and ⁇ 1> is particularly preferable.
  • a cured film can be formed by applying the present resin composition on a substrate and curing it.
  • the resin composition can be solidified and a cured film can be formed by heating at a temperature of 80 ° C. or higher and 350 ° C. or lower.
  • the substrate 100 with a multilayer film it is also possible to provide a substrate with a multilayer film using a cured film obtained by curing the present resin composition as an underlayer film.
  • An example of the substrate 100 with a multilayer film is shown in S0 of FIG.
  • the substrate 100 with a multilayer film has, for example, an organic layer 103 on a substrate 101, a resist underlayer film 105 which is a cured product of the resin composition on the organic layer 103, and a resist layer 107 on the underlayer film 105.
  • a resist underlayer film 105 which is a cured product of the resin composition on the organic layer 103
  • a resist layer 107 on the underlayer film 105 Have.
  • the substrate 101 is selected from silicon wafers, metals, glass, ceramics, and plastic substrates depending on the use of the patterned substrate to be formed.
  • examples of the base material used for semiconductors, displays and the like include silicon, silicon nitride, glass, polyimide (Kapton), polyethylene terephthalate, polycarbonate, polyethylene naphthalate and the like.
  • the base material 101 may have an arbitrary layer of silicon, metal, glass, ceramic, resin, or the like on the surface, and "on the base material" may be on the surface of the base material or via the layer. Make it good.
  • the organic material coating liquid for forming the organic layer 103 is applied to the base material 101.
  • the organic coating liquid used to form the organic layer 103 contains, for example, a novolak resin having a phenol structure, a bisphenol structure, a naphthalene structure, a fluorene structure, a carbazole structure, etc., an epoxy resin, a urea resin, an isocyanate resin or a polyimide resin. Examples thereof include the above-mentioned coating liquid, but the present invention is not particularly limited thereto. Further, the thickness of the organic layer 103 can be 5 nm or more and 20000 nm or less.
  • a coating method on the base material 101 a known coating method such as spin coating, dip coating, spray coating, bar coating, applicator, inkjet or roll coater can be used without particular limitation.
  • the organic layer 103 can be obtained by heating the base material 101 coated with the organic material coating liquid.
  • the heat treatment may be performed as long as the solvent can be removed to the extent that the obtained organic layer 103 does not easily flow or deform.
  • the heat treatment may be performed under the conditions of 100 to 400 ° C. for 30 seconds or more and 30 minutes or less.
  • the underlayer film 105 of the resist can be obtained.
  • the above-mentioned application method can be used.
  • the resin composition can be solidified by heating at a temperature of 80 ° C. or higher and 350 ° C. or lower to form the underlayer film 105.
  • the thickness of the underlayer film 105 can be 5 nm or more and 500 nm or less.
  • the resist layer 107 can be formed by applying a resist solution on the underlayer film 105 and heating it.
  • the resist material that can be used for the substrate 100 with a multilayer film is not particularly limited.
  • the resist layer 107 may be made of a positive resist material or a negative resist material.
  • FIG. 1 is a schematic diagram illustrating a method for manufacturing a patterned substrate 150 according to an embodiment of the present invention.
  • the method for producing the patterned substrate 150 can include the following 0th to 5th steps.
  • 0th step A step of preparing the substrate 100 with the present multilayer film.
  • First step A step of exposing the resist layer 107 via a light-shielding plate (photomask) 109 and then developing the exposed resist layer with a 107 developer to obtain a pattern.
  • Second step A step of performing dry etching of the lower layer film 105 through the pattern of the resist layer 107 to obtain a pattern of the lower layer film 105.
  • Third step A step of performing dry etching of the organic layer 103 through the pattern of the lower layer film 105 to obtain a pattern on the organic layer 103.
  • Fourth step A step of performing dry etching of the base material 101 through the pattern of the organic layer 103 to obtain a pattern on the base material 101.
  • Fifth step A step of removing the organic layer 103 to obtain a patterned substrate 150.
  • Step S0 The step of preparing the substrate 100 with a multilayer film (step S0) may be performed according to the manufacturing process of the substrate 100 with a multilayer film described above, and detailed description thereof will be omitted.
  • the substrate 100 with the multilayer film prepared in the 0th step is shielded with a light-shielding plate (photomask) 109 having a desired shape for forming a desired pattern, and the resist layer 107 is exposed to light.
  • a light-shielding plate (photomask) 109 having a desired shape for forming a desired pattern
  • the resist layer 107 is exposed to light.
  • the resist layer 107 after exposure is obtained.
  • the exposed resist layer 107 includes an exposed portion, which is an exposed portion, and an unexposed portion.
  • a known method can be used for the exposure process.
  • the light source a light ray having a light source wavelength in the range of 1 nm to 600 nm can be used.
  • the exposure amount can be adjusted according to the type and amount of the photoinduced compound used, the manufacturing process, and the like, and is not particularly limited, but is about 1 to 10000 mJ / cm 2 , preferably 10 to 5000 mJ /. It may be about cm 2 .
  • the lower layer film 105 arranged directly under the resist layer 107 is formed of a resin composition which is a uniform liquid containing a metal species having high EUV absorbance, the lower layer film 105 to the resist 107 layer side.
  • the secondary electrons from the EUV photon can be returned to the EUV photon to increase the EUV light sensitivity.
  • post-exposure heating can be performed before the development process.
  • the temperature of the post-exposure heating may be set within a temperature range suitable for the resist material to be used, and the post-exposure heating time may be set to a time suitable for the resist material to be used, and is not particularly limited.
  • step S1 by developing the resist layer 107 after exposure obtained in the first step, the exposed portion can be removed and a pattern having a desired shape can be formed (step S1; FIG. 1 is positive).
  • FIG. 1 it is an explanatory diagram of a method for manufacturing a mold pattern cured film, when a negative type pattern cured film is obtained, it is a so-called exposed portion in which a portion other than the exposed portion is removed by development and the light-shielding plate 109 does not shield the light.
  • the resist layer 107 becomes a pattern.
  • Development is to form a pattern by dissolving, washing and removing an unexposed part or an exposed part using an alkaline solution as a developing solution.
  • the developer to be used is not particularly limited as long as it can remove a desired resist layer by a predetermined developing method.
  • the developing method a known method such as a dipping method, a paddle method, or a spraying method can be used, and the developing time can be set according to the resist material. Then, if necessary, washing, rinsing, drying and the like can be performed to form the desired resist layer 107.
  • step S2 Dry etching of the underlayer film 105 is performed through the pattern of the resist layer 107 (step S2).
  • the underlayer film 105 can be dry-etched with a fluorine-based gas.
  • the pattern of the resist layer 107 serves as a protective film, and after dry etching, the film thickness of the resist layer 107 decreases and remains or disappears.
  • step S2 of FIG. 1 it is described that the pattern of the resist layer 107 disappears after dry etching.
  • the fluorine-based gas used for dry etching of the underlayer film 105 include CF 4 , CH 3 F, CH 2 F 2 , CH F 3 , C 3 F 6 , C 4 F 6 , C 4 F 8 , and the like. It is not limited to these.
  • step S3 dry etching of the organic layer 103 is performed through the pattern of the lower layer film 105 to obtain a pattern on the organic layer 103 (step S3).
  • the organic layer 103 can be dry-etched with an oxygen-based gas.
  • the pattern of the underlayer film 105 serves as a protective film, and after dry etching, the film thickness of the underlayer film 105 decreases and remains or disappears.
  • step S3 of FIG. 1 it is described that the pattern of the underlayer film 105 disappears after dry etching.
  • the oxygen-based gas used for dry etching of the organic layer 103 include, but are not limited to, O 2 , CO, and CO 2 .
  • step S4 dry etching of the base material 101 is performed through the pattern of the organic layer 103 to obtain a pattern on the base material 101 (step S4).
  • the base material can be dry-etched with a fluorine-based gas or a chlorine-based gas.
  • the pattern of the underlayer film 103 becomes a protective film, and the film thickness decreases or almost disappears after dry etching.
  • step S4 of FIG. 1 it is described that the pattern of the underlayer film 103 remains after dry etching.
  • Fluorine-based gas or chlorine-based gas used for dry etching of the base material 101 includes CF 4 , CH 3 F, CH 2 F 2 , CHF 3 , C 3 F 6 , C 4 F 6 , C 4 F 8 , and 3 hooks. Examples thereof include, but are not limited to, chlorinated chlorine, chlorine, trichloroborane, and dichloroboran.
  • Step S5 After forming the pattern, the organic layer 103 is removed (if the resist layer 107 and the underlayer film 105 are also removed, they are also removed), whereby the patterned substrate 150 having a desired pattern can be obtained (. Step S5).
  • the substrate 100 with the multilayer film has the lower layer film 105 formed of the resin composition which is a uniform liquid containing a metal species having high EUV absorbance directly under the resist layer 107, the resist is formed from the lower layer film 105. Secondary electrons from EUV photons can be returned to the 107th layer side to increase EUV light sensitivity, and a patterned substrate 150 having a fine pattern can be obtained.
  • the present resin composition can also be used as a photosensitive resin composition.
  • the photosensitive resin composition further contains the photoinduced compound (D) in addition to the present resin composition.
  • photoinducible compound (D) for example, at least one selected from the group consisting of naphthoquinone diazide, a photoacid generator, a photobase generator and a photoradical generator can be used, but is limited thereto. It's not a thing.
  • the photosensitive coating film containing the quinone diazide compound When exposed, the quinonediazide compound releases nitrogen molecules and decomposes to generate carboxylic acid groups in the molecules, thus improving the solubility of the photosensitive coating film obtained from the above-mentioned photosensitive coating solution in an alkaline developer. In addition, the alkali solubility of the photosensitive coating film is suppressed in the unexposed portion. Therefore, the photosensitive coating film containing the quinone diazide compound has a solubility contrast in the alkaline developer at the unexposed portion and the exposed portion, and can form a positive pattern.
  • the quinone diazide compound is a compound having a quinone diazide group, for example, a 1,2-quinone diazide group.
  • the 1,2-quinone diazide compound include 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid, and 1,2-naphthoquinone-2-diazide.
  • Examples thereof include -4-sulfonyl chloride and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride.
  • a positive photosensitive coating film that is sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (436 nm) of a mercury lamp, which is a general ultraviolet ray, can be obtained.
  • Examples of commercially available quinone diazide compounds include NT series, 4NT series, PC-5 manufactured by Toyo Gosei Co., Ltd., TKF series manufactured by Sanbo Chemical Industrial Co., Ltd., PQ-C, and the like.
  • the amount of the quinonediazide compound as the (D) photoinduced compound in the photosensitive resin composition is not necessarily limited, but when (A) or (a) is 100 parts by mass, for example, 1 It is preferably 5 parts by mass or more and 30 parts by mass or less, and more preferably 5 parts by mass or more and 20 parts by mass or less.
  • (A) or (a) is 100 parts by mass, for example, 1 It is preferably 5 parts by mass or more and 30 parts by mass or less, and more preferably 5 parts by mass or more and 20 parts by mass or less.
  • the photoacid generator will be explained.
  • the photoacid generator is a compound that generates an acid by irradiation with light, and the acid generated at the exposed site promotes the silanol condensation reaction, that is, the solgel polymerization reaction, and the dissolution rate by the alkaline developer is significantly reduced, that is, alkaline development. It is possible to realize resistance to a liquid. Further, when the epoxy group or the oxetane group is contained in (A) or (a), it is preferable because each curing reaction can be promoted. On the other hand, the unexposed portion does not cause this action and is dissolved by the alkaline developer, and a negative pattern corresponding to the shape of the exposed portion is formed.
  • the photoacid generator examples include a sulfonium salt, an iodonium salt, a sulfonyldiazomethane, an N-sulfonyloxyimide or an oxime-O-sulfonate. These photoacid generators may be used alone or in combination of two or more. Specific examples of commercially available products include product names: Irgacure 290, Irgacure PAG121, Irgacure PAG103, Irgacure CGI1380, Irgacure CGI725 (all manufactured by BASF in the United States), and product names: PAI-101, PAI-106, NAI-105.
  • the amount of the photoacid generator as the photoinducible compound (D) in the photosensitive resin composition is not necessarily limited, but when (A) or (a) is 100 parts by mass, for example. , 0.01 part by mass or more and 10 parts by mass or less is preferable, and 0.05 part by mass or more and 5 parts by mass or less is more preferable. By using an appropriate amount of the photoacid generator, it is easy to achieve both sufficient patterning performance and storage stability of the composition.
  • the photobase generator is a compound that generates a base (anion) by irradiation with light, and the base generated at the exposed site promotes the sol-gel reaction, and the dissolution rate by the alkaline developer is significantly reduced, that is, the alkaline developer. Can be resistant to.
  • the unexposed portion does not cause this action and is dissolved by the alkaline developer, and a negative pattern corresponding to the shape of the exposed portion is formed.
  • photobase generators include amides and amine salts.
  • Specific examples of commercially available products include trade names: WPBG-165, WPBG-018, WPBG-140, WPBG-027, WPBG-266, WPBG-300, WPBG-345 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2 -(9-Oxanthen-2-yl) Propionic Acid 1,5,7-Triazabiciclo [4.4.0] dec-5ene Salt, 2- (9-Oxanthen-2-yl) Propionic Acid, Acetophenone O- Benzoyloxime, 2-Nitrobenzyl Cyclohexylcarbate, 1,2-Bis (4-methoxyphenyl) -2-oxoethyl Cyclohexylcarbate (above, Tokyo Kasei), trade name: EIPBG, EIPM It is not limited to these.
  • photoacid generators and photobase generators may be used alone or in combination of two or more, or in combination with other compounds.
  • combination with other compounds include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, diethanolmethylamine, dimethylethanolamine, triethanolamine, and ethyl.
  • amines such as -4-dimethylaminobenzoate and 2-ethylhexyl-4-dimethylaminobenzoate
  • iodonium salts such as diphenyliodonium chloride
  • dyes such as methylene blue and amines, etc.
  • the amount of the photobase generator as the photoinducible compound (D) in the photosensitive resin composition is not necessarily limited, but when (A) or (a) is 100 parts by mass, for example. , 0.01 part by mass or more and 10 parts by mass or less is preferable, and 0.05 part by mass or more and 5 parts by mass or less is more preferable.
  • the photobase generator in the amount shown here, the balance between the chemical resistance of the obtained pattern cured film and the storage stability of the composition can be further improved.
  • the photosensitive resin composition may further contain a sensitizer.
  • a sensitizer By containing the sensitizer, the reaction of the (D) photo-induced compound is promoted in the exposure treatment, and the sensitivity and the pattern resolution are improved.
  • the sensitizer is not particularly limited, but preferably a sensitizer that vaporizes by heat treatment or a sensitizer that fades by light irradiation is used.
  • This sensitizer needs to have light absorption for the exposure wavelength in the exposure process (for example, 365 nm (i line), 405 nm (h line), 436 nm (g line)), but the pattern cured film as it is. If it remains in the visible light region, the transparency will decrease due to the presence of absorption in the visible light region. Therefore, in order to prevent the decrease in transparency due to the sensitizer, the sensitizer used is preferably a compound that vaporizes by heat treatment such as heat curing or a compound that fades by light irradiation such as bleaching exposure described later.
  • the blending amount thereof is preferably 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of (A) or (a).
  • FIG. 2 is a schematic diagram illustrating a method for manufacturing a negative type pattern cured film 211 according to an embodiment of the present invention.
  • the present invention can also manufacture a positive pattern cured film 211.
  • this photosensitive resin composition for producing the patterned substrate 150 shown in FIG.
  • the resist layer 107 becomes unnecessary, and a multilayer film composed of only two layers of the lower layer film 105 and the organic film 103 may be used, which contributes to a significant reduction in the number of processes. Therefore, the photosensitive resin composition is very useful. Is.
  • pattern cured film in the present specification is a cured film obtained by developing to form a pattern after the exposure process and curing the obtained pattern. This will be described below.
  • the method for producing the pattern cured film 211 can include the following first to fourth steps.
  • First step A step of applying the present photosensitive coating liquid on the substrate 201 and heating to form the photosensitive coating film 203.
  • Second step A step of exposing the photosensitive coating film 203 via a light-shielding plate (photomask) 205.
  • Third step A step of developing the photosensitive coating film 203 after exposure to form a pattern film 207.
  • Fourth step A step of heating the pattern film 207, thereby curing the pattern film 207 and converting it into the pattern cured film 211.
  • the base material 201 is prepared (step S11-1).
  • the base material 201 to which the photosensitive resin composition is applied is selected from silicon wafers, metals, glass, ceramics, and plastic base materials, depending on the use of the patterned cured film to be formed.
  • examples of the base material used for semiconductors, displays and the like include silicon, silicon nitride, glass, polyimide (Kapton), polyethylene terephthalate, polycarbonate, polyethylene naphthalate and the like.
  • the base material 201 may have an arbitrary layer of silicon, metal, glass, ceramic, resin, or the like on the surface, and "on the base material" may be on the surface of the base material or via the layer. Make it good.
  • a coating method on the base material 201 a known coating method such as spin coating, dip coating, spray coating, bar coating, applicator, inkjet or roll coater can be used without particular limitation.
  • the photosensitive coating film 203 can be obtained by heating the base material 201 coated with the photosensitive resin composition (step S11-2).
  • the heat treatment may be performed as long as the solvent can be removed to the extent that the obtained photosensitive coating film 203 does not easily flow or deform, and may be heated at, for example, 80 to 120 ° C. for 30 seconds or more and 5 minutes or less.
  • the photosensitive coating film 203 obtained in the first step is shielded from light by a light-shielding plate (photomask) 205 having a desired shape for forming a desired pattern, and the photosensitive coating film 203 is irradiated with light.
  • the photosensitive coating film 203 after exposure can be obtained by performing the exposure treatment (step S12).
  • the photosensitive coating film 203 after exposure includes an exposed portion 203a which is an exposed portion and an unexposed portion.
  • a known method can be used for the exposure process.
  • the light source a light ray having a light source wavelength in the range of 1 nm to 600 nm can be used.
  • the exposure amount can be adjusted according to the type and amount of the photoinduced compound used, the manufacturing process, and the like, and is not particularly limited, but is about 1 to 10000 mJ / cm 2 , preferably 10 to 5000 mJ /. It may be about cm 2 .
  • post-exposure heating can be performed before the development process.
  • the temperature of post-exposure heating is preferably 60 to 180 ° C., and the post-exposure heating time is preferably 30 seconds to 10 minutes.
  • FIG. 2 is an explanatory diagram of a method for manufacturing a negative type pattern cured film, in the case of obtaining a positive type pattern cured film, the exposed portion 203a is removed by developing the film, and the unexposed film is shielded by the light shielding plate 205.
  • the photosensitive coating film 203 which is a portion, becomes the pattern film 207.
  • a photoacid generator is used as the photoinducible compound, and a negative type pattern cured film is obtained when X is a hydrogen atom and a positive type pattern cured film is obtained when X is an acid unstable group.
  • Development is to form a pattern by dissolving, washing and removing an unexposed part or an exposed part using an alkaline solution as a developing solution.
  • the developer to be used is not particularly limited as long as it can remove a desired photosensitive coating film by a predetermined developing method.
  • Specific examples thereof include an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, a quaternary ammonium salt, and an alkaline aqueous solution using a mixture thereof.
  • alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (abbreviation: TMAH) can be mentioned.
  • TMAH tetramethylammonium hydroxide
  • it is preferable to use a TMAH aqueous solution and in particular, it is preferable to use a TMAH aqueous solution of 0.1% by mass or more and 5% by mass or less, more preferably 2% by mass or more and 3% by mass or less.
  • the developing method known methods such as a dipping method, a paddle method, and a spraying method can be used, and the developing time may be 0.1 minutes or more and 3 minutes or less. Further, it is preferably 0.5 minutes or more and 2 minutes or less. After that, washing, rinsing, drying, etc. are performed as necessary to form the desired pattern film 207 on the base material 201.
  • the purpose is to improve the transparency of the finally obtained pattern cured film 211 by photodecomposing the photoinduced compound remaining in the pattern film 207.
  • the same exposure processing as in the second step can be performed.
  • the pattern film (including the pattern film exposed to bleaching) 207 obtained in the third step is heat-treated to obtain the final pattern cured film 211 (step S14).
  • the heat treatment makes it possible to condense the alkoxy group or silanol group that remains as an unreactive group in (A) or (a).
  • the photo-induced compound and the photo-decomposed product of the photo-induced compound can be removed by thermal decomposition.
  • the heating temperature at this time is preferably 80 ° C. or higher and 400 ° C. or lower, and more preferably 100 ° C. or higher and 350 ° C. or lower.
  • the heat treatment time may be 1 minute or more and 90 minutes or less, and preferably 5 minutes or more and 60 minutes or less.
  • Ph-Si Phenyltriethoxysilane
  • PGMEA Propylene glycol monomethyl ether acetate
  • HFA-Si Compound represented by the following chemical formula
  • HFA-PH-MES Compound represented by the following chemical formula
  • the weight average molecular weight (Mw) of the resin composition described below was measured as follows. High-speed GPC equipment manufactured by Tosoh Corporation, device name HLC-8320GPC, TSKgel SuperHZ2000 manufactured by Tosoh Corporation as a column, and tetrahydrofuran (THF) as a solvent were used, and the measurement was carried out by polystyrene conversion.
  • Example 1 To the reaction vessel, 3.25 g (8 mmol) of HFA-Si, 2.02 g (8 mmol) of germanium tetraethoxydo, and 0.19 g (3.2 mmol) of acetic acid were added, and the mixture was stirred at room temperature for 24 hours and then ethanol. After adding 68 g and stirring for 5 minutes, 0.14 g (8 mmol) of pure water was added, and it was confirmed that the uniform solution was maintained as before the addition of pure water. Then, 0.29 g (3.2 mmol) of 69% nitric acid was added, and the mixture was further stirred for 24 hours. The finally obtained reaction solution was also a uniform solution.
  • Example 2 To the reaction vessel, 1.92 g (4.7 mmol) of HFA-Si, 1.19 g (4.7 mmol) of germanium tetraethoxydo, and 3.0 g of ethanol were added, and after stirring at 70 ° C., 12 g of ethanol and 0 of pure water were added. A mixed solution of .24 g and 0.05 g (0.5 mmol) of maleic acid was added dropwise, and the mixture was further stirred for 3 hours. The finally obtained reaction solution was also a uniform solution. Then, 20 g of PGMEA was added and treated with an evaporator at 50 ° C. to obtain 18 g of a uniform solution (solution 2). The weight average molecular weight Mw measured by GPC was 1660. (A), (B) and (C) of the solution 2 are shown in Table 1.
  • Example 3 To the reaction vessel, 1.92 g (4.7 mmol) of HFA-Si, 2.39 g (9.45 mmol) of germanium tetraethoxydo, 1.97 g (9.45 mmol) of tetraethoxysilane, and 6.0 g of ethanol were added, and the temperature was 70 ° C. After stirring with, a mixed solution of 18 g of ethanol, 0.48 g of pure water and 0.14 g (1.2 mmol) of maleic acid was added dropwise, and the mixture was further stirred for 3 hours. The finally obtained reaction solution was also a uniform solution. Then, 20 g of PGMEA was added and treated with an evaporator at 50 ° C. to obtain 20 g of a uniform solution (solution 3). The weight average molecular weight Mw measured by GPC was 6500. (A), (B) and (C) of the solution 3 are shown in Table 1.
  • Example 4 In the reaction vessel, HFA-Si 1.30 g (3.2 mmol), tetraethoxysilane 1.33 g (6.4 mmol), pure water 1.15 g, tin (IV) chloride pentahydrate 2.24 g (6.4 mmol). ), 15 g of ethanol was added and stirred at room temperature, and it was confirmed that a uniform solution was obtained. Then, the mixture was stirred at 80 ° C. for 4 hours, and the finally obtained reaction solution was also a uniform solution. Then, 20 g of PGMEA was added and treated with an evaporator at 50 ° C. to obtain 21 g of a uniform solution (solution 4). The weight average molecular weight Mw measured by GPC was 1800.
  • the solutions 4 (A), (B) and (C) are listed in Table 1.
  • Example 5 To the reaction vessel, add 4.27 g (1.9 mmol) of HFA-Si, 9.45 g (2.4 mmol) of germanium tetraethoxydo, 9.45 g (3.6 mmol) of HFA-PH-MES, and 6.0 g of ethanol. After stirring at 70 ° C., a mixed solution of 18 g of ethanol, 0.5 g of pure water and 0.14 g (1.2 mmol) of maleic acid was added dropwise, and the mixture was further stirred for 24 hours. The finally obtained reaction solution was also a uniform solution. Then, 20 g of PGMEA was added and treated with an evaporator at 50 ° C. to obtain 20 g of a uniform solution (solution 5). The weight average molecular weight Mw measured by GPC was 6700. (A), (B) and (C) of the solution 5 are shown in Tables 1 and 2.
  • the total content of M atoms in the general formula (1-A) was 15 atm% for the cured film 2-1 and 9 atm% for 3-1. 4-1 was 4.1 atm%.
  • the cured films 1-1 and 5-1 were formed on the silicon wafer using the solution 1 obtained in Example 1 and the solution 5 obtained in Example 5, respectively, and X-rays were also formed.
  • the total content of M atoms in the general formula (1-A) was 14 atm% for the cured film 1-1 and 3.1 atm% for 5-1. rice field.
  • the cured film on the obtained silicon wafer is dry-etched with a fluorine-based gas (CF 4 and CHF 3 ) and an oxygen-based gas (CO 2 or O 2 ), and the etching rate for each gas is measured to obtain etching selectivity.
  • a fluorine-based gas CF 4 and CHF 3
  • an oxygen-based gas CO 2 or O 2
  • Etching conditions (1) to (3) are shown below (hereinafter, the etching rate may be simply referred to as a rate, and the etching conditions may be simply referred to as a condition).
  • CF 4 and CHF 3 are used as fluorine-based gas CF 4 flow rate: 150 sccm CHF 3 flow rate: 50 sccm Ar flow rate: 100 sccm Chamber pressure: 10 Pa Applied power: 400W Temperature: 15 ° C
  • CO 2 is used as an oxygen-based gas CO 2 flow rate: 300 sccm Ar flow rate: 100 sccm N 2 flow rate: 100 sccm Chamber pressure: 2Pa Applied power: 400W Temperature: 15 ° C
  • Table 2 shows the measured values of the etching rates under the etching conditions (1) to (3) and the etching rate ratios obtained from them.
  • the etching rate ratio A is a value obtained by dividing the measured value of the velocity under the condition (1) by the measured value of the velocity under the condition (2)
  • the etching rate ratio B is a value obtained by dividing the measured value of the velocity under the condition (1) under the condition (3). ) Divided by the measured value of velocity.
  • the cured film 2-1 obtained from the solution 2 obtained in Example 2 and the cured film 3-1 obtained from the solution 3 obtained in Example 3 are shown in Comparative Example 4.
  • the fluorine-based etching rate value is large, and the O2 plasma etching resistance is excellent (conditions (2) and (3) have high etching rate values.
  • Extreml excellent etching selectivity of fluorine-based gas and oxygen-based gas (both rate ratio A and rate ratio B of etching selectivity are large).
  • Substrate with multilayer film 101 substrate, 103 organic layer, 105 underlayer film, 107 resist layer, 109 photomask, 150 patterned substrate, 201 substrate, 203 photosensitive coating film, 203a exposed part, 205 photomask, 207 Pattern film, 211 Pattern cured film

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