WO2018016615A1 - Composé, résine, composition, procédé de formation de motif de réserve et procédé de formation de circuit - Google Patents

Composé, résine, composition, procédé de formation de motif de réserve et procédé de formation de circuit Download PDF

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Publication number
WO2018016615A1
WO2018016615A1 PCT/JP2017/026423 JP2017026423W WO2018016615A1 WO 2018016615 A1 WO2018016615 A1 WO 2018016615A1 JP 2017026423 W JP2017026423 W JP 2017026423W WO 2018016615 A1 WO2018016615 A1 WO 2018016615A1
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group
carbon atoms
formula
compound
substituted
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PCT/JP2017/026423
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English (en)
Japanese (ja)
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越後　雅敏
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三菱瓦斯化学株式会社
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Priority to KR1020197002661A priority Critical patent/KR20190033536A/ko
Priority to CN201780045278.2A priority patent/CN109476576A/zh
Priority to JP2018528887A priority patent/JP7069529B2/ja
Publication of WO2018016615A1 publication Critical patent/WO2018016615A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
    • C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • the present invention relates to a compound having a specific structure, a resin, and a composition containing these.
  • the present invention also relates to a pattern forming method (resist pattern forming method and circuit pattern forming method) using the composition.
  • the molecular weight is as large as about 10,000 to 100,000, and the molecular weight distribution is wide, resulting in roughness on the pattern surface, making it difficult to control the pattern size, and limiting the miniaturization.
  • various low molecular weight resist materials have been proposed so far in order to provide resist patterns with higher resolution. Since the low molecular weight resist material has a small molecular size, it is expected to provide a resist pattern with high resolution and low roughness.
  • an alkali development negative radiation-sensitive composition for example, see Patent Document 1 and Patent Document 2 below
  • a low molecular weight polynuclear polyphenol compound as a main component
  • a low molecular weight resist having high heat resistance As a candidate for the material, an alkali developing negative radiation-sensitive composition (for example, see Patent Document 3 and Non-Patent Document 1 below) using a low molecular weight cyclic polyphenol compound as a main component has also been proposed.
  • polyphenol compounds are known to be able to impart high heat resistance while having a low molecular weight, and are useful for improving the resolution and roughness of resist patterns (for example, the following non-patent documents) 2).
  • the present inventors have excellent etching resistance, and are resist compositions containing a compound having a specific structure and an organic solvent as a material that is soluble in a solvent and applicable to a wet process (for example, see Patent Document 4 below). ).
  • a material for forming an underlayer film for a multilayer resist process has been proposed that contains at least a resin component having a substituent that generates a sulfonic acid residue and a solvent (see, for example, Patent Document 5 below).
  • resist underlayer film materials containing a polymer having a specific repeating unit have been proposed as a material for realizing a resist underlayer film for lithography having a lower dry etching rate selectivity than resist (for example, the following patents) Reference 6). Furthermore, in order to realize a resist underlayer film for lithography having a low dry etching rate selection ratio compared with a semiconductor substrate, a repeating unit of acenaphthylenes and a repeating unit having a substituted or unsubstituted hydroxy group are copolymerized. A resist underlayer film material containing a polymer is proposed (see, for example, Patent Document 7 below).
  • an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas or the like as a raw material is well known.
  • a resist underlayer film material capable of forming a resist underlayer film by a wet process such as spin coating or screen printing is required.
  • the present inventors have a composition for forming an underlayer film for lithography containing a compound having a specific structure and an organic solvent as a material having excellent etching resistance, high heat resistance, soluble in a solvent and applicable to a wet process.
  • the thing (for example, refer the following patent document 8) is proposed.
  • a silicon nitride film formation method for example, see Patent Document 9 below
  • a silicon nitride film CVD formation method for example, And the following Patent Document 10.
  • an intermediate layer material for a three-layer process a material containing a silsesquioxane-based silicon compound is known (see, for example, Patent Documents 11 and 12 below).
  • optical component forming compositions have been proposed.
  • examples thereof include acrylic resins (see, for example, Patent Documents 13 to 14 below).
  • a polyphenol having a specific structure derived from an alcohol group or an epoxy group has also been proposed (see, for example, Patent Document 15 below).
  • the present invention has been made in view of the above-described problems, and the object thereof is a compound and resin having high solubility in a safe solvent, good heat resistance and etching resistance, a composition using the same, and The present invention relates to a resist pattern forming method and a circuit pattern forming method using the composition.
  • the present inventors have found that the above problems can be solved by using a compound or resin having a specific structure, and have completed the present invention. That is, the present invention is as follows.
  • a compound represented by the following formula (0) (In the formula (0), R Y is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, R Z is an N-valent group having 1 to 60 carbon atoms or a single bond, R T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent.
  • the hydrogen atom is a group substituted with a hydroxyalkyl group or a glycidyl group
  • the alkyl group, the aryl group, the alkenyl group, and the alkoxy group include an ether bond, a ketone bond, or an ester bond.
  • At least one of RT includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, X represents an oxygen atom, a sulfur atom or no bridge, m is each independently an integer of 0 to 9, wherein at least one of m is an integer of 1 to 9, N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulas in N [] may be the same or different, Each r is independently an integer of 0-2. ) ⁇ 2> The compound according to ⁇ 1>, wherein the compound represented by the formula (0) is a compound represented by the following formula (1).
  • R 0 has the same meaning as R Y
  • R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond
  • R 2 to R 5 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
  • a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are an ether bond, a ketone bond, or an ester.
  • R 2 to R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
  • m 2 and m 3 are each independently an integer of 0 to 8
  • m 4 and m 5 are each independently an integer of 0 to 9
  • m 2 , m 3 , m 4 and m 5 are not 0 simultaneously
  • n is synonymous with the above N, and here, when n is an integer of 2 or more, the structural formulas in the n [] may be the same or different
  • p 2 to p 5 have the same meaning as r.
  • the hydrogen atom is a group substituted with a hydroxyalkyl group or a glycidyl group
  • the alkyl group, the aryl group, the alkenyl group, and the alkoxy group include an ether bond, a ketone bond, or an ester bond.
  • R 2A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
  • n A has the same meaning as N above.
  • n A is an integer of 2 or more
  • the structural formulas in n A [] may be the same or different
  • X A is synonymous with X
  • m 2A is each independently an integer of 0 to 7, provided that at least one m 2A is an integer of 1 to 7;
  • q A is each independently 0 or 1.
  • R 0 , R 1 , R 4 , R 5 , n, p 2 to p 5 , m 4 and m 5 are as defined above.
  • R 6 to R 7 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
  • An alkenyl group having 2 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, a carboxylic acid group, or a thiol group, which may have R 10 to R 11 are each independently a hydrogen atom or a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group,
  • at least one of R 10 to R 11 is one group selected from a hydroxyalkyl group, a glycidyloxyalkyl group, or a glycidyl group
  • m 6 and m 7 are each independently an integer of 0 to 7, However, m 4 , m 5 , m 6 and m 7 are not 0 at the same time.
  • Each R 4A is independently a hydrogen atom or a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group;
  • at least one of R 4A is a hydroxyalkyl group, a glycidyloxyalkyl group, or a glycidyl group
  • m 6A is each independently an integer of 0 to 5.
  • the resin according to ⁇ 7> which has a structure represented by the following formula (3).
  • L is an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, or an optionally substituted carbon number.
  • R 0 has the same meaning as R Y
  • R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond
  • R 2 to R 5 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
  • a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are an ether bond, a ketone bond, or an ester.
  • n is synonymous with the above N, and here, when n is an integer of 2 or more, the structural formulas in the n [] may be the same or different, p 2 to p 5 have the same meaning as r.
  • L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent.
  • the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond
  • R 0A has the same meaning as R Y
  • R 1A is an n A valent group having 1 to 30 carbon atoms or a single bond
  • R 2A each independently has an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
  • the hydrogen atom is a group substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
  • the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are ether bonds, ketone bonds Or an ester bond
  • at least one of R 2A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
  • n A has the same meaning as N above.
  • n A is an integer of 2 or more
  • the structural formulas in n A [] may be the same or different
  • X A is synonymous with X
  • m 2A is each independently an integer of 0 to 7, provided that at least one m 2A is an integer of 1 to 6
  • q A is each independently 0 or 1.
  • ⁇ 10> Contains one or more selected from the group consisting of the compound according to any one of ⁇ 1> to ⁇ 6> and the resin according to any one of ⁇ 7> to ⁇ 9>.
  • Composition. ⁇ 11> The composition according to ⁇ 10>, further including a solvent.
  • ⁇ 12> The composition according to ⁇ 10> or ⁇ 11>, further including an acid generator.
  • the crosslinking agent is at least one selected from the group consisting of phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds, and azide compounds.
  • the content of the cross-linking agent is selected from the group consisting of the compound according to any one of the above ⁇ 1> to ⁇ 6> and the resin according to any one of the above ⁇ 7> to ⁇ 9>.
  • the composition according to any one of ⁇ 13> to ⁇ 15> which is 0.1 to 100 parts by mass with respect to 100 parts by mass of the total mass of the composition containing one or more selected.
  • ⁇ 17> The composition according to any one of ⁇ 13> to ⁇ 16>, further including a crosslinking accelerator.
  • the crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines, and Lewis acids.
  • ⁇ 19> The group consisting of the compound according to any one of ⁇ 1> to ⁇ 6> and the resin according to any one of ⁇ 7> to ⁇ 9>, wherein the content of the crosslinking accelerator is The composition according to ⁇ 17> or ⁇ 18>, which is 0.1 to 5 parts by mass with respect to 100 parts by mass of the total mass of the composition containing one or more selected from the above.
  • ⁇ 20> The composition according to any one of ⁇ 10> to ⁇ 19>, further comprising a radical polymerization initiator.
  • ⁇ 21> The ⁇ 10> to ⁇ 20, wherein the radical polymerization initiator is at least one selected from the group consisting of a ketone photopolymerization initiator, an organic peroxide polymerization initiator, and an azo polymerization initiator.
  • the content of the radical polymerization initiator includes the compound according to any one of ⁇ 1> to ⁇ 6> and the resin according to any one of ⁇ 7> to ⁇ 9>.
  • the composition according to any one of the above ⁇ 10> to ⁇ 21> which is 0.05 to 25 parts by mass with respect to 100 parts by mass of the total mass of the composition containing one or more selected from the group.
  • composition according to any one of ⁇ 10> to ⁇ 22> which is used for forming a film for lithography.
  • ⁇ 24> The composition according to any one of ⁇ 10> to ⁇ 22>, which is used for forming a resist permanent film.
  • ⁇ 25> The composition according to any one of ⁇ 10> to ⁇ 22>, which is used for forming an optical component.
  • a resist pattern including a step of forming a photoresist layer on the substrate by using the composition according to the above ⁇ 23>, irradiating a predetermined region of the photoresist layer with radiation, and performing development. Forming method.
  • a lower layer film is formed on the substrate using the composition according to the above ⁇ 23>, and at least one photoresist layer is formed on the lower layer film, and then a predetermined layer of the photoresist layer is formed.
  • a resist pattern forming method including a step of irradiating a region with radiation and performing development.
  • a lower layer film is formed on the substrate using the composition described in ⁇ 23>, an intermediate layer film is formed on the lower layer film using a resist intermediate layer film material, and the intermediate layer film is formed.
  • a circuit pattern including a step of forming a pattern on the substrate by etching the substrate using the obtained intermediate layer film pattern as an etching mask and etching the substrate using the obtained lower layer film pattern as an etching mask Forming method.
  • a compound and a resin having high solubility in a safe solvent and good heat resistance and etching resistance, a composition using the same, and a resist pattern forming method and circuit pattern forming using the composition A method can be provided.
  • the compound of this embodiment is a compound represented by the formula (0) described later, or a resin obtained using the compound as a monomer.
  • the compound and resin of this embodiment can be applied to a wet process, and is useful for forming a photoresist and an underlayer film for photoresist excellent in heat resistance, solubility in a safe solvent, and etching resistance. It can be used for a composition useful for formation, a pattern formation method using the composition, and the like.
  • the compound and resin of the present embodiment are excellent in sensitivity and resolution when used in a photosensitive material, and while maintaining high heat resistance, further, general-purpose organic solvents, other compounds, and resin components , And a resist permanent film having excellent compatibility with the additive.
  • the above-described composition uses a compound or resin having a specific structure that has high heat resistance and high solvent solubility, so that deterioration of the film during high-temperature baking is suppressed, and etching resistance against oxygen plasma etching and the like is also improved. An excellent resist and lower layer film can be formed.
  • the adhesion with the resist layer is also excellent, so that an excellent resist pattern can be formed.
  • the above-described composition has a high refractive index and coloration is suppressed by a wide range of heat treatment from low temperature to high temperature, it is useful as various optical forming compositions.
  • the compound of this embodiment is represented by the following formula (0).
  • (0) (In the formula (0), R Y is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, R Z is an N-valent group having 1 to 60 carbon atoms or a single bond, R T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent.
  • the hydrogen atom is a group substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
  • the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are ether bonds, ketone bonds
  • at least one of R T includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
  • X represents an oxygen atom, a sulfur atom or no bridge
  • m is each independently an integer of 0 to 9, wherein at least one of m is an integer of
  • R Y is an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.
  • the alkyl group a linear, branched or cyclic alkyl group can be used. Since R Y is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, the heat resistance is relatively high and the solvent solubility is improved.
  • R Y is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, the oxidative decomposition of the compound is further suppressed, coloring is suppressed, and heat resistance is improved. From the viewpoint of improving the solubility of the solvent and the solvent.
  • R z is an N-valent group having 1 to 60 carbon atoms or a single bond, and each aromatic ring is bonded through this R z .
  • N is an integer of 1 to 4, and when N is an integer of 2 or more, the structural formulas in N [] may be the same or different.
  • N-valent group examples include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group.
  • the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group.
  • the N-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 60 carbon atoms.
  • R T each independently has an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, or a substituent.
  • the hydrogen atom is a group substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
  • the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are ether bonds, ketone bonds Or it may contain an ester bond.
  • RT includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • the alkyl group, alkenyl group and alkoxy group may be a linear, branched or cyclic group.
  • a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group in which a glycidyl group is substituted means a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group, and a hydrogen atom of the hydroxyl group.
  • a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group and a hydroxyl group (hydroxy group) of the hydroxyalkyl group is substituted with another substituent is also included.
  • the group in which the hydroxyl group of the hydroxyalkyl group is substituted with another substituent is not particularly limited, and examples thereof include a glycidyloxyalkyl group in which the hydroxyl group is substituted with a glycidyl group.
  • the alkyl group in the hydroxyalkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • the hydroxyalkyl group and glycidyl group may be substituted with a hydrogen atom of a hydroxyl group through another linking group.
  • the other linking group include an oxygen atom, an alkylene group, and an oxyalkylene group.
  • X represents an oxygen atom, a sulfur atom or no bridge. When X is an oxygen atom or a sulfur atom, it tends to develop high heat resistance, and is preferably an oxygen atom. X is preferably non-crosslinked from the viewpoint of solubility.
  • M is each independently an integer of 0 to 9, and at least one of m is an integer of 1 to 9.
  • Each r is independently an integer of 0-2.
  • the numerical range of m described above is determined according to the ring structure determined by r.
  • the compound represented by the formula (0) has a relatively low molecular weight, but has high heat resistance due to the rigidity of its structure, and therefore can be used under high temperature baking conditions. Moreover, it has a quaternary carbon in the molecule, the crystallinity is suppressed, and it is suitably used as a film-forming composition for lithography that can be used for manufacturing a film for lithography.
  • the compound represented by the formula (0) has high solubility in a safe solvent, and has good heat resistance and etching resistance, and the resist forming composition for lithography according to this embodiment gives a good resist pattern shape. .
  • the compound represented by the formula (0) has a relatively low molecular weight and a low viscosity, even if the substrate has a step (particularly, a fine space or a hole pattern), the step It is easy to improve the flatness of the film while uniformly filling every corner, and as a result, the underlayer film forming composition for lithography using the same can have relatively advantageous enhancement of embedding and planarization characteristics. . Moreover, since it is a compound having a relatively high carbon concentration, high etching resistance is also imparted.
  • the compound represented by the formula (0) has a high aromatic density and a high refractive index, and is also useful as a composition for forming various optical parts because coloration is suppressed by a wide range of heat treatment from low to high temperatures. It is.
  • the compound represented by the formula (0) preferably has a quaternary carbon from the viewpoint of suppressing oxidative decomposition of the compound, suppressing coloring, high heat resistance, and improving solvent solubility.
  • Optical parts are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms It is useful as an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.
  • R 0 has the same meaning as R Y
  • R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond
  • R 2 to R 5 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
  • a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are an ether bond, a ketone bond, or an ester.
  • R 2 to R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
  • m 2 and m 3 are each independently an integer of 0 to 8
  • m 4 and m 5 are each independently an integer of 0 to 9
  • m 2 , m 3 , m 4 and m 5 are not 0 simultaneously
  • n is synonymous with the above N, and here, when n is an integer of 2 or more, the structural formulas in the n [] may be the same or different
  • p 2 to p 5 have the same meaning as r.
  • R 0 has the same meaning as R Y described above.
  • R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond, and each aromatic ring is bonded through R 1 .
  • n is synonymous with N, and when n is an integer of 2 or more, the structural formulas in n [] may be the same or different.
  • n-valent group examples include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group.
  • the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group.
  • the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 60 carbon atoms.
  • R 2 to R 5 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
  • a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are an ether bond, a ketone bond, or an ester.
  • R 2 to R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group in which a glycidyl group is substituted.
  • the alkyl group, alkenyl group and alkoxy group may be a linear, branched or cyclic group.
  • n 2 and m 3 are each independently an integer of 0 to 8
  • m 4 and m 5 are each independently an integer of 0 to 9.
  • m 2 , m 3 , m 4 and m 5 are not 0 at the same time.
  • p 2 to p 5 are each independently synonymous with r.
  • the compound represented by the formula (1) has a relatively low molecular weight, but has high heat resistance due to the rigidity of its structure, and therefore can be used under high temperature baking conditions. Moreover, it has a quaternary carbon in the molecule, the crystallinity is suppressed, and it is suitably used as a film-forming composition for lithography that can be used for manufacturing a film for lithography.
  • the solubility in a safe solvent is high, the heat resistance and the etching resistance are good, and the resist forming composition for lithography according to this embodiment gives a good resist pattern shape.
  • the film has a relatively low molecular weight and low viscosity, even a substrate having a step (particularly, a fine space or a hole pattern) can be uniformly filled to every corner of the step and the film can be flattened.
  • the composition for forming an underlayer film for lithography using the same can be relatively advantageously enhanced in embedding and planarization characteristics.
  • it is a compound having a relatively high carbon concentration, high etching resistance is also imparted.
  • the compound represented by the formula (1) has a high aromatic density, the refractive index is high, and the coloration is suppressed by a wide range of heat treatment from low temperature to high temperature, so that it is also useful as a composition for forming various optical components. is there.
  • the one having quaternary carbon is preferable from the viewpoint of suppressing oxidative decomposition of the present compound to suppress coloring, high heat resistance, and improving solvent solubility.
  • Optical parts are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms It is useful as an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.
  • the compound represented by the formula (1) is preferably a compound represented by the following formula (1-1) from the viewpoint of easy crosslinking and solubility in an organic solvent. (1-1)
  • R 0 , R 1 , R 4 , R 5 , n, p 2 to p 5 , m 4 and m 5 are as defined above, and R 6 to R 7 are each independently A linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a substituent.
  • R 10 ⁇ R 11 are each independently a hydrogen atom or a hydroxy An alkyl group, a glycidyloxyalkyl group or a glycidyl group;
  • at least one of R 10 to R 11 is a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group
  • m 6 and m 7 are each independently an integer of 0 to 7.
  • m 4 , m 5 , m 6 and m 7 are not 0 at the same time.
  • the compound represented by the formula (1-1) is preferably a compound represented by the following formula (1-2) from the viewpoint of further crosslinkability and solubility in an organic solvent.
  • R 0 , R 1 , R 6 , R 7 , R 10 , R 11 , n, p 2 to p 5 , m 6 and m 7 are as defined above, and R 8 to R 9 has the same meaning as R 6 to R 7 , and R 12 to R 13 have the same meaning as R 10 to R 11 .
  • m 8 and m 9 are each independently an integer of 0 to 8. However, m 6 , m 7 , m 8 and m 9 are not 0 at the same time.
  • the compound represented by the formula (1-2) is preferably a compound represented by the following formula (1a).
  • R 0 to R 5 , m 2 to m 5 and n have the same meaning as described in the formula (1).
  • the compound represented by the formula (1a) is more preferably a compound represented by the following formula (1b) from the viewpoint of solubility in an organic solvent.
  • R 0 , R 1 , R 4 , R 5 , R 10 , R 11 , m 4 , m 5 , and n are as defined in the formula (1), and R 6 , R 7 , R 10 , R 11 , m 6 and m 7 have the same meanings as described in the formula (1-1).
  • the compound represented by the formula (1a) is more preferably a compound represented by the following formula (1b ′) from the viewpoint of reactivity. (1b ')
  • R 0 , R 1 , R 4 , R 5 , R 10 , R 11 , m 4 , m 5 , and n are as defined in the formula (1), and R 6 , R 7 , R 10 , R 11 , m 6 and m 7 have the same meanings as described in the formula (1-1).
  • the compound represented by the formula (1b) is more preferably a compound represented by the following formula (1c) from the viewpoint of solubility in an organic solvent.
  • R 0 , R 1 , R 6 to R 13 , m 6 to m 9 , and n are as defined in the formula (1-2).
  • the compound represented by the formula (1b ′) is more preferably a compound represented by the following formula (1c ′) from the viewpoint of reactivity.
  • R 0 , R 1 , R 6 to R 13 , m 6 to m 9 , and n are as defined in the formula (1-2).
  • X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
  • X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
  • X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
  • X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
  • X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
  • X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
  • X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
  • X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
  • X is the formula (0) have the same meanings as those described in, R T 'has the same meaning as R T described by the formula (0), m each independently 1-6 Is an integer.
  • OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those described in, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is synonymous with what was demonstrated by the said Formula (0).
  • R Z ' are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is synonymous with what was demonstrated by the said Formula (0).
  • R Z ' are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is synonymous with what was demonstrated by the said Formula (0).
  • R Z ' are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is synonymous with what was demonstrated by the said Formula (0).
  • R Z ' are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is synonymous with what was demonstrated by the said Formula (0).
  • R Z ' are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • X is the formula (0) have the same meanings as those explained in, also, R Z 'are as defined R Z described by the formula (0).
  • at least one of OR 4A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • R 2 , R 3 , R 4 , and R 5 have the same meaning as described in the formula (1).
  • m 2 and m 3 are integers from 0 to 6
  • m 4 and m 5 are integers from 0 to 7.
  • at least one selected from R 2 , R 3 , R 4 and R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and m 2 , m 3 , m 4 and m 5 are not 0 at the same time.
  • R 2 , R 3 , R 4 , and R 5 have the same meaning as described in the formula (1).
  • m 2 and m 3 are integers from 0 to 6
  • m 4 and m 5 are integers from 0 to 7.
  • at least one selected from R 2 , R 3 , R 4 and R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and m 2 , m 3 , m 4 and m 5 are not 0 at the same time.
  • R 2 , R 3 , R 4 , and R 5 have the same meaning as described in the formula (1).
  • m 2 and m 3 are integers from 0 to 6
  • m 4 and m 5 are integers from 0 to 7.
  • at least one selected from R 2 , R 3 , R 4 and R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and m 2 , m 3 , m 4 and m 5 are not 0 at the same time.
  • R 2 , R 3 , R 4 , and R 5 have the same meaning as described in the formula (1).
  • m 2 and m 3 are integers from 0 to 6
  • m 4 and m 5 are integers from 0 to 7.
  • at least one selected from R 2 , R 3 , R 4 and R 5 includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and m 2 , m 3 , m 4 and m 5 are not 0 at the same time.
  • R 10 , R 11 , R 12 , R 13 have the same meanings as described in the formula (1-2), and R 10 to R 13 are each independently a hydrogen atom. Or a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group, and at least one of R 10 to R 11 is one group selected from a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group.
  • the compound represented by the formula (1) is particularly preferably a compound represented by the following formulas (BiF-1) to (BiF-5) from the viewpoint of further solubility in an organic solvent (specific examples) R 10 to R 13 therein are as defined above).
  • R 0 , R 1 and n are as defined in the formula (1-1), and R 10 ′ and R 11 ′ are R 10 and R described in the formula (1-1).
  • 11 and R 4 ′ and R 5 ′ each independently represents an alkyl group having 1 to 30 carbon atoms which may have a substituent, and 6 to 6 carbon atoms which may have a substituent.
  • aryl groups an optionally substituted alkenyl group having 2 to 30 carbon atoms, an optionally substituted alkoxy group having 1 to 30 carbon atoms, a halogen atom, a nitro group, an amino group, A carboxylic acid group, a thiol group, a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are Ether bond, ketone bond or ester bond May also comprise, group or at least one of the hydrogen atoms of the hydroxyl group substituted with a hydroxyl group of R 10 'and R 11' includes a group substituted with a glycidyl group, m 4 'and m 5' is , 0 to 8, m 10 ′ and m 11 ′ are integers
  • R 0 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, phenyl group, naphthyl group , Anthracene group, pyrenyl group, biphenyl group and heptacene group.
  • R 4 ′ and R 5 ′ are, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotriacontyl group, norbornyl group, adamantyl group, phenyl group , Naphthyl group, anthracene group, pyrenyl group, biphenyl group, heptacene group, vinyl group
  • R 0 , R 4 ′ and R 5 ′ includes an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • R 10 to R 13 have the same meanings as described in the formula (1-2),
  • R 16 represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, carbon number A bivalent aryl group having 6 to 30 carbon atoms or a divalent alkenyl group having 2 to 30 carbon atoms.
  • R 16 is, for example, a methylene group, ethylene group, propene group, butene group, pentene group, hexene group, heptene group, octene group, nonene group, decene group, undecene group, dodecene group, triacontene group, cyclopropene group, Cyclobutene group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, cyclononene group, cyclodecene group, cycloundecene group, cyclododecene group, cyclotriacontene group, divalent norbornyl group, divalent adamantyl group, divalent Phenyl group, divalent naphthyl group, divalent anthracene group, divalent pyrene group, divalent biphenyl group, divalent heptacene group, divalent
  • R 10 to R 13 have the same meanings as described in the above formula (1-2), and R 14 each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms.
  • m 14 ′ is an integer from 0 to 4, and m 14 is an integer from 0 to 5.
  • R 14 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
  • R 14 includes an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a
  • R 0 , R 4 ′ , R 5 ′ , m 4 ′ , m 5 ′ , m 10 ′ and m 11 ′ are as defined above, and R 1 ′ is a group having 1 to 60 carbon atoms. is there.
  • R 10 to R 13 have the same meanings as described in the above formula (1-2), and R 14 each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms.
  • m 14 is an integer of 0 to 5
  • 14 ′ is an integer from 0 to 4
  • m 14 ′′ is an integer from 0 to 3.
  • R 14 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
  • R 14 includes an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a
  • R 10 to R 13 have the same meanings as described in the formula (1-2),
  • R 15 represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group.
  • R 15 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
  • R 15 includes an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a
  • R 10 to R 13 have the same meanings as described in the formula (1-2). From the viewpoint of availability of raw materials, the following compounds are more preferable.
  • R 10 to R 13 have the same meanings as described in the formula (1-2).
  • the compound represented by the formula (0) preferably has the following structure from the viewpoint of etching resistance.
  • R 0A has the same meaning as the formula R Y
  • R 1A ′ has the same meaning as R Z
  • R 10 to R 13 have the same meaning as described in the formula (1-2).
  • R 0A has the same meaning as the formula R Y
  • R 1A ′ has the same meaning as R Z
  • R 10 to R 13 have the same meaning as described in the formula (1-2).
  • R 14 each independently represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, or 1 to 30 carbon atoms.
  • An alkoxy group, a halogen atom, and a thiol group, and m 14 ′ is an integer of 0 to 4.
  • R 14 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
  • R 14 includes an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • R 10 to R 13 have the same meanings as described in the formula (1-2),
  • R 15 represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group.
  • R 15 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
  • R 15 includes an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • R 10 to R 13 have the same meanings as described in the formula (1-2),
  • R 16 represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, carbon number A bivalent aryl group having 6 to 30 carbon atoms or a divalent alkenyl group having 2 to 30 carbon atoms.
  • R 16 is, for example, a methylene group, ethylene group, propene group, butene group, pentene group, hexene group, heptene group, octene group, nonene group, decene group, undecene group, dodecene group, triacontene group, cyclopropene group, Cyclobutene group, cyclopentene group, cyclohexene group, cycloheptene group, cyclooctene group, cyclononene group, cyclodecene group, cycloundecene group, cyclododecene group, cyclotriacontene group, divalent norbornyl group, divalent adamantyl group, divalent Examples thereof include a phenyl group, a divalent naphthyl group, a divalent anthracene group, a divalent heptacene group, a divalent vinyl group,
  • R 10 ⁇ R 13 have the same meanings as those described by the formula (1-2)
  • R 14 are each independently C 1 -C 30 linear, alkyl branched or cyclic Group, an aryl group having 6 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, and a thiol group
  • m 14 ′ is an integer of 0 to 4.
  • R 14 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
  • R 14 includes an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • R 10 to R 13 have the same meanings as described in the formula (1-2), and each R 14 is independently a linear or branched group having 1 to 30 carbon atoms. Or a cyclic alkyl group, an aryl group having 6 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogen atom, or a thiol group, and m 14 is an integer of 0 to 5 It is.
  • R 14 is, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl.
  • R 14 includes an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • R 10 to R 13 have the same meanings as described in the formula (1-2).
  • compounds having a dibenzoxanthene skeleton are more preferable from the viewpoint of heat resistance.
  • the compound represented by the formula (0) is more preferably a compound listed below from the viewpoint of availability of raw materials.
  • R 10 to R 13 have the same meanings as described in the formula (1-2).
  • the compounds listed above are preferably compounds having a dibenzoxanthene skeleton from the viewpoint of heat resistance.
  • the compound represented by the formula (0) preferably has the following structure from the viewpoint of raw material availability.
  • R 0A has the same meaning as the formula R Y
  • R 1A ′ has the same meaning as R Z
  • R 10 to R 13 have the same meaning as described in the formula (1-2).
  • the compounds listed above are preferably compounds having a xanthene skeleton from the viewpoint of heat resistance.
  • R 10 to R 13 have the same meanings as described in formula (1-2), and R 14 , R 15 , R 16 , m 14 and m 14 ′ have the same meanings as described above.
  • the compound represented by the formula (0) used in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited.
  • the compound represented by formula (1) as an example, the compound represented by formula (0) can be synthesized as follows.
  • the compound represented by the formula (1) is obtained by polycondensation reaction of biphenols, binaphthols or bianthracenols with the corresponding ketones under an acid catalyst under normal pressure to obtain a polyphenol compound, Subsequently, it is obtained by introducing a hydroxyalkyl group or a glycidyl group into at least one phenolic hydroxyl group of the polyphenol compound, or further introducing a glycidyl group into the hydroxy group of the hydroxyalkyl group.
  • combination can also be performed under pressure as needed.
  • transduces a hydroxyalkyl group or a glycidyl group not only after the condensation reaction of binaphthol etc. and ketones, but the stage before a condensation reaction may be sufficient.
  • the timing of introducing the glycidyl group into the hydroxy group of the hydroxyalkyl group may be any stage after the introduction of the hydroxyalkyl group.
  • biphenols examples include, but are not limited to, biphenol, methyl biphenol, methoxy binaphthol, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, it is more preferable to use biphenol from the viewpoint of stable supply of raw materials.
  • binaphthols examples include, but are not limited to, binaphthol, methyl binaphthol, methoxy binaphthol, and the like. These can be used alone or in combination of two or more. Among these, it is more preferable to use binaphthol in terms of increasing the carbon atom concentration and improving heat resistance.
  • bianthraceneols examples include, but are not particularly limited to, bianthraceneol, methylbianthracenol, methoxybianthracenol, and the like. These can be used alone or in combination of two or more. Among these, it is more preferable to use bianthraceneol in terms of increasing the carbon atom concentration and improving heat resistance.
  • ketones examples include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene.
  • Triacetylbenzene Triacetylbenzene, acetonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, benzophenone, diphenylcarbonylbenzene, triphenylcarbonylbenzene, benzonaphthone, diphenylcarbonylnaphthalene, phenylcarbonylbiphenyl, diphenylcarbonylbiphenyl, etc. Is particularly limited to There. These can be used alone or in combination of two or more.
  • the acid catalyst used in the reaction can be appropriately selected from known ones and is not particularly limited.
  • inorganic acids and organic acids are widely known.
  • inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, and succinic acid.
  • Adipic acid sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid Organic acids such as naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid Although it is mentioned, it is not specifically limited to these.
  • an organic acid and a solid acid are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferably used from the viewpoint of production such as availability and ease of handling.
  • an acid catalyst 1 type can be used individually or in combination of 2 or more types.
  • the amount of the acid catalyst used can be appropriately set according to the raw material to be used, the type of catalyst to be used, and further the reaction conditions, and is not particularly limited. It is preferable that it is a mass part.
  • a reaction solvent may be used.
  • the reaction solvent is not particularly limited as long as the reaction between the ketones to be used and biphenols, binaphthols, or bianthracenediol proceeds, and can be appropriately selected from known ones. Examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, or a mixed solvent thereof.
  • a solvent can be used individually by 1 type or in combination of 2 or more types.
  • the amount of these solvents used can be appropriately set according to the raw material used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. It is preferable that it is the range of these.
  • the reaction temperature in the reaction can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 ° C.
  • the reaction temperature is preferably higher, and specifically in the range of 60 to 200 ° C.
  • the reaction method can be appropriately selected from known methods, and is not particularly limited.
  • the reaction method is a method in which biphenols, binaphthols or bianthracenediol, ketones, and a catalyst are charged all together, or biphenols and binaphthols.
  • the obtained compound can be isolated according to a conventional method, and is not particularly limited.
  • reaction conditions 1.0 mol to excess of biphenols, binaphthols or bianthracenediol and 0.001 to 1 mol of an acid catalyst are used with respect to 1 mol of ketones, and 50 to 50 at normal pressure.
  • the reaction proceeds at 150 ° C. for about 20 minutes to 100 hours.
  • the target product can be isolated by a known method.
  • the reaction solution is concentrated, pure water is added to precipitate the reaction product, cooled to room temperature, filtered and separated, and the resulting solid is filtered and dried, followed by column chromatography.
  • the compound represented by the above formula (1), which is the target product can be obtained by separating and purifying from the by-product, and performing solvent distillation, filtration and drying.
  • a method of introducing a hydroxyalkyl group into at least one phenolic hydroxyl group of a polyphenol compound and introducing a hydroxyalkyl group or a glycidyl group into the hydroxy group is also known.
  • a hydroxyalkyl group can be introduced into at least one phenolic hydroxyl group of a polyphenol compound as follows.
  • the hydroxyalkyl group may be introduced into the phenolic hydroxyl group via an oxyalkyl group.
  • a hydroxyalkyloxyalkyl group or a hydroxyalkyloxyalkyloxyalkyl group is introduced.
  • a compound for introducing a hydroxyalkyl group can be synthesized or easily obtained by a known method.
  • chloroethanol bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, 2-iodoethyl acetate, ethylene oxide , Propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and butylene carbonate, but are not particularly limited.
  • a polyphenol compound and the compound for introducing the hydroxyalkyl group described above are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
  • an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
  • metal alkoxide sodium methoxide, sodium ethoxide, potassium methoxide, alkali metal such as potassium ethoxide or alkaline earth metal alkoxide
  • metal hydroxide sodium hydroxide, alkali metal such as potassium hydroxide
  • alkaline earth metal carbonate etc.
  • alkali metal such as sodium hydrogen carbonate, potassium hydrogen carbonate, or alkaline earth hydrogen carbonate
  • amines for example, tertiary amines (trialkylamines such as triethylamine, N, N -Aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole), carboxylic acid metal salts (alkali metal acetates or alkaline earth metal salts such as sodium acetate, calcium acetate, etc.) ) 20-15 at atmospheric pressure in the presence of a base catalyst such as an organic base The reaction is allowed to proceed
  • the reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water or the solvent is evaporated to dryness.
  • the compound in which the hydrogen atom of the hydroxyl group is substituted with a hydroxyalkyl group can be obtained by washing with distilled water if necessary and drying.
  • 2-chloroethyl acetate, 2-bromoethyl acetate, or 2-iodoethyl acetate is used, a hydroxyethyl group is introduced by deacylation after an acetoxyethyl group is introduced.
  • ethylene carbonate, propylene carbonate, or butylene carbonate a hydroxyalkyl group is introduced by adding an alkylene carbonate to cause a decarboxylation reaction.
  • a glycidyl group can be introduced into at least one phenolic hydroxyl group or hydroxyalkyl group of the polyphenol compound as follows.
  • a method of introducing a glycidyl group into the phenolic hydroxyl group or hydroxyalkyl group is also known.
  • a compound for introducing a glycidyl group can be synthesized or easily obtained by a known method, and examples thereof include epichlorohydrin and epibromohydrin, but are not particularly limited.
  • a polyphenol compound and a compound for introducing the glycidyl group described above are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
  • an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
  • metal alkoxide sodium methoxide, sodium ethoxide, potassium methoxide, alkali metal such as potassium ethoxide or alkaline earth metal alkoxide
  • metal hydroxide sodium hydroxide, alkali metal such as potassium hydroxide
  • alkaline earth metal carbonate etc.
  • alkali metal such as sodium hydrogen carbonate, potassium hydrogen carbonate, or alkaline earth hydrogen carbonate
  • amines for example, tertiary amines (trialkylamines such as triethylamine, N, N -Aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole), carboxylic acid metal salts (alkali metal acetates or alkaline earth metal salts such as sodium acetate, calcium acetate, etc.) ) 20-15 at atmospheric pressure in the presence of a base catalyst such as an organic base The reaction is allowed to proceed
  • reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water or the solvent is evaporated to dryness. Accordingly, the compound in which the hydrogen atom of the phenolic hydroxyl group or hydroxyalkyl group is substituted with a glycidyl group can be obtained by washing with distilled water and drying.
  • the group substituted with a hydroxyalkyl group or a glycidyl group reacts in the presence of a radical or an acid / alkali, and has solubility in an acid, an alkali, or an organic solvent used in a coating solvent or a developer.
  • the group substituted with a hydroxyalkyl group or a glycidyl group has a property of causing a chain reaction in the presence of a radical or an acid / alkali in order to enable pattern formation with higher sensitivity and higher resolution. preferable.
  • the compound represented by the formula (0) can be used as it is as a film-forming composition for lithography. Moreover, it can be used also as resin obtained by using the compound represented by the said Formula (0) as a monomer.
  • the resin of this embodiment is a resin having a unit structure derived from the general formula (0).
  • it can also be used as a resin obtained by reacting a compound represented by the formula (0) with a compound having crosslinking reactivity.
  • the resin obtained using the compound represented by the formula (0) as a monomer include those having a structure represented by the following formula (3). That is, the composition of the present embodiment may contain a resin having a structure represented by the following formula (3).
  • L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent.
  • the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond
  • R 0 has the same meaning as R Y
  • R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond
  • R 2 to R 5 are each independently an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
  • a hydroxyl group or a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group are an ether bond, a ketone bond, or an ester.
  • n is synonymous with the above N, and here, when n is an integer of 2 or more, the structural formulas in the n [] may be the same or different, p 2 to p 5 have the same meaning as r. )
  • L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent. It may be an alkoxylene group having 1 to 30 carbon atoms or a single bond.
  • the alkylene group, the arylene group, and the alkoxylene group may include an ether bond, a ketone bond, or an ester bond.
  • the alkylene group and alkoxylene group may be a linear, branched or cyclic group.
  • R 0 , R 1 , R 2 to R 5 , m 2 and m 3 , m 4 and m 5 , p 2 to p 5 , and n are as defined in the formula (1).
  • m 2 , m 3 , m 4 and m 5 are not simultaneously 0, and at least one of R 2 to R 5 is substituted with a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a glycidyl group Group.
  • the resin of the present embodiment can be obtained by reacting the compound represented by the formula (0) with a compound having crosslinking reactivity.
  • a known compound can be used without particular limitation as long as the compound represented by the formula (0) can be oligomerized or polymerized. Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.
  • the resin obtained using the compound represented by the formula (0) as a monomer include, for example, the compound represented by the formula (0) with an aldehyde and / or a ketone having a crosslinking reactivity.
  • examples thereof include resins that have been novolakized by a condensation reaction or the like.
  • aldehyde for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde
  • examples thereof include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural.
  • ketones include the aforementioned ketones. Among these, formaldehyde is more preferable. In addition, these aldehydes and / or ketones can be used individually by 1 type or in combination of 2 or more types.
  • the amount of the aldehyde and / or ketone used is not particularly limited, but is preferably 0.2 to 5 moles, more preferably 0.5 moles relative to 1 mole of the compound represented by the formula (0). ⁇ 2 moles.
  • a catalyst may be used.
  • the acid catalyst used here can be appropriately selected from known ones and is not particularly limited.
  • inorganic acids and organic acids are widely known.
  • inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, and succinic acid.
  • Adipic acid sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid Organic acids such as naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid Although it is mentioned, it is not specifically limited to these.
  • organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferred from the viewpoint of production such as availability and ease of handling.
  • hydrochloric acid or sulfuric acid is preferred from the viewpoint of production such as availability and ease of handling.
  • 1 type can be used individually or in combination of 2 or more types.
  • the amount of the acid catalyst used can be appropriately set according to the raw material to be used, the type of catalyst to be used, and further the reaction conditions, and is not particularly limited. It is preferable that it is a mass part.
  • aldehydes are not necessarily required.
  • a reaction solvent can be used.
  • the reaction solvent in this polycondensation can be appropriately selected from known solvents and is not particularly limited. Examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, and mixed solvents thereof. Illustrated.
  • a solvent can be used individually by 1 type or in combination of 2 or more types.
  • the amount of these solvents used can be appropriately set according to the raw material used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. It is preferable that it is the range of these.
  • the reaction temperature can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 ° C.
  • the reaction method can be appropriately selected from known methods, and is not particularly limited.
  • the reaction method may be a method in which the compound represented by the formula (0), the aldehyde and / or ketone, and a catalyst are charged together, There is a method in which a compound represented by the formula (0), an aldehyde and / or a ketone are dropped in the presence of a catalyst.
  • the obtained compound can be isolated according to a conventional method, and is not particularly limited.
  • a general method such as raising the temperature of the reaction vessel to 130 to 230 ° C. and removing volatile components at about 1 to 50 mmHg is adopted.
  • a novolak resin as the target product can be obtained.
  • the resin having the structure represented by the formula (3) may be a homopolymer of the compound represented by the formula (0), but is a copolymer with other phenols. May be.
  • the copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Although propylphenol, pyrogallol, thymol, etc. are mentioned, it is not specifically limited to these.
  • the resin having the structure represented by the formula (3) may be copolymerized with a polymerizable monomer other than the above-described phenols.
  • the copolymerization monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene.
  • the resin having the structure represented by the formula (3) is a binary or more (for example, a quaternary system) copolymer of the compound represented by the formula (1) and the above-described phenols. Even if it is a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the formula (1) and the above-mentioned copolymerization monomer, it is represented by the formula (1). It may be a ternary or more (for example, ternary to quaternary) copolymer of the above compound, the above-mentioned phenols, and the above-mentioned copolymerization monomer.
  • the molecular weight of the resin having the structure represented by the formula (3) is not particularly limited, but the polystyrene equivalent weight average molecular weight (Mw) is preferably 500 to 30,000, more preferably 750 to 20,000. Further, from the viewpoint of enhancing the crosslinking efficiency and suppressing the volatile components in the baking, the resin having the structure represented by the formula (3) has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.2. Those within the range of ⁇ 7 are preferred. The Mn can be obtained by the method described in Examples described later.
  • the resin having the structure represented by the formula (3) is preferably highly soluble in a solvent from the viewpoint of easier application of a wet process. More specifically, when these compounds and / or resins use 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) as a solvent, the solubility in the solvent is 10% by mass or more. It is preferable that Here, the solubility in PGM and / or PGMEA is defined as “resin mass ⁇ (resin mass + solvent mass) ⁇ 100 (mass%)”. For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin in PGMEA is “10 mass% or more”, and when it is not dissolved, it is “less than 10 mass%”.
  • R 0A has the same meaning as R Y
  • R 1A is an n A valent group having 1 to 60 carbon atoms or a single bond
  • R 2A each independently has an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
  • the hydrogen atom is a group substituted with a hydroxyalkyl group or a glycidyl group
  • the alkyl group, the aryl group, the alkenyl group, and the alkoxy group include an ether bond, a ketone bond, or an ester bond.
  • R 2A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group
  • n A has the same meaning as N above.
  • n A is an integer of 2 or more
  • the structural formulas in n A [] may be the same or different
  • X A is synonymous with X
  • m 2A is each independently an integer of 0 to 7, provided that at least one m 2A is an integer of 1 to 7;
  • q A is each independently 0 or 1.
  • R 0A has the same meaning as R Y described above.
  • R 1A is an n A valent group having 1 to 60 carbon atoms or a single bond.
  • n A is synonymous with N, and is an integer of 1 to 4.
  • the structural formulas in n A [] may be the same or different.
  • n-valent group examples include those having a linear hydrocarbon group, a branched hydrocarbon group, or an alicyclic hydrocarbon group.
  • the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group.
  • the n-valent hydrocarbon group may have an alicyclic hydrocarbon group, a double bond, a hetero atom, or an aromatic group having 6 to 60 carbon atoms.
  • R 2A each independently has an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or a substituent.
  • the hydrogen atom is a group substituted with a hydroxyalkyl group or a glycidyl group
  • the alkyl group, the aryl group, the alkenyl group, and the alkoxy group include an ether bond, a ketone bond, or an ester bond.
  • At least one of R 2A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • the alkyl group, alkenyl group and alkoxy group may be a linear, branched or cyclic group.
  • X A is synonymous with X, and each independently represents an oxygen atom, a sulfur atom, or no bridge.
  • X A is an oxygen atom or a sulfur atom, preferably because of the tendency to exhibit high heat resistance, and more preferably an oxygen atom.
  • X A in terms of solubility, it is preferable that the non-crosslinked.
  • m 2A is each independently an integer of 0 to 6. However, at least one m 2A is an integer of 1 to 6.
  • q A is each independently 0 or 1.
  • the compound represented by the formula (2) has a relatively low molecular weight, but has high heat resistance due to the rigidity of its structure, and therefore can be used under high temperature baking conditions. Moreover, it has tertiary carbon or quaternary carbon in the molecule, the crystallinity is suppressed, and it is suitably used as a film forming composition for lithography that can be used for manufacturing a film for lithography.
  • the solubility in a safe solvent is high, the heat resistance and the etching resistance are good, and the resist forming composition for lithography according to this embodiment gives a good resist pattern shape.
  • the film has a relatively low molecular weight and low viscosity, even a substrate having a step (particularly, a fine space or a hole pattern) can be uniformly filled to every corner of the step and the film can be flattened.
  • the composition for forming an underlayer film for lithography using the same can be relatively advantageously enhanced in embedding and planarization characteristics.
  • it is a compound having a relatively high carbon concentration, high etching resistance is also imparted.
  • the aromatic density is high, the refractive index is high, and coloring is suppressed by a wide range of heat treatments from low to high temperatures, so that it is also useful as a composition for forming various optical parts.
  • the one having quaternary carbon is preferable from the viewpoint of suppressing oxidative decomposition of the present compound to suppress coloring, high heat resistance, and improving solvent solubility.
  • Optical parts are used in the form of films and sheets, as well as plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms It is useful as an optical fiber, a solder resist for flexible printed wiring, a plating resist, an interlayer insulating film for multilayer printed wiring boards, and a photosensitive optical waveguide.
  • the compound represented by the formula (2) is preferably a compound represented by the following formula (2-1) from the viewpoint of easy crosslinking and solubility in an organic solvent. (2-1)
  • R 0A , R 1A , n A and q A and X A have the same meaning as described in the formula (2).
  • R 3A is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, substituted
  • An alkenyl group having 2 to 30 carbon atoms which may have a group, a halogen atom, a nitro group, an amino group, a carboxylic acid group, or a thiol group, and may be the same or different in the same naphthalene ring or benzene ring. May be.
  • R 4A is each independently a hydrogen atom or a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group, wherein at least one of R 4A is a hydroxyalkyl group, a glycidyloxyalkyl group or a glycidyl group; m 6A is each independently an integer of 0 to 5.
  • R 4A is a hydroxyalkyl group, glycidyl An oxyalkyl group or a glycidyl group;
  • R 4A At least one of is a hydrogen atom.
  • the compound represented by the formula (2-1) is preferably a compound represented by the following formula (2a).
  • X A , R 0A to R 2A , m 2A and n A are as defined in the formula (2).
  • the compound represented by the formula (2-1) is more preferably a compound represented by the following formula (2b).
  • X A , R 0A , R 1A , R 3A , R 4A , m 6A and n A are as defined in the formula (2-1).
  • the compound represented by the formula (2-1) is more preferably a compound represented by the following formula (2c).
  • X A , R 0A , R 1A , R 3A , R 4A , m 6A and n A are as defined in the formula (2-1).
  • the compound represented by the formula (2) is represented by the following formulas (BiN-1) to (BiN-4) or (XBiN-1) to (XBiN-3) from the viewpoint of further solubility in an organic solvent. It is particularly preferred that the compound be (R 4A in the specific examples is as defined above).
  • the compound represented by the formula (2) used in the present embodiment can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited.
  • a polyphenol compound is obtained by polycondensation reaction of phenols, naphthols and the corresponding ketones under an acid catalyst under normal pressure, and subsequently, at least one phenolic hydroxyl group of the polyphenol compound is hydroxylated. It can be obtained by introducing an alkyl group or a glycidyl group, or further introducing a glycidyl group into the hydroxy group of the hydroxyalkyl group.
  • combination can also be performed under pressure as needed.
  • transduces a hydroxyalkyl group or a glycidyl group not only after the condensation reaction of naphthols and ketones but the stage before a condensation reaction may be sufficient. Moreover, you may carry out after manufacturing resin mentioned later.
  • the timing for introducing the glycidyl group into the hydroxy group of the hydroxyalkyl group may be any stage after the introduction of the hydroxyalkyl group.
  • the naphthols are not particularly limited, and examples thereof include naphthol, methyl naphthol, methoxy naphthol, naphthalene diol, and the like. It is more preferable to use naphthalene diol because a xanthene structure can be easily formed.
  • the phenols are not particularly limited, and examples thereof include phenol, methylphenol, methoxybenzene, catechol, resorcinol, hydroquinone, and trimethylhydroquinone.
  • ketones examples include acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, acetophenone, diacetylbenzene.
  • the acid catalyst is not particularly limited, and can be appropriately selected from known inorganic acids and organic acids.
  • inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid; oxalic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalene
  • Organic acids such as sulfonic acid and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid Can be mentioned.
  • hydrochloric acid or sulfuric acid from the viewpoint of production such as availability and ease of handling.
  • hydrochloric acid or sulfuric acid from the viewpoint of
  • a reaction solvent may be used.
  • the reaction solvent is not particularly limited as long as the reaction between the ketones to be used and naphthols proceeds.
  • water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, or a mixed solvent thereof can be used.
  • the amount of the solvent is not particularly limited, and is, for example, in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material.
  • the reaction temperature is not particularly limited and can be appropriately selected according to the reactivity of the reaction raw material, but is preferably in the range of 10 to 200 ° C.
  • the lower the temperature, the higher the effect and the more preferable the range is 10 to 60 ° C.
  • the manufacturing method of the said compound is not specifically limited, For example, there exist the method of charging naphthols etc., ketones, and a catalyst collectively, and the method of dripping naphthols and ketones in catalyst presence. After the polycondensation reaction, in order to remove unreacted raw materials, catalysts, etc. existing in the system, the temperature of the reaction vessel can be raised to 130 to 230 ° C., and volatile components can be removed at about 1 to 50 mmHg. .
  • the amount of the raw material for producing the compound represented by the formula (2) is not particularly limited. For example, 2 moles to an excess amount of naphthols and the acid catalyst are added to 0.1 mole of 1 mole of aldehyde. The reaction proceeds by using 001-1 mol and reacting at 20-60 ° C. for 20 minutes to 100 hours at normal pressure.
  • the target product is isolated by a known method after the completion of the reaction.
  • the method for isolating the target product is not particularly limited.
  • the reaction solution is concentrated, pure water is added to precipitate the reaction product, the solution is cooled to room temperature, filtered, and separated to obtain a solid product. After filtering and drying, a method of separating and purifying from by-products by column chromatography, evaporating the solvent, filtering and drying to obtain the target compound can be mentioned.
  • a method for introducing a hydroxyalkyl group into at least one phenolic hydroxyl group of a polyphenol compound is also known.
  • a hydroxyalkyl group can be introduced into at least one phenolic hydroxyl group of the compound as follows.
  • the hydroxyalkyl group may be introduced into the phenolic hydroxyl group via an oxyalkyl group.
  • a hydroxyalkyloxyalkyl group or a hydroxyalkyloxyalkyloxyalkyl group is introduced.
  • a compound for introducing a hydroxyalkyl group can be synthesized or easily obtained by a known method.
  • chloroethanol bromoethanol, 2-chloroethyl acetate, 2-bromoethyl acetate, 2-iodoethyl acetate, ethylene oxide , Propylene oxide, butylene oxide, ethylene carbonate, propylene carbonate, and butylene carbonate, but are not particularly limited.
  • a polyphenol compound and a compound for introducing the above hydroxyalkyl group are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
  • an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
  • metal alkoxide sodium methoxide, sodium ethoxide, potassium methoxide, alkali metal such as potassium ethoxide or alkaline earth metal alkoxide
  • metal hydroxide sodium hydroxide, alkali metal such as potassium hydroxide
  • alkaline earth metal carbonate etc.
  • alkali metal such as sodium hydrogen carbonate, potassium hydrogen carbonate, or alkaline earth hydrogen carbonate
  • amines for example, tertiary amines (trialkylamines such as triethylamine, N, N -Aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole), carboxylic acid metal salts (alkali metal acetates or alkaline earth metal salts such as sodium acetate, calcium acetate, etc.) ) 20-15 at atmospheric pressure in the presence of a base catalyst such as an organic base The reaction is allowed to proceed
  • the reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water or the solvent is evaporated to dryness.
  • the compound in which the hydrogen atom of the hydroxyl group is substituted with a hydroxyalkylene group can be obtained by washing with distilled water if necessary and drying.
  • a hydroxyethyl group is introduced by deacylation after an acetoxyethyl group is introduced.
  • ethylene carbonate, propylene carbonate, or butylene carbonate a hydroxyalkyl group is introduced by adding an alkylene carbonate to cause a decarboxylation reaction.
  • a glycidyl group can be introduced into at least one phenolic hydroxyl group or hydroxyalkyl group of the polyphenol compound as follows.
  • a method of introducing a glycidyl group into the phenolic hydroxyl group or hydroxyalkyl group is also known.
  • a compound for introducing a glycidyl group can be synthesized or easily obtained by a known method, and examples thereof include epichlorohydrin and epibromohydrin, but are not particularly limited.
  • a polyphenol compound and the compound for introducing the glycidyl group described above are dissolved or suspended in an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
  • an aprotic solvent such as acetone, tetrahydrofuran (THF), propylene glycol monomethyl ether acetate or the like.
  • metal alkoxide sodium methoxide, sodium ethoxide, potassium methoxide, alkali metal such as potassium ethoxide or alkaline earth metal alkoxide
  • metal hydroxide sodium hydroxide, alkali metal such as potassium hydroxide
  • alkaline earth metal carbonate etc.
  • alkali metal such as sodium hydrogen carbonate, potassium hydrogen carbonate, or alkaline earth hydrogen carbonate
  • amines for example, tertiary amines (trialkylamines such as triethylamine, N, N -Aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as 1-methylimidazole), carboxylic acid metal salts (alkali metal acetates or alkaline earth metal salts such as sodium acetate, calcium acetate, etc.) ) 20-15 at atmospheric pressure in the presence of a base catalyst such as an organic base The reaction is allowed to proceed
  • reaction solution is neutralized with an acid and added to distilled water to precipitate a white solid, and then the separated solid is washed with distilled water or the solvent is evaporated to dryness. Accordingly, the compound in which the hydrogen atom of the phenolic hydroxyl group or hydroxyalkyl group is substituted with a glycidyl group can be obtained by washing with distilled water and drying.
  • the group substituted with a hydroxyalkyl group or a glycidyl group reacts in the presence of a radical or an acid / alkali, and has solubility in an acid, an alkali, or an organic solvent used in a coating solvent or a developer.
  • the group substituted with a hydroxyalkyl group or a glycidyl group has a property of causing a chain reaction in the presence of a radical or an acid / alkali in order to enable pattern formation with higher sensitivity and higher resolution. preferable.
  • the compound represented by the formula (2) can be used as it is as a film-forming composition for lithography. Moreover, it can be used also as resin obtained by using the compound represented by the said Formula (2) as a monomer. For example, it can also be used as a resin obtained by reacting a compound represented by the formula (2) with a compound having crosslinking reactivity.
  • the resin obtained using the compound represented by the formula (2) as a monomer include those having a structure represented by the following formula (4). That is, the composition of the present embodiment may contain a resin having a structure represented by the following formula (4).
  • L has an optionally substituted alkylene group having 1 to 30 carbon atoms, an optionally substituted arylene group having 6 to 30 carbon atoms, and a substituent.
  • the alkylene group, the arylene group and the alkoxylene group may contain an ether bond, a ketone bond or an ester bond, R 0A , R 1A , R 2A , m 2A , n A , q A and X A are the same as those in the formula (2), When n A is an integer of 2 or more, the structural formulas in the n A [] may be the same or different. However, at least one of R 2A includes a group in which a hydrogen atom of a hydroxyl group is substituted with a hydroxyalkyl group or a group substituted with a glycidyl group.
  • the resin of this embodiment can be obtained by reacting the compound represented by the formula (2) with a compound having a crosslinking reactivity.
  • a known compound can be used without particular limitation as long as the compound represented by the formula (2) can be oligomerized or polymerized.
  • Specific examples thereof include, but are not limited to, aldehydes, ketones, carboxylic acids, carboxylic acid halides, halogen-containing compounds, amino compounds, imino compounds, isocyanates, unsaturated hydrocarbon group-containing compounds, and the like.
  • the resin having the structure represented by the formula (2) include, for example, a condensation reaction of the compound represented by the formula (2) with an aldehyde and / or a ketone having a crosslinking reaction. And a novolak resin.
  • aldehyde for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde
  • examples thereof include, but are not limited to, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde, and furfural.
  • ketones include the aforementioned ketones. Among these, formaldehyde is more preferable. In addition, these aldehydes and / or ketones can be used individually by 1 type or in combination of 2 or more types.
  • the amount of the aldehyde and / or ketone used is not particularly limited, but is preferably 0.2 to 5 mol, more preferably 0.5 mol, relative to 1 mol of the compound represented by the formula (2). ⁇ 2 moles.
  • a catalyst may be used.
  • the acid catalyst used here can be appropriately selected from known ones and is not particularly limited.
  • inorganic acids and organic acids are widely known.
  • inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, and succinic acid.
  • Adipic acid sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid Organic acids such as naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid Although it is mentioned, it is not specifically limited to these.
  • an organic acid or a solid acid is preferable from the viewpoint of manufacturing, and hydrochloric acid or sulfuric acid is preferable from the viewpoint of manufacturing such as availability and ease of handling.
  • an acid catalyst 1 type can be used individually or in combination of 2 or more types.
  • the amount of the acid catalyst used can be appropriately set according to the raw material used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0.01 to 100 per 100 parts by mass of the reactive raw material. It is preferable that it is a mass part.
  • indene hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene, ⁇ -pinene, ⁇ -pinene
  • aldehydes are not necessarily required.
  • a reaction solvent can be used in the condensation reaction between the compound represented by the formula (2) and the aldehyde and / or ketone.
  • the reaction solvent in this polycondensation can be appropriately selected from known solvents and is not particularly limited. Examples thereof include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, and mixed solvents thereof. Illustrated.
  • a solvent can be used individually by 1 type or in combination of 2 or more types.
  • the amount of these solvents used can be appropriately set according to the raw material used, the type of catalyst used, and the reaction conditions, and is not particularly limited, but is 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw material. It is preferable that it is the range of these.
  • the reaction temperature can be appropriately selected according to the reactivity of the reaction raw material, and is not particularly limited, but is usually in the range of 10 to 200 ° C.
  • the reaction method can be appropriately selected from known methods and is not particularly limited.
  • the reaction method may be a method in which the compound represented by the formula (2), the aldehyde and / or ketone, and a catalyst are charged all together, There is a method in which a compound represented by the formula (2), an aldehyde and / or a ketone are added dropwise in the presence of a catalyst.
  • the obtained compound can be isolated according to a conventional method, and is not particularly limited.
  • a general method such as raising the temperature of the reaction vessel to 130 to 230 ° C. and removing volatile components at about 1 to 50 mmHg is adopted.
  • a novolak resin as the target product can be obtained.
  • the resin having the structure represented by the formula (4) may be a homopolymer of the compound represented by the formula (2), but is a copolymer with other phenols. May be.
  • the copolymerizable phenols include phenol, cresol, dimethylphenol, trimethylphenol, butylphenol, phenylphenol, diphenylphenol, naphthylphenol, resorcinol, methylresorcinol, catechol, butylcatechol, methoxyphenol, methoxyphenol, Although propylphenol, pyrogallol, thymol, etc. are mentioned, it is not specifically limited to these.
  • the resin having the structure represented by the formula (4) may be copolymerized with a polymerizable monomer other than the above-described phenols.
  • the copolymerization monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene.
  • the resin having the structure represented by the formula (2) is a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the formula (2) and the above-described phenols. Even in the case of a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the formula (2) and the above-described copolymerization monomer, it is represented by the formula (2). It may be a ternary or more (for example, ternary to quaternary) copolymer of the above compound, the above-mentioned phenols, and the above-mentioned copolymerization monomer.
  • the molecular weight of the resin having the structure represented by the formula (4) is not particularly limited, but the polystyrene-equivalent weight average molecular weight (Mw) is preferably 500 to 30,000, more preferably 750 to 20,000. Further, from the viewpoint of increasing the crosslinking efficiency and suppressing the volatile components in the baking, the resin having the structure represented by the formula (4) has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.2. Those within the range of ⁇ 7 are preferred. The Mn can be obtained by the method described in Examples described later.
  • the resin having the structure represented by the formula (4) is preferably highly soluble in a solvent from the viewpoint of easier application of a wet process. More specifically, when these compounds and / or resins use 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) as a solvent, the solubility in the solvent is 10% by mass or more. It is preferable that Here, the solubility in PGM and / or PGMEA is defined as “resin mass ⁇ (resin mass + solvent mass) ⁇ 100 (mass%)”. For example, when 10 g of the resin is dissolved in 90 g of PGMEA, the solubility of the resin in PGMEA is “10 mass% or more”, and when it is not dissolved, it is “less than 10 mass%”.
  • the compound represented by the formula (0) and the resin obtained using this as a monomer can be purified by the following purification method. That is, the compound and / or resin purification method of the present embodiment includes a compound represented by the formula (0) and a resin obtained using the compound as a monomer (for example, a compound represented by the formula (1), the formula A resin obtained using the compound represented by (1) as a monomer, one or more selected from a compound represented by the formula (2) and a resin obtained using the compound represented by the formula (2) as a monomer) A step of obtaining a solution (S) by dissolving in a solvent, and a step of contacting the obtained solution (S) with an acidic aqueous solution to extract impurities in the compound and / or the resin (first extraction) And a solvent used in the step of obtaining the solution (S) includes an organic solvent that is arbitrarily immiscible with water.
  • a solvent used in the step of obtaining the solution (S) includes an organic solvent that is arbitrarily immis
  • the resin is, for example, a resin obtained by a reaction between the compound represented by the formula (1) and / or the compound represented by the formula (2) and a compound having a crosslinking reaction.
  • a resin obtained by a reaction between the compound represented by the formula (1) and / or the compound represented by the formula (2) and a compound having a crosslinking reaction Preferably there is.
  • the purification method content of the various metals which can be contained as an impurity in the compound or resin which has the specific structure mentioned above can be reduced. More specifically, in the purification method, the compound and / or the resin is dissolved in an organic solvent that is arbitrarily immiscible with water to obtain a solution (S), and the solution (S) is further converted into an acidic aqueous solution.
  • the extraction process can be performed by contact. Thereby, after transferring the metal content contained in the solution (S) to the aqueous phase, the organic phase and the aqueous phase can be separated to obtain a compound and / or resin having a reduced
  • the compound and resin used in the purification method may be used alone or in combination of two or more.
  • the said compound and resin may contain various surfactant, various crosslinking agents, various acid generators, various stabilizers, etc.
  • the solvent that is arbitrarily miscible with water used in the purification method is not particularly limited, but is preferably an organic solvent that can be safely applied to a semiconductor manufacturing process. Specifically, the solubility in water at room temperature is 30%.
  • the organic solvent is less than 20%, more preferably less than 20%, particularly preferably less than 10%.
  • the amount of the organic solvent used is preferably 1 to 100 times by mass with respect to the total amount of the compound to be used and the resin.
  • ethers such as diethyl ether and diisopropyl ether
  • esters such as ethyl acetate, n-butyl acetate, and isoamyl acetate, methyl ethyl ketone, and methyl isobutyl.
  • Ketones such as ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone; ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl Glycol ether acetates such as ether acetate; Aliphatic hydrocarbons such as n-hexane and n-heptane; Aromatic hydrocarbons such as toluene and xylene Methylene chloride, halogenated hydrocarbons such as chloroform and the like.
  • toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, methyl isobutyl ketone, ethyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate are more preferable, More preferred are methyl isobutyl ketone and ethyl acetate. Methyl isobutyl ketone, ethyl acetate, etc.
  • solvents are removed when the solvent is industrially distilled off or dried because the compound and the resin containing the compound as a constituent component have a relatively high saturation solubility and a relatively low boiling point. It is possible to reduce the load in the process.
  • These solvents can be used alone or in combination of two or more.
  • the acidic aqueous solution used in the purification method is appropriately selected from aqueous solutions in which generally known organic compounds or inorganic compounds are dissolved in water.
  • a mineral acid aqueous solution in which a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or the like is dissolved in water, or acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid
  • acidic aqueous solutions can be used alone or in combination of two or more.
  • one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or acetic acid, propionic acid, succinic acid, malonic acid, succinic acid, fumaric acid, maleic acid,
  • One or more organic acid aqueous solutions selected from the group consisting of tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid are preferred, and sulfuric acid, nitric acid, acetic acid, oxalic acid,
  • An aqueous solution of carboxylic acid such as tartaric acid and citric acid is more preferable
  • an aqueous solution of sulfuric acid, succinic acid, tartaric acid and citric acid is more preferable, and
  • the pH of the acidic aqueous solution used in the purification method is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the influence on the compound and the resin.
  • the pH range is about 0 to 5, preferably about pH 0 to 3.
  • the amount of the acidic aqueous solution used in the purification method is not particularly limited, but from the viewpoint of reducing the number of extractions for metal removal and from the viewpoint of securing operability in consideration of the total amount of liquid, the amount used is It is preferable to adjust. From the above viewpoint, the amount of the acidic aqueous solution used is preferably 10 to 200% by mass, and more preferably 20 to 100% by mass with respect to 100% by mass of the solution (S).
  • a metal component can be extracted from the compound or the resin in the solution (S) by bringing the acidic aqueous solution into contact with the solution (S).
  • the solution (S) further contains an organic solvent arbitrarily mixed with water.
  • an organic solvent arbitrarily mixed with water is included, the amount of the compound and / or resin charged can be increased, the liquid separation property is improved, and purification can be performed with high pot efficiency.
  • the method for adding an organic solvent arbitrarily mixed with water is not particularly limited.
  • any of a method of adding to a solution containing an organic solvent in advance, a method of adding to water or an acidic aqueous solution in advance, and a method of adding after bringing a solution containing an organic solvent into contact with water or an acidic aqueous solution may be used.
  • the method of adding to the solution containing an organic solvent in advance is preferable from the viewpoint of the workability of the operation and the ease of management of the charged amount.
  • the organic solvent arbitrarily mixed with water used in the purification method is not particularly limited, but an organic solvent that can be safely applied to a semiconductor manufacturing process is preferable.
  • the amount of the organic solvent arbitrarily mixed with water is not particularly limited as long as the solution phase and the aqueous phase are separated from each other, but is 0.1 to 100 times by mass with respect to the total amount of the compound and the resin to be used. It is preferably 0.1 to 50 times by mass, more preferably 0.1 to 20 times by mass.
  • organic solvent arbitrarily mixed with water used in the purification method include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol and isopropanol; acetone And ketones such as N-methylpyrrolidone; aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and propylene glycol monoethyl ether.
  • ethers such as tetrahydrofuran and 1,3-dioxolane
  • alcohols such as methanol, ethanol and isopropanol
  • acetone And ketones such as N-methylpyrrolidone
  • aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glyco
  • N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferable, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferable.
  • These solvents can be used alone or in combination of two or more.
  • the temperature at the time of the extraction treatment is usually 20 to 90 ° C, preferably 30 to 80 ° C.
  • the extraction operation is performed, for example, by mixing the mixture well by stirring or the like and then allowing it to stand. Thereby, the metal part contained in solution (S) transfers to an aqueous phase. Moreover, the acidity of a solution falls by this operation and the quality change of a compound and / or resin can be suppressed.
  • the solution phase is recovered by decantation or the like.
  • the standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation between the solvent-containing solution phase and the aqueous phase.
  • the time for standing is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.
  • the extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times.
  • the solution phase containing the compound or the resin is further brought into contact with water to extract impurities in the compound or the resin (second extraction step). It is preferable. Specifically, for example, after performing the extraction treatment using an acidic aqueous solution, the solution phase containing the compound and / or resin and solvent extracted and recovered from the aqueous solution is further subjected to an extraction treatment with water. It is preferable.
  • the above-described extraction treatment with water is not particularly limited. For example, after the solution phase and water are mixed well by stirring or the like, the obtained mixed solution can be left still.
  • the solution phase can be recovered by decantation or the like.
  • the water used here is water with a small metal content, for example, ion-exchanged water or the like in accordance with the purpose of the present embodiment.
  • the extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separation a plurality of times. Further, the use ratio of both in the extraction process, conditions such as temperature and time are not particularly limited, but they may be the same as those in the contact process with the acidic aqueous solution.
  • the water that can be mixed into the solution containing the compound and / or resin and solvent thus obtained can be easily removed by performing an operation such as vacuum distillation. Moreover, a solvent can be added to the said solution as needed, and the density
  • the method for isolating the compound and / or resin from the solution containing the obtained compound and / or resin and solvent is not particularly limited, and known methods such as removal under reduced pressure, separation by reprecipitation, and combinations thereof. Can be done. If necessary, known processes such as a concentration operation, a filtration operation, a centrifugal separation operation, and a drying operation can be performed.
  • composition contains 1 or more types chosen from the group which consists of a compound and resin of the above-mentioned this embodiment.
  • the composition of this embodiment can further contain a solvent, an acid generator, a crosslinking agent, a crosslinking accelerator, a radical polymerization initiator, and the like.
  • the composition of the present embodiment can be used for a film forming application for lithography (that is, a film forming composition for lithography) and an optical component forming application.
  • the composition of the present embodiment is one or more selected from the group consisting of the compound of the present embodiment and a resin (for example, a compound represented by the formula (1), a compound represented by the formula (1) Resin as a monomer, one or more selected from the group consisting of a compound represented by the formula (2) and a resin obtained by using the compound represented by the formula (2) as a monomer) as a resist base material can do.
  • a resin for example, a compound represented by the formula (1), a compound represented by the formula (1) Resin as a monomer, one or more selected from the group consisting of a compound represented by the formula (2) and a resin obtained by using the compound represented by the formula (2) as a monomer
  • the composition of this embodiment can be used as a film-forming composition for lithography for chemical amplification resist applications (hereinafter also referred to as a resist composition).
  • the resist composition contains, for example, one or more selected from the group consisting of the compound and resin of the present embodiment.
  • the resist composition preferably contains a solvent.
  • the solvent include, but are not limited to, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, and ethylene glycol mono-n-butyl ether acetate.
  • Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono -Propylene glycol such as n-butyl ether acetate Cole monoalkyl ether acetates; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, n-amyl lactate, etc.
  • PGMEA propylene glycol monomethyl ether acetate
  • PGMEA propylene glycol monoethyl ether acetate
  • Lactate esters aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, n-amyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate; Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyrate Other esters such as acetate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate and ethyl pyruvate; aromatic hydrocarbons such as toluene and xylene Ketones such as 2-heptan
  • the solvent used in this embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA, PGME, CHN, CPN, 2-heptanone, anisole, butyl acetate, ethyl propionate and ethyl lactate.
  • a seed more preferably at least one selected from PGMEA, PGME and CHN.
  • the amount of the solid component and the amount of the solvent are not particularly limited, but 1 to 80% by weight of the solid component and 20 to 99% of the solvent with respect to 100% by weight of the total amount of the solid component and the solvent.
  • the solid component is preferably 1 to 50% by mass, more preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, further preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent, and particularly preferably solid
  • the component is 2 to 10% by mass and the solvent is 90 to 98% by mass.
  • the resist composition contains, as another solid component, at least one selected from the group consisting of an acid generator (C), a crosslinking agent (G), an acid diffusion controller (E), and other components (F). May be.
  • a solid component means components other than a solvent.
  • the acid generator (C), the crosslinking agent (G), the acid diffusion controller (E) and other components (F), known ones can be used, and are not particularly limited. Those described in Japanese Patent No. / 024778 are preferable.
  • the content of the compound and resin of the above-described embodiment used as a resist base material is not particularly limited, but the total mass of the solid components (resist base material, acid generator (C), cross-linking agent ( G), the total amount of solid components including optionally used components such as the acid diffusion controller (E) and other components (F), the same shall apply hereinafter)) is preferably 50 to 99.4% by mass, More preferred is 55 to 90% by mass, still more preferred is 60 to 80% by mass, and particularly preferred is 60 to 70% by mass. In the case of the content, the resolution is further improved and the line edge roughness (LER) is further reduced. In addition, when containing both a compound and resin as a resist base material, the said content is the total amount of both components.
  • additives such as thermosetting resins, photocurable resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants, etc. 1 type (s) or 2 or more types can be added.
  • another component (F) may be called arbitrary component (F).
  • contents of a resist base material (hereinafter also referred to as component (A)), an acid generator (C), a crosslinking agent (G), an acid diffusion controller (E), and an optional component (F)
  • component (A) / Acid generator (C) / Crosslinking agent (G) / Acid diffusion controller (E) / Optional component (F)
  • component (A) is mass% based on solid matter, Preferably 50 to 99.4 / 0.001 to 49 / 0.5 to 49 / 0.001 to 49/0 to 49, More preferably 55 to 90/1 to 40 / 0.5 to 40 / 0.01 to 10/0 to 5, More preferably 60 to 80/3 to 30/1 to 30 / 0.01 to 5/0 to 1, Particularly preferred is 60 to 70/10 to 25/2 to 20 / 0.01 to 3/0.
  • the blending ratio of each component is selected from each range so that the sum is 100% by mass. When the above composition is used, the performance such as sensitivity, resolution and developability is excellent.
  • the resist composition is usually prepared by dissolving each component in a solvent at the time of use to obtain a uniform solution, and then filtering with a filter having a pore size of about 0.2 ⁇ m, for example, as necessary.
  • the resist composition may contain a resin other than the compound and resin of the present embodiment as long as the object of the present invention is not impaired.
  • the resin is not particularly limited, and for example, a novolac resin, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and a polymer containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units. A combination or a derivative thereof may be used.
  • the content of the resin is not particularly limited and is appropriately adjusted according to the type of the component (A) to be used, but is preferably 30 parts by mass or less, more preferably 100 parts by mass of the component (A). It is 10 mass parts or less, More preferably, it is 5 mass parts or less, Most preferably, it is 0 mass part.
  • the resist composition can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process. Either a positive resist pattern or a negative resist pattern can be created depending on the type of compound and resin of the present embodiment and / or the type of developer used.
  • the dissolution rate of the amorphous film formed by spin-coating the resist composition in a developing solution at 23 ° C. is preferably 5 ⁇ / sec or less, more preferably 0.05 to 5 ⁇ / sec, More preferred is .0005 to 5 liters / sec.
  • the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist.
  • the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumed that the contrast between the exposed portion dissolved in the developer and the unexposed portion not dissolved in the developer increases due to the change in solubility of the compound and resin of the present embodiment before and after exposure. Is done.
  • the dissolution rate of the amorphous film formed by spin-coating the resist composition in a developer at 23 ° C. is preferably 10 ⁇ / sec or more.
  • the dissolution rate is 10 ⁇ / sec or more, it is easily dissolved in a developer and more suitable for a resist.
  • the dissolution rate is 10 ⁇ / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the compound and resin of the present embodiment described above dissolves and LER is reduced. There is also an effect of reducing defects.
  • the dissolution rate can be determined by immersing the amorphous film in a developer at a temperature of 23 ° C. for a predetermined time, and measuring the film thickness before and after the immersion by a known method such as visual observation, an ellipsometer, or a QCM method.
  • the dissolution rate of the amorphous film formed by spin-coating the resist composition in a developer at 23 ° C. at a portion exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray is It is preferably 10 ⁇ / sec or more.
  • the dissolution rate is 10 ⁇ / sec or more, it is easily dissolved in a developer and more suitable for a resist.
  • the dissolution rate is 10 ⁇ / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the compound and resin of the present embodiment described above dissolves and LER is reduced. There is also an effect of reducing defects.
  • the dissolution rate in a developing solution at 23 ° C. of a portion exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray of an amorphous film formed by spin coating the resist composition is 5 ⁇ / sec or less is preferable, 0.05 to 5 ⁇ / sec is more preferable, and 0.0005 to 5 ⁇ / sec is more preferable.
  • the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist.
  • the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved.
  • the composition of this embodiment can be used as a film-forming composition for lithography for non-chemically amplified resist applications (hereinafter also referred to as a radiation-sensitive composition).
  • the component (A) (the compound and resin of the above-described embodiment) contained in the radiation-sensitive composition is used in combination with the diazonaphthoquinone photoactive compound (B) described later, and g-line, h-line, i-line, KrF.
  • a positive resist substrate that becomes a compound that is easily soluble in a developer by irradiation with an excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray.
  • G-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray does not change the property of component (A) greatly, but diazonaphthoquinone photoactivity is hardly soluble in the developer.
  • the component (A) contained in the radiation-sensitive composition is a compound having a relatively low molecular weight, the roughness of the obtained resist pattern is very small.
  • at least one selected from the group consisting of R 0 to R 5 is preferably a group containing an iodine atom.
  • R 0A , R 1A and R 2A It is preferable that at least one selected from the group consisting of is a group containing an iodine atom.
  • the glass transition temperature of the component (A) (resist base material) contained in the radiation-sensitive composition is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. It is. Although the upper limit of the glass transition temperature of a component (A) is not specifically limited, For example, it is 400 degreeC. When the glass transition temperature of the component (A) is within the above range, the semiconductor lithography process has heat resistance capable of maintaining the pattern shape, and performance such as high resolution is improved.
  • the crystallization calorific value obtained by differential scanning calorimetric analysis of the glass transition temperature of the component (A) contained in the radiation-sensitive composition is preferably less than 20 J / g.
  • (crystallization temperature) ⁇ glass transition temperature is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, and particularly preferably 130 ° C. or higher.
  • crystallization heat generation amount is less than 20 J / g, or (crystallization temperature) ⁇ (glass transition temperature) is in the above range, an amorphous film can be easily formed by spin-coating the radiation-sensitive composition, and The film formability required for the resist can be maintained for a long time, and the resolution can be improved.
  • the crystallization heat generation amount, the crystallization temperature, and the glass transition temperature can be obtained by differential scanning calorimetry using DSC / TA-50WS manufactured by Shimadzu Corporation.
  • About 10 mg of a sample is put into an aluminum non-sealed container and heated to a melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (50 mL / min).
  • the temperature is raised again to the melting point or higher at a temperature rising rate of 20 ° C./min in a nitrogen gas stream (30 mL / min). Further, after rapid cooling, the temperature is increased again to 400 ° C.
  • the temperature at the midpoint of the step difference of the baseline that has changed in a step shape is the glass transition temperature (Tg), and the temperature of the exothermic peak that appears thereafter is the crystallization temperature.
  • Tg glass transition temperature
  • the calorific value is obtained from the area of the region surrounded by the exothermic peak and the baseline, and is defined as the crystallization calorific value.
  • the component (A) contained in the radiation-sensitive composition is sublimated under normal pressure at 100 or less, preferably 120 ° C. or less, more preferably 130 ° C. or less, further preferably 140 ° C. or less, particularly preferably 150 ° C. or less. It is preferable that the property is low.
  • the low sublimation property means that in thermogravimetric analysis, the weight loss when held at a predetermined temperature for 10 minutes is 10% or less, preferably 5% or less, more preferably 3% or less, still more preferably 1% or less, particularly preferably. Indicates 0.1% or less. Since the sublimation property is low, it is possible to prevent exposure apparatus from being contaminated by outgas during exposure. In addition, a good pattern shape can be obtained with low roughness.
  • Component (A) contained in the radiation-sensitive composition is propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone, anisole, A solvent selected from butyl acetate, ethyl propionate and ethyl lactate and having the highest solubility in component (A) at 23 ° C., preferably 1% by mass or more, more preferably 5% by mass or more, More preferably 10% by mass or more, particularly preferably selected from PGMEA, PGME, CHN, and (A) 20% by mass or more at 23 ° C. in a solvent having the highest solubility in the resist base material, Particularly preferably, it dissolves in PGMEA at 20 ° C. or more at 23 ° C.
  • the semiconductor manufacturing process can be used in actual production.
  • the diazonaphthoquinone photoactive compound (B) contained in the radiation-sensitive composition is a diazonaphthoquinone substance containing a polymeric and non-polymeric diazonaphthoquinone photoactive compound.
  • a photosensitive component As long as it is used as (photosensitive agent), one or two or more kinds can be arbitrarily selected and used without particular limitation.
  • a photosensitizer it was obtained by reacting naphthoquinone diazide sulfonic acid chloride, benzoquinone diazide sulfonic acid chloride, etc. with a low molecular compound or a high molecular compound having a functional group capable of condensation reaction with these acid chlorides.
  • Compounds are preferred.
  • the functional group capable of condensing with acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amino group, and a hydroxyl group is particularly preferable.
  • the compound capable of condensing with an acid chloride containing a hydroxyl group is not particularly limited.
  • hydroquinone, resorcin, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,4,4′-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2 ′, 3,4,6′- Hydroxybenzophenones such as pentahydroxybenzophenone, hydroxyphenylalkanes such as bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) propane 4,4 ', 3 ", 4" -tetrahydroxy-3,5, Hydroxytriphenylmethane such as 3 ', 5'-tetramethyltriphenylmethane, 4,4', 2 ", 3", 4 "-pentahydroxy-3,5,3 ', 5'-tetrate
  • acid chlorides such as naphthoquinone diazide sulfonic acid chloride and benzoquinone diazide sulfonic acid chloride include 1,2-naphthoquinone diazide-5-sulfonyl chloride, 1,2-naphthoquinone diazide-4-sulfonyl chloride, and the like. Can be mentioned.
  • the radiation-sensitive composition is prepared by, for example, dissolving each component in a solvent at the time of use to obtain a uniform solution, and then filtering, for example, with a filter having a pore size of about 0.2 ⁇ m as necessary. Is preferred.
  • the radiation-sensitive composition can form an amorphous film by spin coating. Further, it can be applied to a general semiconductor manufacturing process. Depending on the type of developer used, either a positive resist pattern or a negative resist pattern can be created.
  • the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition in a developing solution at 23 ° C. is preferably 5 ⁇ / sec or less, more preferably 0.05 to 5 ⁇ / sec. 0.0005 to 5 cm / sec is more preferable. When the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist.
  • the dissolution rate when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is due to the contrast of the interface between the exposed portion dissolved in the developer and the unexposed portion not dissolved in the developer due to a change in the solubility of the resin containing the compound and resin of the present embodiment as constituents before and after exposure. Is estimated to be larger. Further, there is an effect of reducing LER and reducing defects.
  • the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition in a developing solution at 23 ° C. is preferably 10 ⁇ / sec or more.
  • the dissolution rate When the dissolution rate is 10 ⁇ / sec or more, it is easily dissolved in a developer and more suitable for a resist. Further, when the dissolution rate is 10 ⁇ / sec or more, the resolution may be improved. This is presumed to be because the micro surface portion of the resin containing the compound and resin of the present embodiment described above as constituent components dissolves and LER is reduced. There is also an effect of reducing defects.
  • the dissolution rate can be determined by immersing the amorphous film in a developer at a temperature of 23 ° C. for a predetermined time, and measuring the film thickness before and after the immersion by a known method such as visual observation, an ellipsometer, or a QCM method.
  • the amorphous film formed by spin-coating the radiation-sensitive composition is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, or at 20 to 500 ° C.
  • the dissolution rate of the exposed portion after heating in the developing solution at 23 ° C. is preferably 10 ⁇ / sec or more, more preferably 10 to 10000 ⁇ / sec, and further preferably 100 to 1000 ⁇ / sec.
  • the dissolution rate is 10 ⁇ / sec or more, it is easily dissolved in a developer and more suitable for a resist.
  • the dissolution rate is 10000 kg / sec or less, the resolution may be improved.
  • the amorphous film formed by spin-coating the radiation-sensitive composition is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, or at 20 to 500 ° C.
  • the dissolution rate of the exposed portion after heating with respect to the developer at 23 ° C. is preferably 5 K / sec or less, more preferably 0.05 to 5 K / sec, and further preferably 0.0005 to 5 K / sec.
  • the resist When the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and can be a resist. In addition, when the dissolution rate is 0.0005 kg / sec or more, the resolution may be improved. This is presumed that the contrast of the unexposed portion that dissolves in the developer and the interface between the exposed portion that does not dissolve in the developer increases due to the change in solubility of the compound and resin of the present embodiment before and after exposure. Is done. Further, there is an effect of reducing LER and reducing defects.
  • the content of the component (A) is the solid component total weight (component (A), diazonaphthoquinone photoactive compound (B) and other components (D), etc.)
  • the total of the components is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, and particularly preferably 25 to 75% by mass.
  • the radiation-sensitive composition can obtain a pattern with high sensitivity and small roughness.
  • the content of the diazonaphthoquinone photoactive compound (B) is arbitrarily selected from the total weight of the solid component (component (A), diazonaphthoquinone photoactive compound (B), and other components (D)).
  • the total of solid components used, the same shall apply hereinafter) is preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, and particularly preferably 25 to 75%. % By mass.
  • the radiation-sensitive composition of the present embodiment can obtain a highly sensitive and small roughness pattern.
  • an acid generator In the radiation-sensitive composition, an acid generator, a cross-linking agent, an acid may be used as a component other than the component (A) and the diazonaphthoquinone photoactive compound (B) as necessary, as long as the object of the present invention is not impaired.
  • Diffusion control agent dissolution accelerator, dissolution control agent, sensitizer, surfactant, organic carboxylic acid or phosphorus oxo acid or derivative thereof, heat and / or photocuring catalyst, polymerization inhibitor, flame retardant, filler, Coupling agents, thermosetting resins, photocurable resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants, etc.
  • Another component (D) may be called arbitrary component (D).
  • the blending ratio of each component is mass% based on the solid component, Preferably 1 to 99/99 to 1/0 to 98, More preferably 5 to 95/95 to 5/0 to 49, More preferably, 10 to 90/90 to 10/0 to 10, Particularly preferably 20 to 80/80 to 20/0 to 5, Most preferably, it is 25 to 75/75 to 25/0.
  • the blending ratio of each component is selected from each range so that the sum is 100% by mass.
  • the radiation-sensitive composition is excellent in performance such as sensitivity and resolution in addition to roughness when the blending ratio of each component is in the above range.
  • the radiation-sensitive composition may contain compounds and resins other than the present embodiment as long as the object of the present invention is not impaired.
  • resins include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, or vinyl phenol as monomer units, or these resins. Derivatives and the like.
  • the compounding quantity of these resin is suitably adjusted according to the kind of component (A) to be used, 30 mass parts or less are preferable with respect to 100 mass parts of components (A), More preferably, 10 mass parts or less More preferably, it is 5 parts by mass or less, and particularly preferably 0 part by mass.
  • the method for forming a resist pattern according to the present embodiment includes forming a photoresist layer using the above-described composition of the present embodiment (the resist composition or the radiation sensitive composition), and then a predetermined region of the photoresist layer. And a step of performing development by irradiating the substrate with radiation.
  • the method for forming a resist pattern according to the present embodiment includes a step of forming a resist film on a substrate, a step of exposing the formed resist film, and developing the resist film to form a resist pattern.
  • the resist pattern in this embodiment can also be formed as an upper layer resist in a multilayer process.
  • the method for forming the resist pattern is not particularly limited, and examples thereof include the following methods.
  • a resist film is formed by applying the resist composition or radiation sensitive composition on a conventionally known substrate by a coating means such as spin coating, cast coating, roll coating or the like.
  • the conventionally known substrate is not particularly limited, and examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. More specifically, a silicon substrate, a metal substrate such as copper, chromium, iron, and aluminum, a glass substrate, and the like can be given. Examples of the wiring pattern material include copper, aluminum, nickel, and gold. Further, if necessary, an inorganic and / or organic film may be provided on the substrate.
  • inorganic BARC inorganic antireflection film
  • organic BARC organic antireflection film
  • Surface treatment with hexamethylene disilazane or the like may be performed.
  • the coated substrate is heated as necessary.
  • the heating conditions vary depending on the composition of the resist composition, but are preferably 20 to 250 ° C., more preferably 20 to 150 ° C. Heating may improve the adhesion of the resist to the substrate, which is preferable.
  • the resist film is exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-ray, and ion beam.
  • the exposure conditions and the like are appropriately selected according to the composition of the resist composition or the radiation sensitive composition.
  • heating is preferably performed after radiation irradiation.
  • the heating conditions vary depending on the composition of the resist composition or the radiation-sensitive composition, but are preferably 20 to 250 ° C, more preferably 20 to 150 ° C.
  • a predetermined resist pattern is formed by developing the exposed resist film with a developer.
  • a solvent having a solubility parameter (SP value) close to that of the compound and resin of the above-described embodiment to be used ketone solvent, ester solvent, alcohol solvent, amide solvent.
  • SP value solubility parameter
  • a polar solvent such as a solvent, an ether solvent, a hydrocarbon solvent, or an alkaline aqueous solution can be used.
  • ketone solvent examples include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone.
  • ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3 -Ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate and the like.
  • the alcohol solvent examples include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol (2-propanol), n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, Alcohols such as 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl Ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene Glycol monoethyl ether, and triethylene glycol monoethyl ether and methoxymethyl butanol.
  • Alcohols such as 4-methyl-2-pentanol, n-heptyl alcohol, n
  • ether solvent examples include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
  • amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
  • hydrocarbon solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
  • the water content of the developer as a whole is less than 70% by mass, preferably less than 50% by mass, and more preferably less than 30% by mass.
  • it is more preferably less than 10% by mass, and it is particularly preferable that it contains substantially no water.
  • the content of the organic solvent with respect to the developer is 30% by mass to 100% by mass, preferably 50% by mass to 100% by mass, and preferably 70% by mass to 100% by mass with respect to the total amount of the developer. More preferably, it is 90 mass% or less, More preferably, it is 90 mass% or more and 100 mass% or less, It is especially preferable that it is 95 mass% or more and 100 mass% or less.
  • alkaline aqueous solution examples include alkaline compounds such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and choline. Can be mentioned.
  • alkaline compounds such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), and choline. Can be mentioned.
  • the developer is a developer containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents, such as resist pattern resolution and roughness. It is preferable for improving the resist performance.
  • the vapor pressure of the developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
  • vapor pressure of 5 kPa or less examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl Ketone solvents such as isobutyl ketone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Esters such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate
  • Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone.
  • Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ester solvents such as ethyl lactate, butyl lactate and propyl lactate, n-butyl alcohol alcohol solvents such as sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol , Glycol solvents such as triethylene glycol, and
  • the surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.
  • fluorine and / or silicon surfactants include, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950.
  • Nonionic surfactant it is a nonionic surfactant.
  • a fluorochemical surfactant or a silicon-type surfactant is more preferable to use.
  • the amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.
  • a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously applying the developer while scanning the developer application nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method) ) Etc.
  • the time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.
  • a step of stopping development may be performed while substituting with another solvent.
  • the rinsing liquid used in the rinsing step after development is not particularly limited as long as the resist pattern cured by crosslinking is not dissolved, and a solution or water containing a general organic solvent can be used.
  • a rinsing liquid containing at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents.
  • a cleaning step is performed using a rinse solution containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents.
  • a washing step is performed using a rinse solution containing an alcohol solvent or an ester solvent. Even more preferably, after the development, a step of washing with a rinsing solution containing a monohydric alcohol is performed. Particularly preferably, after the development, a washing step is performed using a rinsing liquid containing a monohydric alcohol having 5 or more carbon atoms.
  • the time for rinsing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.
  • examples of the monohydric alcohol used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol, 2-butanol, 3-methyl- 1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2- Heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used.
  • Particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4 -Methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It is possible to have.
  • a plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.
  • the water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics can be obtained.
  • the vapor pressure of the rinsing solution used after development is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less.
  • An appropriate amount of a surfactant can be added to the rinse solution.
  • the developed wafer is cleaned using a rinsing solution containing the organic solvent described above.
  • the method of the cleaning treatment is not particularly limited.
  • a method of continuously applying the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time.
  • a method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied.
  • a cleaning process is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.
  • the pattern wiring board is obtained by etching.
  • the etching can be performed by a known method such as dry etching using plasma gas and wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like.
  • Plating can be performed after forming the resist pattern.
  • Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating.
  • the residual resist pattern after etching can be peeled off with an organic solvent.
  • organic solvent include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), EL (ethyl lactate), and the like.
  • peeling method include a dipping method and a spray method.
  • the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.
  • the wiring substrate obtained in this embodiment can also be formed by a method of depositing a metal in a vacuum after forming a resist pattern and then dissolving the resist pattern with a solution, that is, a lift-off method.
  • the composition of this embodiment can also be used as a film forming composition for lithography for use in lower layer films (hereinafter also referred to as a lower layer film forming material).
  • the lower layer film-forming material contains at least one substance selected from the group consisting of the compound and resin of the above-described embodiment.
  • the substance is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and more preferably 50 to 100% by mass in the lower layer film-forming material from the viewpoints of coatability and quality stability. % Is more preferable, and 100% by mass is particularly preferable.
  • the lower layer film forming material can be applied to a wet process and has excellent heat resistance and etching resistance. Furthermore, since the material for forming the lower layer film uses the substance, it is possible to form a lower layer film that suppresses deterioration of the film during high-temperature baking and has excellent etching resistance against oxygen plasma etching and the like. Furthermore, since the lower layer film forming material is also excellent in adhesion to the resist layer, an excellent resist pattern can be obtained.
  • the underlayer film forming material may contain a known underlayer film forming material for lithography and the like as long as the effects of the present invention are not impaired.
  • the lower layer film forming material may contain a solvent.
  • a solvent used for the lower layer film forming material a known one can be appropriately used as long as it can dissolve at least the above-described substances.
  • the solvent include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; cellosolv solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate and methyl acetate Ester solvents such as ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate; alcohol solvents such as methanol, ethanol, isopropanol, 1-ethoxy-2-propanol; toluene, xylene And aromatic hydrocarbons such as anisole. These solvents can be used alone or in combination of two or more.
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and
  • cyclohexanone propylene glycol monomethyl ether
  • propylene glycol monomethyl ether acetate propylene glycol monomethyl ether acetate
  • ethyl lactate methyl hydroxyisobutyrate
  • anisole is particularly preferable from the viewpoint of safety.
  • the content of the solvent is not particularly limited, but from the viewpoint of solubility and film formation, it is preferably 100 to 10,000 parts by mass with respect to 100 parts by mass of the lower layer film-forming material, and 200 to 5, The amount is more preferably 000 parts by mass, and even more preferably 200 to 1,000 parts by mass.
  • the lower layer film-forming material may contain a crosslinking agent as necessary from the viewpoint of suppressing intermixing.
  • a crosslinking agent which can be used in this embodiment is not specifically limited, For example, the crosslinking agent as described in international publication 2013/024779 can be used.
  • crosslinking agent examples include, for example, phenol compounds, epoxy compounds, cyanate compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanates. Examples thereof include, but are not limited to, compounds and azide compounds.
  • crosslinking agents can be used alone or in combination of two or more. Among these, a benzoxazine compound, an epoxy compound, or a cyanate compound is preferable, and a benzoxazine compound is more preferable from the viewpoint of improving etching resistance.
  • phenol compound known compounds can be used.
  • phenols include phenols, alkylphenols such as cresols and xylenols, polyhydric phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalenediols, and bisphenols such as bisphenol A and bisphenol F.
  • polyfunctional phenol compounds such as phenol novolac and phenol aralkyl resin.
  • aralkyl type phenol resins are preferable from the viewpoint of heat resistance and solubility.
  • epoxy compound known compounds can be used and selected from those having two or more epoxy groups in one molecule.
  • These epoxy resins may be used alone or in combination of two or more. From the viewpoint of heat resistance and solubility, an epoxy resin that is solid at room temperature such as an epoxy resin obtained from phenol aralkyl resins or biphenyl aralkyl resins is preferable.
  • the cyanate compound is not particularly limited as long as it is a compound having two or more cyanate groups in one molecule, and a known one can be used.
  • a preferred cyanate compound one having a structure in which a hydroxyl group of a compound having two or more hydroxyl groups in one molecule is substituted with a cyanate group can be mentioned.
  • the cyanate compound preferably has an aromatic group, and a cyanate compound having a structure in which the cyanate group is directly connected to the aromatic group can be suitably used.
  • cyanate compounds include bisphenol A, bisphenol F, bisphenol M, bisphenol P, bisphenol E, phenol novolac resin, cresol novolac resin, dicyclopentadiene novolac resin, tetramethylbisphenol F, bisphenol A novolac resin, bromine.
  • Bisphenol A brominated phenol novolak resin, trifunctional phenol, tetrafunctional phenol, naphthalene type phenol, biphenyl type phenol, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, dicyclopentadiene aralkyl resin, alicyclic phenol, phosphorus
  • cyanate compounds may be used alone or in combination of two or more. Further, the cyanate compound described above may be in any form of a monomer, an oligomer and a resin.
  • amino compound examples include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3 , 3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl Sulfide, 3,3′-diaminodiphenyl sulfide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene
  • benzoxazine compound examples include Pd-type benzoxazine obtained from bifunctional diamines and monofunctional phenols, and Fa-type benzoxazine obtained from monofunctional diamines and bifunctional phenols. It is done.
  • the melamine compound examples include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl.
  • examples thereof include compounds in which 1 to 6 methylol groups of melamine and hexamethylolmelamine are acyloxymethylated, or a mixture thereof.
  • the guanamine compound include, for example, tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine And compounds in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof.
  • glycoluril compound examples include, for example, tetramethylol glycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound in which 1 to 4 methylol groups of tetramethylolglycoluril are methoxymethylated, or a mixture thereof, Examples thereof include compounds in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxymethylated, or mixtures thereof.
  • urea compound examples include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated or a mixture thereof, tetramethoxyethyl urea, and the like.
  • a crosslinking agent having at least one allyl group may be used from the viewpoint of improving the crosslinkability.
  • Specific examples of the crosslinking agent having at least one allyl group include 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2 -Bis (3-allyl-4-hydroxyphenyl) propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl) ) Allylphenols such as ether, 2,2-bis (3-allyl-4-cyanatophenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3 -Allyl-4-cyanatophenyl) propane, bis (3-allyl-4-cyanatosiphenyl) sulfone, bis (3-allyl-4-cyanatophenyl) sulfide, bis (3- Examples
  • 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-allyl-4-hydroxyphenyl) Preference is given to allylphenols such as propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide, bis (3-allyl-4-hydroxyphenyl) ether.
  • the content of the crosslinking agent in the composition is not particularly limited, but is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the total composition including the above-described compound or resin.
  • the amount is more preferably part by mass, and further preferably 10 to 40 parts by mass.
  • Crosslinking accelerator In the lower layer film forming material of the present embodiment, a crosslinking accelerator for accelerating the crosslinking and curing reaction can be used as necessary.
  • the crosslinking accelerator is not particularly limited as long as it promotes crosslinking and curing reaction, and examples thereof include amines, imidazoles, organic phosphines, and Lewis acids. These crosslinking accelerators can be used alone or in combination of two or more. Among these, imidazoles or organic phosphines are preferable, and imidazoles are more preferable from the viewpoint of lowering the crosslinking temperature.
  • crosslinking accelerator examples include, but are not limited to, for example, 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylamino).
  • Tertiary amines such as methyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, 2,4,5- Imidazoles such as triphenylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium tetraphenylborate, teto Tetraphenyl such as phenylphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate, etc., 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine /
  • the content of the crosslinking accelerator is usually preferably 0.1 to 10 parts by mass, more preferably 100 parts by mass when the total mass of the composition is 100 parts by mass. From the viewpoint of ease and economy, it is 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass.
  • a radical polymerization initiator can be blended as necessary.
  • the radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization with light or a thermal polymerization initiator that initiates radical polymerization with heat.
  • the radical polymerization initiator can be, for example, at least one selected from the group consisting of ketone photopolymerization initiators, organic peroxide polymerization initiators, and azo polymerization initiators.
  • Such a radical polymerization initiator is not particularly limited, and those conventionally used can be appropriately employed.
  • 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis ( 2-methylpropionamidine) dihydrochloride, 2,2′-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2′-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] Dihydride chloride, 2,2′-azobis [N- (4-hydrophenyl) -2-methylpropionamidine] dihydrochloride, 2, '-Azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2
  • the content of the radical polymerization initiator may be any stoichiometrically required amount, but 0.05 to 25 masses when the total mass of the composition containing the compound or resin is 100 mass parts. Part is preferable, and 0.1 to 10 parts by mass is more preferable.
  • the content of the radical polymerization initiator is 0.05 parts by mass or more, there is a tendency that curing can be prevented from being insufficient.
  • the content of the radical polymerization initiator is 25 parts by mass or less. In such a case, the long-term storage stability of the lower layer film-forming material at room temperature tends to be prevented from being impaired.
  • the lower layer film-forming material may contain an acid generator as required from the viewpoint of further promoting the crosslinking reaction by heat.
  • an acid generator those that generate an acid by thermal decomposition and those that generate an acid by light irradiation are known, and any of them can be used. For example, those described in International Publication No. 2013/024779 can be used.
  • the content of the acid generator is not particularly limited, but is preferably 0.1 to 50 parts by weight, more preferably 0.5 parts by weight with respect to 100 parts by weight of the lower layer film forming material. ⁇ 40 parts by mass.
  • the lower layer film-forming material may contain a basic compound from the viewpoint of improving storage stability.
  • the basic compound serves as a quencher for the acid to prevent the acid generated in a trace amount from the acid generator from causing the crosslinking reaction to proceed.
  • a basic compound is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.
  • the content of the basic compound is not particularly limited, but is preferably 0.001 to 2 parts by mass, more preferably 0.01 to 100 parts by mass of the lower layer film forming material. ⁇ 1 part by mass.
  • the lower layer film forming material in the present embodiment may contain other resins and / or compounds for the purpose of imparting curability by heat or light and controlling the absorbance.
  • other resins and / or compounds include naphthol resins, xylene resins, naphthol-modified resins, phenol-modified resins of naphthalene resins, polyhydroxystyrene, dicyclopentadiene resins, (meth) acrylates, dimethacrylates, trimethacrylates, tetra Resins containing no heterocyclic ring or aromatic ring such as methacrylate, vinyl naphthalene, polyacenaphthylene and other naphthalene rings, phenanthrenequinone, biphenyl rings such as fluorene, hetero rings having hetero atoms such as thiophene and indene; rosin resins; Examples thereof include resins or compounds containing an alicyclic structure such
  • the lower layer film-forming material in the present embodiment may contain a known additive.
  • the known additives include, but are not limited to, for example, heat and / or photocuring catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, photocurable resins, dyes, Examples thereof include pigments, thickeners, lubricants, antifoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, and nonionic surfactants.
  • the lower layer film for lithography can be formed using the lower layer film forming material.
  • a step (A-1) of forming a lower layer film on the substrate using the lower layer film forming material (the composition of the present embodiment), and at least one photoresist layer is formed on the lower layer film.
  • a resist pattern forming method comprising: a forming step (A-2); and a step (A-3) of irradiating a predetermined region of the photoresist layer with radiation after the second forming step and developing Can be used.
  • another pattern forming method (circuit pattern forming method) of the present embodiment is a step (B-1) of forming a lower layer film on a substrate using the lower layer film forming material (the composition of the present embodiment).
  • the intermediate layer film is etched using the resist pattern as a mask
  • the lower layer film is etched using the obtained intermediate layer film pattern as an etching mask
  • the substrate is etched using the obtained lower layer film pattern as an etching mask.
  • the resist intermediate layer film material may contain silicon atoms.
  • the formation method of the lower layer film for lithography in the present embodiment is not particularly limited as long as it is formed from the lower layer film forming material, and a known method can be applied.
  • a known method such as spin coating or screen printing or a printing method, and removing the organic solvent by volatilizing the organic solvent
  • the lower layer film material is crosslinked by a known method. And cured to form the lower layer film for lithography of the present embodiment.
  • the crosslinking method include methods such as thermosetting and photocuring.
  • the baking temperature is not particularly limited, but is preferably in the range of 80 to 450 ° C., more preferably 200 to 400 ° C.
  • the baking time is not particularly limited, but is preferably within the range of 10 to 300 seconds.
  • the thickness of the lower layer film can be appropriately selected according to the required performance and is not particularly limited, but is usually preferably about 30 to 20,000 nm, more preferably 50 to 15,000 nm. It is preferable.
  • a silicon-containing resist layer is formed thereon, or a single-layer resist made of ordinary hydrocarbons.
  • a silicon-containing intermediate layer is formed thereon, and further thereon. It is preferable to produce a single-layer resist layer that does not contain silicon. In this case, a well-known thing can be used as a photoresist material for forming this resist layer.
  • a silicon-containing resist layer or a single layer resist made of ordinary hydrocarbon can be formed on the lower layer film.
  • a silicon-containing intermediate layer can be formed on the lower layer film, and a single-layer resist layer not containing silicon can be formed on the silicon-containing intermediate layer.
  • the photoresist material for forming the resist layer can be appropriately selected from known materials and is not particularly limited.
  • a silicon-containing resist material for a two-layer process from the viewpoint of oxygen gas etching resistance, a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative is used as a base polymer, and an organic solvent, an acid generator, If necessary, a positive photoresist material containing a basic compound or the like is preferably used.
  • a silicon atom-containing polymer a known polymer used in this type of resist material can be used.
  • a polysilsesquioxane-based intermediate layer is preferably used as the silicon-containing intermediate layer for the three-layer process.
  • the intermediate layer By giving the intermediate layer an effect as an antireflection film, reflection tends to be effectively suppressed.
  • the k value increases and the substrate reflection tends to increase, but the reflection is suppressed in the intermediate layer.
  • the substrate reflection can be reduced to 0.5% or less.
  • the intermediate layer having such an antireflection effect is not limited to the following, but for 193 nm exposure, a polysilsesquioxy crosslinked with acid or heat into which a light absorbing group having a phenyl group or a silicon-silicon bond is introduced. Sun is preferably used.
  • an intermediate layer formed by a chemical vapor deposition (CVD) method can also be used.
  • the intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following, but for example, a SiON film is known.
  • the formation of the intermediate layer by a wet process such as spin coating or screen printing has a simpler and more cost-effective advantage than the CVD method.
  • the upper layer resist in the three-layer process may be either a positive type or a negative type, and the same one as a commonly used single layer resist can be used.
  • the lower layer film in this embodiment can also be used as an antireflection film for a normal single layer resist or a base material for suppressing pattern collapse. Since the lower layer film of this embodiment is excellent in etching resistance for the base processing, it can be expected to function as a hard mask for the base processing.
  • a wet process such as spin coating or screen printing is preferably used as in the case of forming the lower layer film.
  • prebaking is usually performed, but this prebaking is preferably performed at 80 to 180 ° C. for 10 to 300 seconds.
  • a resist pattern can be obtained by performing exposure, post-exposure baking (PEB), and development.
  • the thickness of the resist film is not particularly limited, but is generally preferably 30 to 500 nm, more preferably 50 to 400 nm.
  • the exposure light may be appropriately selected and used according to the photoresist material to be used.
  • high energy rays having a wavelength of 300 nm or less, specifically, 248 nm, 193 nm, 157 nm excimer laser, 3 to 20 nm soft X-ray, electron beam, X-ray and the like can be mentioned.
  • the resist pattern formed by the above-described method is one in which pattern collapse is suppressed by the lower layer film in the present embodiment. Therefore, by using the lower layer film in the present embodiment, a finer pattern can be obtained, and the exposure amount necessary for obtaining the resist pattern can be reduced.
  • gas etching is preferably used as the etching of the lower layer film in the two-layer process.
  • gas etching etching using oxygen gas is suitable.
  • an inert gas such as He or Ar, or CO, CO 2 , NH 3 , SO 2 , N 2 , NO 2 or H 2 gas may be added.
  • gas etching can be performed only with CO, CO 2 , NH 3 , N 2 , NO 2, and H 2 gas without using oxygen gas.
  • the latter gas is preferably used for side wall protection for preventing undercut of the pattern side wall.
  • gas etching is also preferably used for etching the intermediate layer in the three-layer process.
  • the gas etching the same gas etching as described in the above two-layer process can be applied.
  • the processing of the intermediate layer in the three-layer process is preferably performed using a fluorocarbon gas and a resist pattern as a mask.
  • the lower layer film can be processed by, for example, oxygen gas etching using the intermediate layer pattern as a mask.
  • a silicon oxide film, a silicon nitride film, or a silicon oxynitride film is formed by a CVD method, an ALD method, or the like.
  • the method for forming the nitride film is not limited to the following, but for example, the method described in Japanese Patent Application Laid-Open No. 2002-334869 (the above-mentioned Patent Document 6) and WO 2004/066377 (the above-mentioned Patent Document 7) is used. it can.
  • a photoresist film can be formed directly on such an intermediate film, but an organic antireflection film (BARC) is formed on the intermediate film by spin coating, and a photoresist film is formed thereon. May be.
  • BARC organic antireflection film
  • an intermediate layer based on polysilsesquioxane is also preferably used.
  • the resist intermediate layer film By providing the resist intermediate layer film with an effect as an antireflection film, reflection tends to be effectively suppressed.
  • Specific materials of the polysilsesquioxane-based intermediate layer are not limited to the following, but examples thereof include Japanese Patent Application Laid-Open No. 2007-226170 (the above-mentioned Patent Document 8) and Japanese Patent Application Laid-Open No. 2007-226204 (the above-mentioned Patent Document). Those described in 9) can be used.
  • Etching of the next substrate can also be performed by a conventional method.
  • the substrate is SiO 2 or SiN
  • etching mainly using a chlorofluorocarbon gas if p-Si, Al, or W is chlorine or bromine, Etching mainly with gas can be performed.
  • the substrate is etched with a chlorofluorocarbon gas, the silicon-containing resist of the two-layer resist process and the silicon-containing intermediate layer of the three-layer process are peeled off simultaneously with the substrate processing.
  • the silicon-containing resist layer or the silicon-containing intermediate layer is separately peeled, and generally, dry etching peeling with a chlorofluorocarbon-based gas is performed after the substrate is processed. .
  • the lower layer film is characterized by excellent etching resistance of these substrates.
  • a known substrate can be appropriately selected and used, and is not particularly limited. Examples thereof include Si, ⁇ -Si, p-Si, SiO 2 , SiN, SiON, W, TiN, and Al. .
  • the substrate may be a laminate having a film to be processed (substrate to be processed) on a base material (support). Examples of such processed films include various low-k films such as Si, SiO 2 , SiON, SiN, p-Si, ⁇ -Si, W, W-Si, Al, Cu, and Al-Si, and their stopper films. In general, a material different from the base material (support) is used.
  • the thickness of the substrate to be processed or the film to be processed is not particularly limited, but is usually preferably about 50 to 10,000 nm, more preferably 75 to 5,000 nm.
  • the resist permanent film which can produce a resist permanent film using the said composition is a permanent film which remains also in the final product after forming a resist pattern as needed. It is suitable as.
  • the permanent film include a solder resist, a package material, an underfill material, a package adhesive layer such as a circuit element, an adhesive layer between an integrated circuit element and a circuit board, and a thin film display protective film for a thin display. Examples include a liquid crystal color filter protective film, a black matrix, and a spacer.
  • the permanent film made of the above composition has excellent heat resistance and moisture resistance, and also has a very excellent advantage of less contamination due to sublimation components.
  • a display material is a material having high sensitivity, high heat resistance, and moisture absorption reliability with little image quality deterioration due to important contamination.
  • composition When the composition is used for a resist permanent film, other additives such as other resins, surfactants and dyes, fillers, cross-linking agents, and dissolution accelerators are added in addition to the curing agent. By dissolving in an organic solvent, a resist permanent film composition can be obtained.
  • the film forming composition for lithography and the composition for resist permanent film can be prepared by blending the above components and mixing them using a stirrer or the like. Further, when the resist underlayer film composition or resist permanent film composition contains a filler or a pigment, it is adjusted by dispersing or mixing using a dispersing device such as a dissolver, a homogenizer, or a three-roll mill. I can do it.
  • a dispersing device such as a dissolver, a homogenizer, or a three-roll mill. I can do it.
  • Carbon concentration and oxygen concentration were measured by organic elemental analysis using the following apparatus.
  • Apparatus CHN coder MT-6 (manufactured by Yanaco Analytical Industries)
  • the molecular weight of the compound was measured by LC-MS analysis using Water's Acquity UPLC / MALDI-Synapt HDMS. Moreover, the gel permeation chromatography (GPC) analysis was performed on the following conditions, and the polystyrene conversion weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) were calculated
  • Apparatus Shodex GPC-101 (manufactured by Showa Denko KK) Column: KF-80M x 3 Eluent: THF 1mL / min Temperature: 40 ° C
  • the obtained resin (R1-BiP-1) had Mn: 1875, Mw: 3550, and Mw / Mn: 1.89.
  • the obtained resin (R2-BiP-1) was Mn: 1682, Mw: 2910, and Mw / Mn: 1.73.
  • the thermal decomposition temperature was 375 ° C. and the glass transition point was 80 ° C., confirming high heat resistance.
  • the thermal decomposition temperature was 380 ° C. and the glass transition point was 90 ° C., confirming high heat resistance.
  • the obtained resin (E-R1-BiP-1) had Mn: 2476, Mw: 4542, and Mw / Mn: 1.83.
  • the obtained resin (G-R1-BiP-1) had Mn: 2799, Mw: 4982, and Mw / Mn: 1.78.
  • the obtained resin (GE-R1-BiP-1) had Mn: 3216, Mw: 5845, and Mw / Mn: 1.82.
  • the obtained resin (E-R2-BiP-1) was Mn: 2649, Mw: 4531, and Mw / Mn: 1.71.
  • the obtained resin (G-R2-BiP-1) had Mn: 2630, Mw: 4682, and Mw / Mn: 1.78.
  • the obtained resin (GE-R1-BiP-1) was Mn: 2712, Mw: 5641, and Mw / Mn: 2.08.
  • ethylbenzene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) as a diluent solvent was added to the reaction solution, and after standing, the lower aqueous phase was removed. Further, neutralization and washing with water were performed, and ethylbenzene and unreacted 1,5-dimethylnaphthalene were distilled off under reduced pressure to obtain 1.25 kg of a light brown solid dimethylnaphthalene formaldehyde resin. The molecular weight of the obtained dimethylnaphthalene formaldehyde was Mn: 562.
  • a four-necked flask having an internal volume of 0.5 L equipped with a Dimroth condenser, a thermometer, and a stirring blade was prepared.
  • This four-necked flask was charged with 100 g (0.51 mol) of the dimethylnaphthalene formaldehyde resin obtained as described above and 0.05 g of paratoluenesulfonic acid in a nitrogen stream, and the temperature was raised to 190 ° C. Stir after heating for hours. Thereafter, 52.0 g (0.36 mol) of 1-naphthol was further added, and the temperature was further raised to 220 ° C. to react for 2 hours.
  • the obtained resin (CR-1) was Mn: 885, Mw: 2220, and Mw / Mn: 4.17.
  • materials for forming a lower layer film for lithography having the compositions shown in Table 6 below were prepared.
  • these lower-layer film forming materials for lithography were spin-coated on a silicon substrate, and then baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds to prepare 200 nm-thick underlayer films.
  • the following were used about the acid generator, the crosslinking agent, and the organic solvent.
  • Acid generator Ditertiary butyl diphenyliodonium nonafluoromethanesulfonate (DTDDPI) manufactured by Midori Chemical Co., Ltd.
  • Crosslinking agent Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.
  • Organic solvent Propylene glycol monomethyl ether acetate acetate (PGMEA)
  • Novolac PSM4357 manufactured by Gunei Chemical Co., Ltd.
  • materials for forming a lower layer film for lithography having the compositions shown in Table 7 below were prepared.
  • these lower layer film forming materials for lithography are spin-coated on a silicon substrate, and then baked at 110 ° C. for 60 seconds to remove the solvent of the coating film. Then, an integrated exposure amount of 600 mJ is obtained with a high-pressure mercury lamp. / cm 2, and is cured by irradiation time of 20 seconds to produce each an underlying film having a thickness of 200 nm.
  • the photo acid generator, the crosslinking agent, and the organic solvent described in Table 6 were used.
  • Photo acid generator WPA Pure Chemicals WPAG-336 (diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate) ⁇
  • Crosslinking agent Diallyl bisphenol A cyanate manufactured by Mitsubishi Gas Chemical (DABPA-CN) Konishi Chemical Industry Diallylbisphenol A (BPA-CA) Benzoxazine (BF-BXZ) manufactured by Konishi Chemical Industries Nippon Kayaku Biphenyl Aralkyl Epoxy Resin (NC-3000-L) ⁇
  • Organic solvent Propylene glycol monomethyl ether acetate acetate (PGMEA)
  • the structure of the crosslinking agent is shown by the following formula.
  • Etching system “RIE-10NR” manufactured by Samco International Output: 50W Pressure: 20Pa Time: 2min Etching gas
  • Ar gas flow rate: CF 4 gas flow rate: O 2 gas flow rate 50: 5: 5 (sccm)
  • Etching resistance was evaluated according to the following procedure. First, novolak was used under the same conditions as in Example 1-1 except that novolak (“PSM4357” manufactured by Gunei Chemical Co., Ltd.) was used instead of the compound (E-BiN-1) used in Example 1-1. A lower layer film was produced. And the above-mentioned etching test was done for the lower layer film of this novolak, and the etching rate at that time was measured.
  • the above-mentioned etching test was similarly performed for the lower layer films of the examples and comparative examples, and the etching rate at that time was measured. Then, the etching resistance was evaluated according to the following evaluation criteria based on the etching rate of the novolak underlayer film.
  • each solution of an underlayer film forming material for lithography containing E-BiN-1, E-BiP-1, G-BiN-1, G-BiP-1, GE-BiN-1, and GE-BiP-1
  • the coating was applied on a SiO 2 substrate having a thickness of 300 nm and baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds to form a lower layer film having a thickness of 70 nm.
  • an ArF resist solution was applied and baked at 130 ° C. for 60 seconds to form a 140 nm-thick photoresist layer.
  • the compound of the following formula (11) was prepared as follows. First, 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy- ⁇ -butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, 0.38 g of azobisisobutyronitrile, tetrahydrofuran The reaction solution was dissolved in 80 mL. This reaction solution was polymerized for 22 hours under a nitrogen atmosphere while maintaining the reaction temperature at 63 ° C., and then the reaction solution was dropped into 400 mL of n-hexane. The product resin thus obtained was coagulated and purified, and the resulting white powder was filtered and obtained by drying overnight at 40 ° C. under reduced pressure.
  • the photoresist layer was exposed using an electron beam drawing apparatus (ELIONX, ELS-7500, 50 keV), baked at 115 ° C. for 90 seconds (PEB), and 2.38 mass% tetramethylammonium hydroxide (A positive resist pattern was obtained by developing with an aqueous solution of TMAH for 60 seconds.
  • ELIONX electron beam drawing apparatus
  • ELS-7500 ELS-7500, 50 keV
  • PEB baked at 115 ° C. for 90 seconds
  • TMAH 2.38 mass% tetramethylammonium hydroxide
  • the shapes of the obtained resist patterns of 55 nm L / S (1: 1) and 80 nm L / S (1: 1) were observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd.
  • S-4800 electron microscope
  • the resist pattern was evaluated as “good” when the pattern was not collapsed and the rectangularity was good, and “bad”.
  • the minimum line width with no pattern collapse and good rectangularity was used as an evaluation index as “resolution”.
  • the minimum electron beam energy amount capable of drawing a good pattern shape was defined as “sensitivity” and used as an evaluation index. The results are shown in Table 8.
  • Example 54 to 59 A solution of the material for forming a lower layer film for lithography of Examples 1-1 to 2-3 was applied on a SiO 2 substrate having a film thickness of 300 nm, and baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds. A lower layer film having a thickness of 80 nm was formed. On this lower layer film, a silicon-containing intermediate layer material was applied and baked at 200 ° C. for 60 seconds to form an intermediate layer film having a thickness of 35 nm. Further, the ArF resist solution was applied on this intermediate layer film and baked at 130 ° C. for 60 seconds to form a 150 nm-thick photoresist layer. As the silicon-containing intermediate layer material, a silicon atom-containing polymer described in JP-A-2007-226170 ⁇ Synthesis Example 1> was used.
  • the photoresist layer was subjected to mask exposure using an electron beam lithography apparatus (ELIONX, ELS-7500, 50 keV), baked at 115 ° C. for 90 seconds (PEB), and 2.38 mass% tetramethylammonium hydroxide.
  • ELIONX electron beam lithography apparatus
  • PEB baked at 115 ° C. for 90 seconds
  • TMAH tetramethylammonium hydroxide
  • an optical component-forming composition was prepared with the formulation shown in Table 9 below.
  • the following were used for the acid generator, crosslinking agent, acid diffusion inhibitor, and solvent.
  • Acid generator Ditertiary butyl diphenyliodonium nonafluoromethanesulfonate (DTDDPI) manufactured by Midori Chemical Co., Ltd.
  • Crosslinking agent Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.
  • Organic solvent Propylene glycol monomethyl ether acetate acetate (PGMEA)
  • PMEA Propylene glycol monomethyl ether acetate acetate
  • the optical component-forming composition in a uniform state was spin-coated on a clean silicon wafer, and then pre-baked (PB) in an oven at 110 ° C. to form an optical component-forming film having a thickness of 1 ⁇ m.
  • the prepared optical component-forming composition was evaluated as “A” when the film formation was good and “C” when the formed film had defects.
  • a uniform optical component-forming composition was spin-coated on a clean silicon wafer, and then PB was performed in an oven at 110 ° C. to form a film having a thickness of 1 ⁇ m.
  • a resist composition was prepared according to the formulation shown in Table 10 below.
  • the following were used for the acid generator, crosslinking agent, acid diffusion inhibitor, and solvent.
  • Acid generator Triphenylphosphonium trifluoromethanesulfonate manufactured by Midori Kagaku Co., Ltd.
  • Crosslinking agent Nicalak MX270 manufactured by Sanwa Chemical Co., Ltd.
  • Acid diffusion inhibitor Trioctylamine manufactured by Tokyo Chemical Industry Co., Ltd.
  • Organic solvent Propylene glycol monomethyl ether (PGME) manufactured by Tokyo Chemical Industry Co., Ltd.
  • the line and space was observed with a scanning electron microscope (S-4800, manufactured by Hitachi High-Technology Corporation), and the reactivity of the resist composition by electron beam irradiation was evaluated.
  • Sensitivity was expressed as the minimum amount of energy per unit area necessary for obtaining a pattern, and was evaluated according to the following.
  • the obtained pattern shape is transferred to an SEM (Scanning Electron Microscope). And evaluated according to the following.
  • C When a non-rectangular pattern is obtained
  • the compound and resin of this embodiment have high solubility in a safe solvent, good heat resistance and etching resistance, and the resist composition provides a good resist pattern shape.
  • a wet process can be applied, and a compound, a resin, and a film forming composition for lithography useful for forming a photoresist underlayer film having excellent heat resistance and etching resistance can be realized.
  • this film-forming composition for lithography uses a compound or resin having a specific structure that has high heat resistance and high solvent solubility, deterioration of the film during high-temperature baking is suppressed, oxygen plasma etching, etc. It is possible to form a resist and an underlayer film that are also excellent in etching resistance to.
  • the adhesion with the resist layer is also excellent, so that an excellent resist pattern can be formed. Furthermore, since the refractive index is high and coloring is suppressed by low-temperature to high-temperature treatment, it is useful as various optical component-forming compositions.
  • the present invention provides, for example, an electrical insulating material, a resist resin, a semiconductor sealing resin, an adhesive for a printed wiring board, an electrical laminate mounted on an electrical device / electronic device / industrial device, etc. ⁇ Matrix resin for prepregs, built-up laminate materials, resin for fiber reinforced plastics, sealing resin for liquid crystal display panels, paints, various coating agents, adhesives, and coatings for semiconductors installed in electronic equipment and industrial equipment
  • resin resist resin for semiconductors, resin for forming lower layer film, film and sheet, plastic lens (prism lens, lenticular lens, micro lens, Fresnel lens, viewing angle control lens, contrast enhancement lens, etc.) , Retardation film, electromagnetic shielding film, prism, optical fiber, flexible Solder resist printed wiring, plating resist, multilayer printed wiring boards interlayer insulating film, the optical component such as a photosensitive optical waveguide, it is widely and effectively available.
  • the present invention can be used particularly effectively in the fields of lithography resists, lithography resists,

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  • Materials For Photolithography (AREA)
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Abstract

L'invention concerne un composé représenté par la formule générale (0) ci-dessous. Dans la formule générale (0) (RY représente: un groupe alkyle ayant de 1 à 30 atomes de carbone ou un groupe aryle ayant de 6 à 30 atomes de carbone, RZ représente: un groupe à valence N ayant de 1 à 60 atomes de carbone, ou une liaison simple, RT représente: un groupe alkyle ayant de 1 à 30 atomes de carbone, un groupe aryle ayant de 6 à 30 atomes de carbone, un groupe alcényle ayant de 2 à 30 atomes de carbone, un groupe alcoxy ayant de 1 à 30 atomes de carbone, un atome d'halogène, un groupe nitro, un groupe amino, un groupe d'acide carboxylique, un groupe thiol, un groupe dans lequel le groupe hydroxy ou l'atome d'hydrogène du groupe hydroxy a été substitué par un groupe contenant hydroxy-alkyle ou par un groupe glycidyle (les groupes alkyle, aryle, alcényle et alcoxy ci-dessus pouvant contenir une liaison éther, une liaison cétone, ou une liaison ester), au moins un RT contenant un groupe substitué dans lequel un atome d'hydrogène du groupe hydroxy a été substitué par un groupe hydroxy-alkyle ou par un groupe glycidyle. X représente un atome d'oxygène, un atome de soufre ou étant non réticulé, m est un nombre entier entre 0 et 9 (au moins un m étant un nombre entier entre 1 et 9), N est un nombre entier entre 1 et 4, et r est un nombre entier entre 0 et 2.
PCT/JP2017/026423 2016-07-21 2017-07-21 Composé, résine, composition, procédé de formation de motif de réserve et procédé de formation de circuit WO2018016615A1 (fr)

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WO2023190508A1 (fr) * 2022-03-31 2023-10-05 群栄化学工業株式会社 Élément optique, matériau de formation d'élément optique et son procédé de fabrication, et procédé de fabrication d'élément optique

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