WO2018052026A1 - Composé, résine, composition, procédé de formation de motif de réserve, et procédé de formation de motif de circuit - Google Patents

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

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Publication number
WO2018052026A1
WO2018052026A1 PCT/JP2017/033063 JP2017033063W WO2018052026A1 WO 2018052026 A1 WO2018052026 A1 WO 2018052026A1 JP 2017033063 W JP2017033063 W JP 2017033063W WO 2018052026 A1 WO2018052026 A1 WO 2018052026A1
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group
carbon atoms
integer
compound
independently
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PCT/JP2017/033063
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English (en)
Japanese (ja)
Inventor
越後　雅敏
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三菱瓦斯化学株式会社
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Priority to CN201780055990.0A priority Critical patent/CN109715591A/zh
Priority to KR1020197007278A priority patent/KR20190049731A/ko
Priority to JP2018539752A priority patent/JP7452947B2/ja
Publication of WO2018052026A1 publication Critical patent/WO2018052026A1/fr
Priority to JP2022094792A priority patent/JP2022130463A/ja

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    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/205—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings
    • C07C39/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings with at least one hydroxy group on a non-condensed ring
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
    • 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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to a compound having a specific structure, a resin, a composition, a resist pattern forming method, and a circuit pattern forming method.
  • 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 type negative radiation sensitive composition for example, see Patent Document 1 and Patent Document 2 using a low molecular weight polynuclear polyphenol compound as a main component
  • a low molecular weight resist material having high heat resistance As candidates, an alkali development negative radiation-sensitive composition using a low molecular weight cyclic polyphenol compound as a main component (see, for example, Patent Document 3 and Non-Patent Document 1) has also been proposed.
  • Non-Patent Document 2 a polyphenol compound as a base compound for a resist material can impart high heat resistance despite its low molecular weight, and is useful for improving the resolution and roughness of a resist pattern (for example, Non-Patent Document 2). reference).
  • the present inventors have so far developed a resist composition containing a compound having a specific structure and an organic solvent as a material excellent in etching resistance, soluble in a solvent and applicable to a wet process (for example, Patent Document 4). See).
  • a terminal layer is removed by applying a predetermined energy as a resist underlayer film for lithography having a dry etching rate selection ratio close to that of a resist.
  • a material for forming a lower layer film for a multilayer resist process which contains at least a resin component having a substituent that generates a sulfonic acid residue and a solvent (see, for example, Patent Document 5).
  • 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, Patent Documents). 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).
  • 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 patent document 8) is proposed.
  • a silicon nitride film formation method for example, Patent Document 9
  • a silicon nitride film CVD formation method for example, 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).
  • compositions for optical members have been proposed. However, none of them has a combination of heat resistance, transparency and refractive index at a high level, and the development of new materials is required.
  • the present invention has been made in view of the above-described problems of the prior art, and the purpose thereof is to form a photoresist and a lower layer film for photoresist that can be applied with a wet process and have excellent heat resistance, solubility, and etching resistance. It is in providing a compound, a resin, and a composition useful for the purpose.
  • the present inventors have found that the problems of the prior art can be solved by a compound or resin having a specific structure, and have completed the present invention. It was. That is, the present invention is as follows. [1] The compound represented by following formula (0). (0) (In Formula (0), R Y is a hydrogen atom, 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 alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond, wherein at least one of R T is a hydroxyl group, and R T At least one of these is an alkenyl group having 2 to 30 carbon atoms, X represents an oxygen atom, a sulfur atom, a single bond or no bridge, m is each independently an integer of 0 to 9, wherein at least one of m is an integer of 2 to 9 or at least two of m is an integer of 1 to 9, N is an integer of 1 to 4, where, 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.
  • the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond, wherein at least one of R 2A is a hydroxyl group.
  • at least one of R 2A is an alkenyl group having 2 to 30 carbon atoms, 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 represents an oxygen atom, a sulfur atom, a single bond or no bridge
  • m 2A is each independently an integer from 0 to 7, provided that at least one m 2A is an integer from 2 to 7 or at least two m 2A is an integer from 1 to 7
  • q A is each independently 0 or 1.
  • the compound according to [2], wherein the compound represented by the formula (1) is a compound represented by the following formula (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.
  • 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.
  • 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.
  • R 8 to R 9 have the same meanings as R 6 to R 7
  • R 12 to R 13 have the same meanings as R 10 to R 11
  • m 8 and m 9 are each independently an integer of 0 to 8, provided that m 6 , m 7 , m 8 and m 9 are not 0 at the same time.
  • [6] The compound according to [3], wherein the compound represented by the formula (2) is a compound represented by the following formula (2-1).
  • R 0A , R 1A , n A , q A and X A are as defined above
  • R 3A 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.
  • R 4A is each independently a hydrogen atom; m 6A is each independently an integer of 0 to 5.
  • L is a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may have a substituent, and 6 to 6 carbon atoms which may have a substituent.
  • R 30 arylene group, an alkoxylene group having 1 to 30 carbon atoms which may have a substituent, or a single bond, wherein the alkylene group, the arylene group and the alkoxylene group are an ether bond, a ketone bond or an ester May contain bonds, 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.
  • the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond, wherein at least one of R 2A is a hydroxyl group, and R 2A At least one of these is an alkenyl group having 2 to 30 carbon atoms, 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 represents an oxygen atom, a sulfur atom, a single bond or no bridge
  • m 2A is each independently an integer from 0 to 7, provided that at least one m 2A is an integer from 2 to 7 or at least two m 2A is an integer from 1 to 7
  • q A is each independently 0 or 1.
  • a composition comprising at least one 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].
  • the composition according to [10] further comprising a solvent.
  • 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 crosslinking accelerator is at least one selected from the group consisting of amines, imidazoles, organic phosphines and Lewis acids.
  • the content of the crosslinking accelerator is 0.1 to 5% by mass of the total mass of the solid component.
  • a composition according to 1. [22] The composition according to any one of [10] to [21], wherein the content of the radical polymerization initiator is 0.05 to 25% by mass of the total mass of the solid component. [23] The 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 permanent resist film.
  • a method for forming a resist pattern comprising: forming a photoresist layer on a substrate using the composition described in [23]; and irradiating a predetermined region of the photoresist layer with radiation and developing.
  • a lower layer film is formed on the substrate using the composition described in [23], and at least one photoresist layer is formed on the lower layer film, and then radiation is applied to a predetermined region of the photoresist layer.
  • a resist pattern forming method including a step of irradiating and developing.
  • a lower layer film is formed 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 at least on the intermediate layer film,
  • a predetermined region of the photoresist layer is irradiated with radiation, developed to form a resist pattern, and then the intermediate layer film is etched using the resist pattern as a mask,
  • a circuit pattern forming method comprising: etching the lower layer film 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 to form a pattern on the substrate.
  • the compound and resin according to the present invention are highly soluble in a safe solvent, and have good heat resistance and etching resistance. Moreover, the composition containing the compound and / or resin according to the present invention gives a good resist pattern shape.
  • the present embodiment a mode for carrying out the present invention (hereinafter also referred to as “the present embodiment”) will be described.
  • the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.
  • the compound, resin, and composition containing the compound in the present embodiment can be applied to a wet process, and are useful for forming a photoresist underlayer film having excellent heat resistance and etching resistance.
  • the composition in the present embodiment uses a compound or resin having a specific structure with high heat resistance and solvent solubility, deterioration of the film during high-temperature baking is suppressed, and etching resistance against oxygen plasma etching and the like
  • 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 refractive index is high and coloring due to a wide range of heat treatments from low to high temperatures is suppressed, it is also useful as various optical forming compositions.
  • R Y is a hydrogen atom
  • 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 alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond, wherein at least one of R T is a hydroxyl group, and R T At least one of these is an alkenyl group having 2 to 30 carbon atoms, X represents an oxygen atom, a sulfur atom, a single bond or no bridge, m is each independently an integer of 0 to 9, wherein at least one of m is an integer of 2 to 9 or at least two of m is an integer of 1 to 9, N is an integer of 1 to 4, where, 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. )
  • R Y is a hydrogen atom.
  • the alkyl group a linear, branched or cyclic alkyl group can be used.
  • RY is a hydrogen atom, excellent heat resistance and solvent solubility can be imparted.
  • R Z is an N-valent group having 1 to 60 carbon atoms or a single bond, and each aromatic ring is bonded through 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.
  • Examples of the N-valent group 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 alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond, wherein at least one of R T is a hydroxyl group, and R T At least one of them includes an alkenyl group having 2 to 30 carbon atoms.
  • the alkyl group, alkenyl group and alkoxy group may be linear, branched or cyclic groups.
  • X represents an oxygen atom, a sulfur atom, a single bond or no bridge, and when X is an oxygen atom or a sulfur atom, it tends to develop high heat resistance, and is preferably an oxygen atom. preferable.
  • 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 2 to 9, or at least two 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 (0) in the present embodiment is preferably a compound represented by the following formula (1) from the viewpoints of heat resistance and solvent solubility.
  • R 0 is synonymous with R Y and is a hydrogen atom.
  • R 0 is a hydrogen atom, the heat resistance is relatively high and the solvent solubility tends to be improved.
  • R 1 is an n-valent group having 1 to 60 carbon atoms or a single bond, and each aromatic ring is bonded via R 1 .
  • 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.
  • n has the same meaning as N above, and is an integer of 1 to 4.
  • p 2 to p 5 are each independently synonymous with r and are integers of 0 to 2.
  • the alkyl group, alkenyl group and alkoxy group may be linear, branched or cyclic groups.
  • An alkanepropyl group having 2 to 60 carbon atoms, and when n 4, an alkanetetrayl group having 3 to 60 carbon atoms.
  • Examples of the n-valent group 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 group may have an aromatic group having 6 to 60 carbon atoms.
  • 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.
  • the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group.
  • the compound represented by the above 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 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 film production for lithography.
  • the resist formation composition for lithography containing the compound represented by said Formula (1) may give a favorable resist pattern shape. it can.
  • 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 a lower layer film for lithography using the same has good embedding and planarization characteristics.
  • it is a compound having a relatively high carbon concentration, high etching resistance can be 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 compound which has quaternary carbon from a viewpoint which suppresses oxidative decomposition of a compound, suppresses coloring, and improves heat resistance and solvent solubility is preferable.
  • Optical parts include film and sheet parts, plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic shielding films, It is useful as a prism, 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 above formula (1) is more 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, 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.
  • the compound represented by the above formula (1-1) is more preferably a compound represented by the following formula (1-2) from the viewpoint of further crosslinking 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
  • R 8 to R 9 have the same meanings as R 6 to R 7 above
  • R 12 to R 13 have the same meanings as R 10 to R 11 above
  • m 8 and m 9 are each independently an integer of 0 to 8.
  • m 6 , m 7 , m 8 and m 9 are not 0 at the same time.
  • the compound represented by the above formula (1-1) is more preferably a compound represented by the following formula (1a) from the viewpoint of raw material supply.
  • R 0 to R 5 , m 2 to m 5 and n have the same meaning as described in the above formula (1).
  • the compound represented by the above 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 , m 4 , m 5 , and n are as defined in the above formula (1), and R 6 , R 7 , R 10 , R 11 , m 6 and m 7 have the same meanings as described in the above 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.
  • R 0 , R 1 , R 4 , R 5 , m 4 , m 5 , and n are the same as those described in the above formula (1), and R 6 , R 7 , R 10 , R 11 , m 6 and m 7 have the same meanings as described in the above 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 above formula (1-2).
  • the compound represented by the above 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 above formula (1-2).
  • X is the same as those described in the above formula (0)
  • R T ' has the same meaning as R T described by the above formula (0)
  • m are each independently 0-9
  • at least one of m is an integer of 2 to 9, or at least two of m is an integer of 1 to 9.
  • at least one of R T ′ is a hydroxyl group
  • at least one of R T ′ is an alkenyl group having 2 to 30 carbon atoms.
  • X is the same as those described in the above formula (0)
  • R Y ', R Z' are as defined R Y, R Z described by the above formula (0).
  • each R 4A is independently a hydrogen atom.
  • R 2 , R 3 , R 4 and R 5 have the same meanings as described in the above formula (1).
  • m 2 and m 3 are integers from 0 to 8
  • m 4 and m 5 are integers from 0 to 9.
  • at least one selected from R 2 , R 3 , R 4 and R 5 is a hydroxyl group
  • at least one selected from R 2 , R 3 , R 4 and R 5 is an alkenyl having 2 to 30 carbon atoms. It is a group.
  • m 2 , m 3 , m 4 , and m 5 are not 0 at the same time.
  • the compound represented by the above 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 6 ′ to R 9 ′ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a carboxylic acid group or a thiol
  • at least one of R 6 ′ to R 9 ′ is an alkenyl group having 2 to 30 carbon atoms
  • R 10 to R 13 have the same meaning as described in the above formula (1c).
  • R 10 to R 13 have the same meanings as described in the above formula (1-2), and each R 14 independently represents a linear, branched or cyclic alkyl having 1 to 30 carbon atoms.
  • m 14 is an integer of 0 to 5; 14 ′ is an integer from 0 to 4, and 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.
  • 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, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group .
  • R 14 includes an isomer.
  • the butyl group includes n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
  • R 10 to R 13 have the same meanings as described in the above 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.
  • 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, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group .
  • R 15 includes an isomer.
  • the butyl group includes n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
  • the compound represented by the above formula is preferably a compound represented by the following structure from the viewpoint of etching resistance.
  • R 0A is synonymous with the above formula R Y
  • R 1A ′ is synonymous with R Z
  • R 10 to R 13 are synonymous with those explained in the above 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.
  • 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, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group.
  • R 14 includes an isomer.
  • the butyl group includes n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
  • R 10 to R 13 have the same meanings as described in the above 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.
  • 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, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group.
  • R 15 includes an isomer.
  • the butyl group includes n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
  • R 10 to R 13 have the same meanings as described in the above formula (1-2),
  • R 16 represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms, 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 16 includes an isomer.
  • the butyl group includes n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
  • R 10 to R 13 have the same meanings as described in the above formula (1-2), and each R 14 independently represents a linear, branched or cyclic alkyl having 1 to 30 carbon atoms.
  • 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.
  • 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, heptacene group, vinyl group, allyl group, triacontenyl group, methoxy group, ethoxy group, triacontoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, thiol group.
  • R 14 includes an isomer.
  • the butyl group includes n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group.
  • R 10 to R 13 have the same meanings as described in the above formula (1-2). From the viewpoint of heat resistance, the above formula preferably has a dibenzoxanthene skeleton.
  • the above compound is more preferably a compound represented below from the viewpoint of availability of raw materials.
  • R 10 to R 13 have the same meanings as described in the above formula (1-2). From the viewpoint of heat resistance, the above formula preferably has a dibenzoxanthene skeleton.
  • the above formula is preferably represented by the following structure from the viewpoint of raw material availability, and more preferably a compound having a dibenzoxanthene skeleton from the viewpoint of heat resistance.
  • R 0A is synonymous with the above formula R Y
  • R 1A ′ is synonymous with R Z
  • R 10 to R 13 are synonymous with those explained in the above formula (1-2).
  • the above formula is more preferably a compound having a xanthene skeleton from the viewpoint of heat resistance.
  • R 10 to R 13 have the same meanings as described in the above 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) in this embodiment can be appropriately synthesized by applying a known technique, and the synthesis technique is not particularly limited.
  • the compound represented by the formula (0) will be described by taking the compound represented by the formula (1) as an example.
  • a polyphenol compound is obtained by polycondensation reaction of biphenols, binaphthols or bianthraceneol with a corresponding aldehyde under an acid catalyst under normal pressure, and then at least one phenolic compound of the polyphenol compound is obtained. It can be obtained by introducing an allyl group into the hydroxyl group, and then causing the Claisen transition by heating. Moreover, it can also carry out under pressure as needed.
  • the timing for introducing the allyl group may be introduced before or after the condensation reaction or after the production of the resin described later.
  • 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 from the viewpoint of increasing the carbon atom concentration and improving the heat resistance.
  • aldehydes examples include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, Examples include naphthaldehyde, anthracene carbaldehyde, phenanthrene carbaldehyde, pyrene carbaldehyde, furfural, and the like, but are not limited thereto.
  • benzaldehyde phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracene Carbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde and furfural are preferably used.
  • benzaldehyde hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, Hexyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, anthracene carbaldehyde, phenanthrene carbaldehyde, pyrene carbaldehyde, it is preferable to use a furfural.
  • aldehydes it is preferable to use an aldehyde having an aromatic ring from the viewpoint of having both high heat resistance and high etching resistance.
  • the acid catalyst used in the above 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, 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, and boron trifluoride; solid acids such as silicotungstic acid, phosphotungstic acid,
  • an organic acid and a solid acid are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is more 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 the catalyst, and further the reaction conditions, and is not particularly limited, but is 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material. It is preferable that
  • a reaction solvent may be used.
  • the reaction solvent is not particularly limited as long as the reaction between the aldehyde to be used and the biphenols, binaphthols, or bianthracenediol proceeds, and can be appropriately selected from known ones.
  • Examples of the reaction solvent 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 reaction solvents used can be appropriately set according to the types of raw materials and catalysts to be used, reaction conditions, and the like, and is not particularly limited, but is 0 to 2000 parts by mass with respect to 100 parts by mass of the reaction raw materials. A range is preferable.
  • the reaction temperature in the above 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.
  • reaction temperature is preferable, and specifically, a range of 60 to 200 ° C. is preferable.
  • 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, aldehydes, and a catalyst are charged together, or biphenols and binaphthols. Or the method of dripping a bianthracenediol and aldehydes in presence of a catalyst is mentioned.
  • 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.
  • the target compound can be isolated.
  • Preferable reaction conditions are as follows: 1 mol to an excess of biphenols, binaphthols or bianthracenediol, and 0.001 to 1 mol of an acid catalyst with respect to 1 mol of aldehyde, and 50 to 150 ° C. at normal pressure. 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 product represented by the above formula (1), which is the target product can be obtained by separating and purifying the product from the by-product, distilling off the solvent, filtering and drying.
  • an allyl group can be introduced into at least one phenolic hydroxyl group of the compound as follows.
  • a compound for introducing an allyl group can be synthesized or easily obtained by a known method, and examples thereof include allyl chloride, allyl bromide, and allyl iodide, but are not particularly limited thereto.
  • the above compound is 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.
  • the reaction is carried out at 20 to 150 ° C. for 6 to 72 hours at normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide and the like.
  • 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, and washed with distilled water as necessary.
  • a compound in which the hydrogen atom of the hydroxy group is substituted with an allyl group can be obtained.
  • the allyl group introduced into the phenolic hydroxyl group can be transferred by Claisen transition by heating.
  • an allyl group reacts in the presence of a radical or an acid / alkali, and the solubility in an acid, alkali or organic solvent used in a coating solvent or a developer changes.
  • the group substituted with the allyl group preferably 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.
  • composition used for forming a film for lithography or forming an optical component.
  • a resin obtained using the compound represented by the above formula (0) as a monomer can also be used as a composition.
  • the resin is obtained, for example, by reacting a compound represented by the above formula (0) with a compound having a crosslinking reactivity.
  • a resin obtained using the compound represented by the formula (0) as a monomer and a resin obtained using the compound represented by the formula (1) as a monomer will be described as examples.
  • Examples of the resin obtained using the compound represented by the above formula (1) as a monomer include those having a structure represented by the following formula (3). That is, the composition in 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 have 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 above formula (1).
  • m 2 , m 3 , m 4 and m 5 are not 0 simultaneously, and at least one of m 2 , m 3 , m 4 and m 5 is an integer of 2 to 8, 2 to 9, or m 2 , M 3 , m 4 and m 5 are each an integer of 1 to 8 or 1 to 9, at least one of R 2 to R 5 is a hydroxyl group, and at least one of R 2 to R 5 Is an alkenyl group having 2 to 30 carbon atoms.
  • the resin in the present embodiment is obtained by reacting the compound represented by the above formula (1) with a compound having crosslinking reactivity.
  • a known compound can be used without particular limitation as long as the compound represented by the above formula (1) 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 above formula (3) include, for example, a condensation reaction of the compound represented by the above formula (1) with an aldehyde and / or a ketone having a crosslinking reactivity.
  • a novolak resin may be used.
  • 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 above 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 1 mol with respect to 1 mol of the compound represented by the formula (1). 0.5 to 2 moles.
  • an acid catalyst can be used.
  • the acid catalyst used here can be appropriately selected from known ones and is not particularly limited.
  • As such an acid catalyst 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, 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, and boron trifluoride; solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid However, it is not particularly limited to these.
  • an organic acid and a solid acid are preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferable 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 the catalyst, and further the reaction conditions, and is not particularly limited, but is 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material. It is preferable that However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene, ⁇ -pinene, ⁇ -pinene In the case of a copolymerization reaction with a compound having a nonconjugated double bond such as limonene, 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. Can be mentioned.
  • 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 types of raw materials and catalysts to be used, and further the reaction conditions, and is not particularly limited, but is in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the reactive raw materials. It is preferable that Furthermore, 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.
  • reaction method may be a method in which the compound represented by the above formula (1), the aldehyde and / or ketone, and a catalyst are charged together, The method of dripping the compound represented by the said Formula (1), an aldehyde, and / or ketones in catalyst presence is mentioned.
  • 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.
  • the novolak resin as the target product can be isolated.
  • the resin having the structure represented by the above formula (3) may be a homopolymer of the compound represented by the above formula (1), 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 above 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 above formula (3) is a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the above 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 above formula (1) and the above-mentioned copolymerization monomer, it is represented by the above 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 above formula (3) is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene 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 above formula (3) has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.2. It is preferably within the range of ⁇ 7. In addition, said Mw and Mn can be calculated
  • the resin having the structure represented by the above formula (3) is preferably highly soluble in a solvent from the viewpoint of easier application of a wet process. More specifically, when 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) is used as a solvent, the solubility in the solvent is preferably 10% by mass or more.
  • the solubility in PGM and / or PGMEA is defined as “resin mass ⁇ (resin mass + solvent mass) ⁇ 100 (mass%)”.
  • 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) in the present embodiment is preferably a compound represented by the following formula (2) from the viewpoints of heat resistance and solvent solubility.
  • R 0A has the same meaning as R Y above, and is a hydrogen atom.
  • R 1A is an n A valent group having 1 to 30 carbon atoms or a single bond
  • R 2A is each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and 6 to 30 carbon atoms which may have a substituent.
  • An acid group, a thiol group, or a hydroxyl group, and the alkyl group, the aryl group, the alkenyl group, and the alkoxy group may include an ether bond, a ketone bond, or an ester bond, wherein at least one of R 2A One is a hydroxyl group, and at least one of R 2A is an alkenyl group having 2 to 30 carbon atoms.
  • n A has the same meaning as N above, and is an integer of 1 to 4, where, in formula (2), when n A is an integer of 2 or more, the structural formulas in n A [] are the same. It may or may not be.
  • X A each independently represents an oxygen atom, a sulfur atom, a single bond or no bridge.
  • X A because there is a tendency to exhibit excellent heat resistance, it is preferable that an oxygen atom or a sulfur atom, more preferably 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 2 to 6, or at least two m 2A is an integer of 1 to 6.
  • q A is each independently 0 or 1.
  • An alkanepropyl group having 2 to 60 carbon atoms, and when n 4, an alkanetetrayl group having 3 to 60 carbon atoms.
  • Examples of the n-valent group 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 group may have an aromatic group having 6 to 60 carbon atoms.
  • 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.
  • 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 30 carbon atoms.
  • the alicyclic hydrocarbon group includes a bridged alicyclic hydrocarbon group.
  • the compound represented by the above formula (2) has a relatively low molecular weight, but has high heat resistance due to the rigidity of the structure, and thus 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 film production for lithography.
  • the resist formation composition for lithography containing the compound represented by said Formula (2) may give a favorable resist pattern shape. it can.
  • 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 a lower layer film for lithography using the same has good embedding and planarization characteristics.
  • it is a compound having a relatively high carbon concentration, high etching resistance can be 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.
  • a compound having a quaternary carbon is preferable from the viewpoint of suppressing oxidative decomposition of the compound, suppressing coloring, and improving heat resistance and solvent solubility.
  • Optical parts include film and sheet parts, plastic lenses (prism lenses, lenticular lenses, micro lenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic shielding films, It is useful as a prism, 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 above formula (2) is more preferably a compound represented by the following formula (2-1) from the viewpoint of easy crosslinking and solubility in an organic solvent.
  • R 0A , R 1A , n A , q A and X A have the same meaning as described in the above 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.
  • at least one of R 3A is an alkenyl group having 2 to 30 carbon atoms
  • R 4A is each independently a hydrogen atom
  • m 6A is each independently an integer of 0 to 5.
  • R 4A is an acid dissociable group. It is.
  • R At least one of 4A is a hydrogen atom.
  • the compound represented by the above formula (2-1) is more preferably a compound represented by the following formula (2a) from the viewpoint of raw material supply.
  • the compound represented by the above formula (2-1) is more preferably a compound represented by the following formula (2b) from the viewpoint of solubility in an organic solvent.
  • X A , R 0A , R 1A , R 3A , R 4A , m 6A and n A are as defined in the above formula (2-1).
  • the compound represented by the above formula (2-1) is more preferably a compound represented by the following formula (2c) from the viewpoint of solubility in an organic solvent.
  • the compound represented by the above formula (2) is represented by the following formulas (BisN-1) to (BisN-4), (XBisN-1) to (XBisN-3) from the viewpoint of further solubility in an organic solvent. It is very particularly preferred that
  • R 3A and R 4A have the same meanings as explained in the above formula (2-1). However, at least one of R 3A is an alkenyl group having 2 to 30 carbon atoms.
  • the compound represented by formula (2) 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 corresponding aldehydes or ketones under an acid catalyst under normal pressure, and then at least one phenolic hydroxyl group of the polyphenol compound.
  • An allyl group can be introduced into the resin and then heated to cause a Claisen transition. Moreover, it can also carry out under pressure as needed.
  • the timing for introducing the allyl group may be introduced before or after the condensation reaction or after the production of the resin described later.
  • the naphthols are not particularly limited, and examples thereof include naphthol, methyl naphthol, methoxy naphthol, naphthalene diol, and the like.
  • naphthalene diol is preferably used from the viewpoint that 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.
  • aldehydes examples include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, biphenylaldehyde, Examples include naphthaldehyde, anthracene carbaldehyde, phenanthrene carbaldehyde, pyrene carbaldehyde, furfural, and the like, but are not limited thereto.
  • benzaldehyde phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracene Carbaldehyde, phenanthrenecarbaldehyde, pyrenecarbaldehyde and furfural are preferably used.
  • benzaldehyde hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, ethylbenzaldehyde, butylbenzaldehyde, Hexyl benzaldehyde, biphenyl aldehyde, naphthaldehyde, anthracene carbaldehyde, phenanthrene carbaldehyde, pyrene carbaldehyde, it is preferable to use a furfural.
  • the acid catalyst used in the above reaction can be appropriately selected from known ones and is not particularly limited.
  • the acid catalyst can be appropriately selected from known inorganic acids and organic acids.
  • inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid and hydrofluoric acid; oxalic acid, formic acid, p-toluenesulfone Acids, organic acids such as methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride; Examples thereof include solid acids such as tungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid. Among these, it is preferable to use hydrochloric acid or sulfuric acid from the viewpoint of production such as availability and
  • a reaction solvent may be used.
  • the reaction solvent is not particularly limited as long as the reaction between the aldehyde to be used and the naphthol proceeds, but for example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, or a mixed solvent thereof can be used.
  • the amount of the reaction 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. From the viewpoint of synthesizing the compound represented by the formula (2) in the present embodiment with good selectivity, the temperature is preferably lower and more preferably in the range of 10 to 60 ° C.
  • the reaction method is not particularly limited, and examples thereof include a method in which naphthols and the like, aldehydes or ketones, and a catalyst are charged all at once, and a method in which naphthols and aldehydes are dropped in the presence of a catalyst.
  • the temperature of the reaction kettle can be raised to 130-230 ° C., and volatile matter can be removed at about 1-50 mmHg. .
  • the amount of the raw material is not particularly limited. For example, 2 mol to excess of naphthol and the like and 0.001 to 1 mol of acid catalyst are used with respect to 1 mol of aldehyde, and 20 to 60 ° C. at normal pressure. For about 20 minutes to 100 hours.
  • the target product is isolated by a known method.
  • 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, and after cooling to room temperature, the product is separated by filtration.
  • the product can be filtered and dried, and then separated and purified from by-products by column chromatography, followed by solvent distillation, filtration and drying to isolate the target compound.
  • a method for introducing an allyl group into at least one phenolic hydroxyl group of a polyphenol compound is also known.
  • an allyl group can be introduced into at least one phenolic hydroxyl group of the compound as follows.
  • a compound for introducing an allyl group can be synthesized or easily obtained by a known method, and examples thereof include allyl chloride, allyl bromide, and allyl iodide, but are not particularly limited thereto.
  • the above compound is 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.
  • the reaction is carried out at 20 to 150 ° C. for 6 to 72 hours at normal pressure in the presence of a base catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide and the like.
  • 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, and washed with distilled water as necessary.
  • a compound in which the hydrogen atom of the hydroxy group is substituted with an allyl group can be obtained.
  • an allyl group reacts in the presence of a radical or an acid / alkali, and the solubility in an acid, alkali or organic solvent used in a coating solvent or a developer changes.
  • the group substituted with the allyl group preferably 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.
  • the allyl group introduced into the phenolic hydroxyl group can be transferred by Claisen transition by heating.
  • the compound represented by the above formula (2) can be used as it is as a film forming composition for lithography or a composition used for forming an optical component.
  • a resin obtained using the compound represented by the above formula (2) as a monomer can be used as a composition.
  • the resin is obtained, for example, by reacting a compound represented by the above formula (2) with a compound having crosslinking reactivity.
  • Examples of the resin obtained using the compound represented by the above formula (2) as a monomer include those having a structure represented by the following formula (4). That is, the composition in the present embodiment may contain a resin having a structure represented by the following formula (4).
  • L is a linear or branched alkylene group having 1 to 30 carbon atoms or a single bond.
  • R 0A , R 1A , R 2A , m 2A , n A , q A and X A are synonymous with those in the above formula (2), However, when n A is an integer of 2 or more, the structural formulas in n A [] may be the same or different, and at least one m 2A is an integer of 2 to 6 or at least 2 m 2A is an integer of 1 to 6, at least one of R 2A is a hydroxyl group, and at least one is an alkenyl group having 2 to 30 carbon atoms.
  • the resin in the present embodiment is obtained by reacting the compound represented by the above formula (2) with a compound having crosslinking reactivity.
  • a known compound can be used without particular limitation as long as the compound represented by the above 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 above formula (4) include, for example, a condensation reaction of the compound represented by the above formula (2) with an aldehyde and / or a ketone having a crosslinking reactivity.
  • a novolak resin may be used.
  • 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 above 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 1 mol with respect to 1 mol of the compound represented by the formula (2). 0.5 to 2 moles.
  • an acid catalyst can be used.
  • the acid catalyst used here can be appropriately selected from known ones and is not particularly limited.
  • As such an acid catalyst 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, 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, and boron trifluoride; solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid However, it is not particularly limited to these.
  • an organic acid or a solid acid is preferable from the viewpoint of production, and hydrochloric acid or sulfuric acid is preferable 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 the catalyst, and further the reaction conditions, and is not particularly limited, but is 0.01 to 100 parts by mass with respect to 100 parts by mass of the reaction raw material. It is preferable that However, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2-ene, ⁇ -pinene, ⁇ -pinene In the case of a copolymerization reaction with a compound having a nonconjugated double bond such as limonene, 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. Can be mentioned.
  • 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 types of raw materials and catalysts to be used, and further the reaction conditions, and is not particularly limited, but is in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the reactive raw materials. It is preferable that Furthermore, 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.
  • reaction method may be a method in which the compound represented by the above formula (2), the aldehyde and / or ketone, and a catalyst are charged together, The method of dripping the compound represented by the said Formula (2), an aldehyde, and / or ketones in catalyst presence is mentioned.
  • 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.
  • the novolak resin as the target product can be isolated.
  • the resin having the structure represented by the above formula (4) may be a homopolymer of the compound represented by the above 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 above formula (4) may be copolymerized with a polymerizable monomer in addition to the above-described other 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 above formula (4) is a binary or more (for example, 2-4 quaternary) copolymer of the compound represented by the above formula (2) 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 above formula (2) and the above-mentioned copolymerization monomer, it is represented by the above 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 above formula (4) is not particularly limited, but the polystyrene equivalent weight average molecular weight (Mw) is preferably from 500 to 30,000, more preferably from 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 above formula (4) has a dispersity (weight average molecular weight Mw / number average molecular weight Mn) of 1.2. It is preferably within the range of ⁇ 7. In addition, said Mw and Mn can be calculated
  • the resin having the structure represented by the above formula (4) is preferably one having high solubility in a solvent from the viewpoint of easier application of a wet process. More specifically, when 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) is used as a solvent, the solubility in the solvent is preferably 10% by mass or more.
  • the solubility in PGM and / or PGMEA is defined as “resin mass ⁇ (resin mass + solvent mass) ⁇ 100 (mass%)”.
  • 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 method for purifying the compound and / or resin in the present embodiment is more specifically at least one of the compound represented by the above formula (0) or the resin obtained by using the compound represented by the above formula (0) as a monomer. Is represented by the compound represented by the above formula (1), the resin obtained by using the compound represented by the above formula (1) as a monomer, the compound represented by the above formula (2), and the above formula (2).
  • the resin is 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 reactivity. preferable.
  • the content of various metals that can be contained as impurities in the compound or resin having the specific structure described above can be reduced. More specifically, in the purification method of the present embodiment, 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 obtained.
  • the extraction treatment can be performed in contact with an acidic aqueous solution. 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 metal content.
  • the compounds and / or resins used in the purification method of this embodiment 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 not arbitrarily miscible with water used in the purification method of the present embodiment is not particularly limited, but an organic solvent that can be safely applied to a semiconductor manufacturing process is preferable, and specifically, solubility in water at room temperature. Is less than 30%, more preferably less than 20%, and even more 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.
  • toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate are preferable, methyl isobutyl ketone, ethyl acetate, cyclohexanone and propylene glycol monomethyl ether acetate are more preferable, and methyl More preferred are 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 above 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 of the present embodiment is appropriately selected from aqueous solutions in which generally known organic compounds or inorganic compounds are dissolved in water.
  • the acidic aqueous solution include, but are not limited to, for example, a mineral acid aqueous solution in which a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid is dissolved in water; acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric 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
  • the water used here is preferably water having a low metal content, such as ion-exchanged water, in accordance with the purpose of the purification method of the present embodiment.
  • the pH of the acidic aqueous solution used in the purification method of the present embodiment 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 of the acidic aqueous solution is usually about 0 to 5, preferably about 0 to 3.
  • the amount of the acidic aqueous solution used in the purification method of the present embodiment is not particularly limited, but is used from the viewpoint of reducing the number of extractions for metal removal and ensuring operability in consideration of the total liquid amount. It is preferable to adjust the amount. 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).
  • the 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 includes an organic solvent that is arbitrarily mixed with water.
  • the solution (S) contains an organic solvent that is arbitrarily miscible with water, the amount of the compound and / or resin charged can be increased, the liquid separation property is improved, and purification is performed with high pot efficiency.
  • the method of adding an organic solvent arbitrarily mixed with water is not particularly limited, for example, a method of adding to a solution containing an organic solvent in advance, a method of adding to a water or acidic aqueous solution in advance, a solution containing an organic solvent and water or an acidic aqueous solution. Any of the methods of adding after contacting may be used. Among these, 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 of the present embodiment 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 of the present embodiment include, but are not limited to, ethers such as tetrahydrofuran and 1,3-dioxolane; alcohols such as methanol, ethanol and isopropanol Ketones such as acetone and 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 Can be mentioned.
  • ethers such as tetrahydrofuran and 1,3-dioxolane
  • alcohols such as methanol, ethanol and isopropanol Ketones such as acetone and N-methylpyrrolidone
  • aliphatic hydrocarbons such as glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl
  • N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferable, and N-methylpyrrolidone and propylene glycol monomethyl ether are more preferable.
  • Each of 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 well by stirring and then allowing 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).
  • second extraction 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 extraction treatment with water. It is preferable.
  • the extraction treatment with water is not particularly limited, and can be performed, for example, by thoroughly mixing the solution phase and water by stirring or the like and then allowing the obtained mixed solution to stand. Since the mixed solution after standing is separated into a solution phase containing a compound and / or a resin and a solvent and an aqueous phase, the solution phase can be recovered by decantation or the like.
  • the water used here is preferably water having a low metal content, for example, ion-exchanged water, 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 in the case of 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. Further, if necessary, a solvent can be added to the above solution to adjust the concentration of the compound and / or resin to an arbitrary concentration.
  • 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 in the present embodiment is a resin obtained by using the compound represented by the above formula (0) and the compound represented by the above formula (0) as a monomer, more specifically represented by the above formula (1).
  • a compound, a resin obtained by using the compound represented by the above formula (1) as a monomer, a compound represented by the above formula (2), a resin obtained by using the compound represented by the above formula (2) as a monomer, a solvent, 1 or more types chosen from the group which consists of an acid generator, a crosslinking agent, a crosslinking accelerator, a radical polymerization initiator, etc. are contained.
  • composition of the present embodiment can be a film forming composition for lithography or an optical component forming composition.
  • the film forming composition for lithography for chemical amplification resist application in the present embodiment (hereinafter also referred to as “resist composition”) is represented by the compound represented by the above formula (0) and the above formula (0).
  • Resin obtained by using a compound as a monomer more specifically, a compound represented by the above formula (1), a resin obtained by using a compound represented by the above formula (1) as a monomer, and represented by the above formula (2)
  • One or more selected from the group consisting of a compound and a resin obtained using the compound represented by the above formula (2) as a monomer is contained as a resist base material.
  • composition (resist composition) in the present embodiment preferably further 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 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-methoxybutyl A
  • Other esters such as tate, butyl 3-methoxy-3-methylpropionate, butyl 3-methoxy-3-methylbutyrate, methyl acetoacetate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene Ketones such as 2-h
  • 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.
  • composition (resist composition) of the present embodiment is selected from the group consisting of an acid generator (C), a crosslinking agent (G), an acid diffusion controller (E), and other components (F) as other solid components. You may further contain at least 1 type chosen.
  • solid component refers to a component 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 / or resin used as the resist base material is not particularly limited, but the total mass of the solid component (resist base material, acid generator (C), crosslinking agent (G ), Acid diffusion controller (E) and other components (F) and the like, and the total amount of solid components including the optionally used components, the same shall apply hereinafter)).
  • the amount is preferably 55 to 90% by mass, more preferably 60 to 80% by mass, and particularly preferably 60 to 70% by mass.
  • the content of the compound and / or resin used as the resist base is in the above range, the resolution is further improved and the line edge roughness (LER) tends to be further reduced.
  • the said content is a total amount of both components.
  • the resist composition in the present embodiment includes, as necessary, other than the resist base material, the acid generator (C), the cross-linking agent (G), and the acid diffusion controller (E) as long as the object of the present invention is not impaired.
  • a dissolution accelerator As a component, a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant, an organic carboxylic acid or a phosphorus oxo acid or a derivative thereof, a heat and / or photocuring catalyst, a polymerization inhibitor, a flame retardant, a filler, Coupling agents, thermosetting resins, photocurable resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants, etc.
  • another component (F) may be called arbitrary component (F).
  • a resist base material hereinafter also referred to as “component (A)”
  • an acid generator C
  • a crosslinking agent G
  • an acid diffusion controller E
  • an optional component The content of F (component (A) / acid generator (C) / crosslinking agent (G) / acid diffusion controller (E) / optional component (F)) is mass% based on solids, 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 blending ratio of each component is within the above range, the performance such as sensitivity, resolution, develop
  • the resist composition of this embodiment is usually prepared by dissolving each component in a solvent at the time of use to make 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 of the present embodiment can contain other resins other than the resin of the present embodiment as long as the object of the present invention is not impaired.
  • Other resins are not particularly limited.
  • novolak resins polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and acrylic acid, vinyl alcohol, or vinylphenol as monomer units. Examples thereof include polymers or derivatives thereof.
  • the content of other resins is not particularly limited and is appropriately adjusted according to the type of component (A) to be used, but is preferably 30 parts by mass or less with respect to 100 parts by mass of component (A). More preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts or less, Most preferably, it is 0 mass part.
  • An amorphous film can be formed by spin coating using the resist composition of the present embodiment.
  • the resist composition of this embodiment can be applied to a general semiconductor manufacturing process.
  • the type of resin obtained using these as monomers and / or the type of developer used either a positive resist pattern or a negative resist pattern is used. Can be made separately.
  • the dissolution rate of the amorphous film formed by spin-coating the resist composition of the present embodiment with respect to the developer at 23 ° C. is preferably 5 ⁇ / sec or less, and 0.05 to 5 ⁇ / It is more preferable that it is sec, and it is more preferable that it is 0.0005 to 5 cm / sec.
  • the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and tends to be easily formed as a resist. Further, when the dissolution rate is 0.0005 K / sec or more, the resolution may be improved.
  • the dissolution rate of the amorphous film formed by spin-coating the resist composition of the present embodiment in a developing solution at 23 ° C. is preferably 10 ⁇ / sec or more.
  • the dissolution rate is 10 kg / sec or more, it is easily dissolved in a developer and suitable for a resist.
  • the dissolution rate is 10 ⁇ / sec or more, the resolution may be improved. This is presumably because the compound represented by the above formulas (1) and (2) and / or the micro surface portion of the resin containing the compound as a constituent component dissolves and LER is reduced. Defect reduction effect is also seen.
  • the dissolution rate can be determined by immersing the amorphous film in a developing solution at 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.
  • a portion exposed to 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 of this embodiment is applied to a developer at 23 ° C.
  • the dissolution rate is preferably 10 ⁇ / sec or more.
  • the dissolution rate is 10 kg / sec or more, it is easily dissolved in a developer and suitable for a resist.
  • the dissolution rate is 10 ⁇ / sec or more, the resolution may be improved. This is presumably because the compound represented by the above formulas (1) and (2) and / or the micro surface portion of the resin containing the compound as a constituent component dissolves and LER is reduced. Defect reduction effect is also seen.
  • the amorphous film formed by spin-coating the resist composition of this embodiment is exposed to a developing solution at 23 ° C. at a portion exposed by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray.
  • the dissolution rate is preferably 5 kg / sec or less, more preferably 0.05 to 5 kg / sec, and further preferably 0.0005 to 5 kg / sec.
  • the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and tends to be easily formed as a resist. Further, when the dissolution rate is 0.0005 K / sec or more, the resolution may be improved.
  • the component (A) contained in the film forming composition for lithography for non-chemically amplified resist application of the present embodiment is a diazonaphthoquinone photoactive compound (B) described later.
  • a positive resist base material that is easily soluble in a developer by irradiating g-line, h-line, i-line, KrF excimer laser, ArF excimer laser, extreme ultraviolet light, electron beam or X-ray. Useful as.
  • 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. Since the compound (B) changes to a readily soluble compound, a resist pattern can be formed by a development process.
  • the component (A) contained in the radiation-sensitive composition of the present embodiment is a compound having a relatively low molecular weight, the roughness of the resulting 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, and in the formula (2), R 0A , R 1A and It is preferable that at least one selected from the group consisting of R 2A is a group containing an iodine atom.
  • the radiation-sensitive composition increases the ability to absorb radiation such as electron beams, extreme ultraviolet rays (EUV), and X-rays. This is preferable because the sensitivity can be increased.
  • EUV extreme ultraviolet rays
  • the glass transition temperature of the component (A) contained in the radiation-sensitive composition of the present embodiment 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.
  • the upper limit of the glass transition temperature of a component (A) is not specifically limited, For example, it is 400 degreeC.
  • the semiconductor lithography process has heat resistance capable of maintaining the pattern shape and tends to improve performance such as high resolution.
  • 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 of the present embodiment is preferably less than 20 J / g.
  • the (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 resist Therefore, it is likely that the film forming property required for the above can be maintained for a long period of 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 of the present embodiment is 100 or less, preferably 120 ° C. or less, more preferably 130 ° C. or less, further preferably 140 ° C. or less, and particularly preferably 150 ° C. or less under normal pressure. It is preferable that sublimability is low. Low sublimation 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, even 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 of the present embodiment is propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), cyclopentanone (CPN), 2-heptanone Selected from the group consisting of anisole, butyl acetate, ethyl propionate and ethyl lactate and exhibiting the highest solubility in component (A) at 23 ° C., preferably 1% by mass or more, more preferably Dissolves in an amount of 5% by mass or more, more preferably 10% by mass or more.
  • it is selected from the group consisting of PGMEA, PGME, and CHN, and (A) a solvent that exhibits the highest solubility in the resist base material, at 23 ° C., 20% by mass or more, and particularly preferably PGMEA On the other hand, 20 mass% or more dissolves at 23 ° C.
  • the diazonaphthoquinone photoactive compound (B) contained in the radiation-sensitive composition of the present embodiment is a diazonaphthoquinone substance containing a polymeric and non-polymeric diazonaphthoquinone photoactive compound.
  • a photosensitive component photosensitive agent
  • one or more kinds can be arbitrarily selected and used without any particular limitation.
  • the component (B) a compound obtained by reacting naphthoquinone diazide sulfonic acid chloride, benzoquinone diazide sulfonic acid chloride and the like with a low molecular compound or a high molecular compound having a functional group capable of condensation reaction with these acid chlorides.
  • 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 that can be condensed with an acid chloride containing a hydroxyl group is not particularly limited, and examples thereof include 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′-tetramethyltriphenylmethane And the like.
  • hydroxyphenylalkanes such as bis (2,4-dihydroxyphenyl) methane
  • 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 of the present embodiment is prepared by, for example, dissolving each component in a solvent at the time of use to obtain a uniform solution, and then filtering by, for example, a filter having a pore size of about 0.2 ⁇ m as necessary. It is preferred that
  • An amorphous film can be formed by spin coating using the radiation-sensitive composition of the present embodiment. Moreover, the radiation sensitive composition of this embodiment 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 of this embodiment at 23 ° C. with respect to the developing solution is preferably 5 ⁇ / sec or less, and 0.05 to More preferably, it is 5 ⁇ / sec, and further preferably 0.0005 to 5 ⁇ / sec.
  • the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and tends to be easily formed as a resist. Further, when the dissolution rate is 0.0005 K / sec or more, the resolution may be improved.
  • the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment 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 suitable for a resist.
  • the dissolution rate is 10 ⁇ / sec or more, the resolution may be improved. This is presumably because the compound represented by the above formulas (1) and (2) and / or the micro surface portion of the resin containing the compound as a constituent component dissolves and LER is reduced. Defect reduction effect is also seen.
  • the dissolution rate can be determined by immersing the amorphous film in a developing solution for a predetermined time at 23 ° C., 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 of this embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, or 20 to
  • the dissolution rate of the exposed portion after heating at 500 ° C. in the developer at 23 ° C. is preferably 10 ⁇ / sec or more, more preferably 10 to 10000 ⁇ / sec, and even more preferably 100 to 1000 ⁇ / sec.
  • the dissolution rate is 10 kg / sec or more, it is easily dissolved in a developer and suitable for a resist.
  • the dissolution rate is 10,000 kg / sec or less, the resolution may be improved. This is presumably because the compound represented by the above formulas (1) and (2) and / or the micro surface portion of the resin containing the compound as a constituent component dissolves and LER is reduced. Defect reduction effect is also seen.
  • the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment is irradiated with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray, or 20 to
  • the dissolution rate of the exposed portion after heating at 500 ° C. with respect to the developer at 23 ° C. is preferably 5 K / sec or less, more preferably from 0.05 to 5 K / sec, more preferably from 0.0005 to More preferably, it is 5 kg / sec.
  • the dissolution rate is 5 kg / sec or less, the resist is insoluble in the developer and tends to be easily formed as a resist.
  • the resolution may be improved. This is because an unexposed portion that dissolves in a developer due to a change in solubility before and after exposure of the compound represented by the above formulas (1) and (2) and / or a resin containing the compound as a constituent component, and a developer This is presumably because the contrast at the interface with the exposed portion that does not dissolve in the substrate increases. In addition, LER reduction and defect reduction effects are also seen.
  • the content of the component (A) is arbitrarily selected from the total mass 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 content of the component (A) is within the above range, the radiation-sensitive composition of the present embodiment tends to obtain a pattern with high sensitivity and small roughness.
  • the content of the diazonaphthoquinone photoactive compound (B) is the total mass of the solid components (component (A), diazonaphthoquinone photoactive compound (B) and other components (D). Etc.), preferably 1 to 99% by mass, more preferably 5 to 95% by mass, still more preferably 10 to 90% by mass, and particularly preferably Is 25 to 75% by mass.
  • the radiation-sensitive composition of the present embodiment tends to obtain a highly sensitive and small roughness pattern.
  • an acid generator, a cross-linkage, and a component other than the component (A) and the diazonaphthoquinone photoactive compound (B) are included as necessary, as long as the object of the present invention is not impaired.
  • Agent acid diffusion controller, dissolution accelerator, dissolution controller, sensitizer, surfactant, organic carboxylic acid or phosphorus oxo acid or derivative thereof, heat and / or photocuring catalyst, polymerization inhibitor, flame retardant, Fillers, coupling agents, thermosetting resins, photocurable resins, dyes, pigments, thickeners, lubricants, antifoaming agents, leveling agents, UV absorbers, surfactants, colorants, nonionic surfactants 1 type, or 2 or more types can be added.
  • 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, Even more preferably, 20-80 / 80-20 / 0-5, Particularly preferred 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. When the blending ratio of each component of the radiation-sensitive composition of the present embodiment is in the above range, it tends to be excellent in performance such as sensitivity and resolution in addition to roughness.
  • the radiation-sensitive composition of the present embodiment may contain other resins as long as the object of the present invention is not impaired.
  • other 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 derivatives are mentioned.
  • the blending amount of these resins is appropriately adjusted according to the type of component (A) used, but is preferably 30 parts by mass or less, more preferably 10 parts per 100 parts by mass of component (A). It is not more than part by mass, more preferably not more than 5 parts by mass, particularly preferably 0 part by mass.
  • a resist pattern is formed by forming a photoresist layer on a substrate using the resist composition or radiation-sensitive composition of the present embodiment described above, and then applying radiation to a predetermined region of the photoresist layer. And developing. More specifically, a step of forming a resist film on a substrate using the resist composition or radiation-sensitive composition of the present embodiment described above, a step of exposing the formed resist film, and developing the resist film And a step of forming 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 a resist composition or a 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 on the substrate.
  • the substrate coated with the resist composition or radiation-sensitive composition is heated.
  • the heating conditions vary depending on the composition of the resist composition or radiation-sensitive composition, but are preferably 20 to 250 ° C, more preferably 20 to 150 ° C. Heating is preferred because the adhesion of the resist to the substrate tends to be improved.
  • 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.
  • 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 solubility parameter (SP value) for the compound obtained by using the compound represented by the formula (1) or (2) or the compound represented by the formula (1) or (2) as a monomer is used. It is preferable to select a solvent close to), and polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, etc., hydrocarbon solvents or alkaline aqueous solutions 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, glycol monoethyl ether and methoxymethyl butanol.
  • Alcohols such as 4-methyl-2-pentanol, n-heptyl alcohol, n-oc
  • 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 mentioned.
  • 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 preferably less than 70% by mass, more preferably less than 50% by mass, and less than 30% by mass. More preferably, it is still more preferable that it is less than 10 mass%, and it is especially preferable not to contain water
  • 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 at least selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent from the viewpoint of improving resist performance such as resist pattern resolution and roughness.
  • a developer containing one solvent is preferred.
  • the vapor pressure of the developer is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less at 20 ° C.
  • the vapor pressure of the developing solution is 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, temperature uniformity in the wafer surface is improved, and as a result, dimensional uniformity in the wafer surface is good. It tends to become.
  • Examples of specific developers having a vapor pressure of 5 kPa or less at 20 ° C. include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, methyl Ketone solvents such as cyclohexanone, phenylacetone, methyl 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-ethoxypro Pionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, milk Ester solvent
  • ether solvents such as tetrahydrofuran; N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide amide solvents; toluene, xylene and other aromatic hydrocarbon solvents; Aliphatic hydrocarbon solvents such as octane and decane are listed.
  • Examples of specific developers having a vapor pressure of 2 kPa or less at 20 ° C. include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, methyl Ketone solvents such as cyclohexanone and 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 -Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate; n-butyl alcohol alcohol solvents such as sec-
  • 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.
  • 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 development 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 coating nozzle on the 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 cleaning 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.
  • 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 rinsing liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. When the water content in the rinsing liquid is 10% by mass or less, better development characteristics tend to be obtained.
  • the vapor pressure of the rinsing liquid 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 0.12 kPa or more and 3 kPa or less. Is more preferable.
  • the vapor pressure of the rinsing liquid is 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is further improved, and further, the swelling due to the penetration of the rinsing liquid is further suppressed, and the dimension in the wafer surface is uniform. Tend to be better.
  • 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.
  • the cleaning method is not particularly limited. For example, a method of continuously applying a rinsing liquid onto a substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a bath filled with the rinsing liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), etc. can be applied. Among them, a cleaning process is performed by a spin coating method, and the substrate is rotated at a rotational speed of 2000 rpm to 4000 rpm after cleaning. It is preferable to 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 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 stripped 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 board 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.
  • a film forming composition for lithography for use in an underlayer film includes a compound represented by the above formula (0) and a compound represented by the above formula (0).
  • a resin obtained by using the compound represented by the above formula (1), a resin obtained by using the compound represented by the above formula (1) as a monomer, a compound represented by the formula (2) and the formula (2) It contains at least one substance selected from the group consisting of resins obtained using the compound represented by 2) as a monomer.
  • the above substance is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and more preferably 50 to 100%, based on the total mass of the solid component, from the viewpoints of coatability and quality stability. More preferably, it is 100% by weight, and particularly preferably 100% by weight.
  • the underlayer film forming material of this embodiment can be applied to a wet process and has excellent heat resistance and etching resistance. Furthermore, since the lower layer film forming material of the present embodiment uses the above-mentioned substances, 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 of this embodiment is also excellent in adhesion to the resist layer, an excellent resist pattern can be obtained. In addition, the lower layer film forming material of the present embodiment may include a known lower layer 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 in the present embodiment 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, ethyl lactate, methyl hydroxyisobutyrate and anisole are 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 10000 parts by mass, and 200 to 5000 parts by mass with respect to 100 parts by mass of the total mass of the solid components. More preferred is 200 to 1000 parts by mass.
  • the lower layer film-forming material in the present embodiment may contain a crosslinking agent as necessary from the viewpoint of suppressing intermixing. Although it does not specifically limit as a crosslinking agent, For example, what was described in the 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.
  • Examples thereof include epoxidized products of aralkyl type phenol resins, and epoxidized products of naphthol aralkyl resins synthesized from naphthols and paraxylylene dichloride. 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 known compounds 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.
  • 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
  • Alicyclic amines such as heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decane, 1,3-bisaminomethylcyclohexane, isophoronediamine , Ethylenediamine, hexamethylenediamine Octamethylene diamine, decamethylene diamine, diethylene triamine, aliphatic amines such as triethylenetetramine, and the like.
  • 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 include, for example, hexamethylol melamine, hexamethoxymethyl melamine, a compound obtained by methoxymethylating 1 to 6 methylol groups of hexamethylol melamine 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, for example, 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
  • the content of the crosslinking agent in the lower layer film-forming material is not particularly limited, but is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, and still more preferably 10%, based on the total mass of the solid component. ⁇ 40% by weight.
  • 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 0.1 to 10% by mass of the total mass of the solid component, and more preferably 0.1 to 5 from the viewpoint of ease of control and economy. % By mass, more preferably 0.1 to 3% 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 2,2′-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2′-azo
  • the radical polymerization initiator may be contained in a stoichiometrically necessary amount, but the total mass of the solid component is preferably 0.05 to 25% by mass, preferably 0.1 to 10% by mass. It is more preferable that When the content of the radical polymerization initiator is 0.05% by mass or more, there is a tendency that curing can be prevented from being insufficient. On the other hand, the content of the radical polymerization initiator is 25% 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 in the present embodiment may contain an acid generator as necessary from the viewpoint of further promoting the crosslinking reaction by heat.
  • an acid generator those that generate an acid by thermal decomposition, those that generate an acid by light irradiation, and the like are known, and any of them can be used.
  • an acid generator what was described in the international publication 2013/024779 can be used, for example.
  • the content of the acid generator in the lower layer film-forming material is not particularly limited, but is preferably 0.1 to 50% by mass, more preferably 0.5 to 40% by mass based on the total mass of the solid component. .
  • the acid generation amount tends to increase and the crosslinking reaction tends to be enhanced, and the occurrence of the mixing phenomenon with the resist layer tends to be suppressed.
  • the lower layer film-forming material in the present embodiment may contain a basic compound from the viewpoint of improving storage stability.
  • the basic compound serves as a quencher for the acid to prevent a slight amount of acid generated 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 in the lower layer film-forming material is not particularly limited, but is preferably 0.001 to 2% by mass, more preferably 0.01 to 1% by mass, based on the total mass of the solid component. .
  • 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.
  • Such other resins and / or compounds include: naphthol resins, xylene resins, naphthol modified resins, phenol modified resins of naphthalene resins; polyhydroxystyrene, dicyclopentadiene resin, (meth) acrylate, dimethacrylate, trimethacrylate, tetra Resins containing no heteroaromatic ring such as methacrylate, vinylnaphthalene, naphthalene rings such as polyacenaphthylene, biphenyl rings such as phenanthrenequinone and fluorene, heterocycles having heteroatoms such as thiophene, indene, etc .; rosin resins; Examples thereof include resins or compounds containing an alicyclic structure such as cyclodextr, cyclodext
  • the lower layer film-forming material in the present embodiment may contain a known additive.
  • 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, and pigments. , Thickeners, lubricants, antifoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, nonionic surfactants, and the like.
  • the lower layer film for lithography in the present embodiment is formed from the lower layer film forming material described above.
  • a lower layer film is formed on a substrate using the composition, and at least one photoresist layer is formed on the lower layer film.
  • a step of performing development by irradiating a predetermined region with radiation More specifically, a step (A-1) of forming a lower layer film on the substrate using the lower layer film forming material of the present embodiment, and a step of forming at least one photoresist layer on the lower layer film ( A-2) and a step (A-3) of performing development by irradiating a predetermined region of the photoresist layer with radiation after the step (A-2).
  • the lower layer film is formed on the substrate using the composition, the intermediate layer film is formed on the lower layer film using the resist intermediate layer film material, and the intermediate layer is formed.
  • 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, and the substrate is etched using the obtained lower layer film pattern as an etching mask. Forming a pattern.
  • a step (B-1) of forming a lower layer film on the substrate using the lower layer film forming material of the present embodiment, and a resist intermediate layer material containing silicon atoms on the lower layer film are used.
  • a step (B-4) of irradiating a predetermined region of the photoresist layer and developing to form a resist pattern and after the step (B-4), the intermediate layer film using the resist pattern as a mask Etching the lower layer film 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 to form a pattern on the substrate (B-5) Including the.
  • 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 of the present embodiment, and a known method can be applied.
  • a known method can be applied.
  • the lower layer film material of the present embodiment 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 20000 nm, and more preferably 50 to 15000 nm.
  • a silicon-containing resist layer thereon in the case of a two-layer process, a silicon-containing resist layer thereon, or a single-layer resist made of normal hydrocarbon, and in the case of a three-layer process, a silicon-containing intermediate layer is further formed thereon. It is preferable to prepare 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 With 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 polysilsesquide crosslinked with an acid or heat in which a light absorbing group having a phenyl group or a silicon-silicon bond is introduced. Oxane is preferably used.
  • an intermediate layer formed by a chemical vapor deposition (CVD) method can also be used.
  • the intermediate layer produced by the CVD method and having a high effect as an antireflection film is not limited to the following, for example, a SiON film is known.
  • 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 has excellent 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. 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 using only 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 one 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, a method described in Japanese Patent Application Laid-Open No. 2002-334869 (Patent Document 6) and WO 2004/066377 (Patent Document 7) can be used.
  • 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
  • a polysilsesquioxane-based intermediate layer 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 are described, for example, in JP-A-2007-226170 (Patent Document 8) and JP-A-2007-226204 (Patent Document 9). Can be used.
  • Etching of the next substrate can also be performed by a conventional method.
  • the substrate is SiO2 or SiN
  • etching mainly using a chlorofluorocarbon gas and if p-Si, Al, or W is chlorine or bromine gas, Etching mainly composed of can be performed.
  • p-Si, Al, or W is chlorine or bromine gas
  • Etching mainly composed of 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 in the present embodiment has a feature that the etching resistance of the substrate is excellent.
  • known substrates can be appropriately selected and used, and are not particularly limited. Examples thereof include Si, ⁇ -Si, p-Si, SiO 2 , SiN, SiON, W, TiN, and Al. It is done.
  • 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 and stoppers thereof such as Si, SiO 2 , SiON, SiN, p-Si, ⁇ -Si, W, W-Si, Al, Cu, and Al—Si. A film etc.
  • the thing of a different material from a base material (support body) is used normally.
  • the thickness of the substrate to be processed or the film to be processed is not particularly limited, but it is usually preferably about 50 to 10000 nm, more preferably 75 to 5000 nm.
  • the resist permanent film which can also produce a resist permanent film
  • 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.
  • a 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.
  • the above-mentioned film-forming composition for lithography and the composition for permanent resist 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 Carbon concentration and oxygen concentration (mass%) were measured by organic elemental analysis using the following apparatus. Apparatus: CHN coder MT-6 (manufactured by Yanaco Analytical Co., Ltd.)
  • 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 compound had a thermal decomposition temperature of 400 ° C. and a glass transition temperature of 211 ° C., and was confirmed to have high heat resistance.
  • the thermal decomposition temperature was 390 ° C.
  • the glass transition temperature was 200 ° C., and it was confirmed to have high heat resistance.
  • Synthesis Examples 3 to 10 The raw materials of Synthesis Example 1 were changed to 2,6-naphthalenediol and 4-biphenylcarboxaldehyde as shown in Raw Material 1 and Raw Material 2 of Table 1, and the others were performed in the same manner as in Synthesis Example 1 to obtain each target product. . Each was identified by 1H-NMR (Table 2).
  • the obtained resin (R1-XBisN-1) had Mn: 1975, Mw: 3650, and Mw / Mn: 1.84.
  • reaction solution was cooled in an ice bath to precipitate crystals, which were separated by filtration.
  • 40 g of the crystal, 80 g of methanol, 100 g of THF, and 24% aqueous sodium hydroxide were charged into a 100 ml container equipped with a stirrer, a condenser and a burette, and the reaction was stirred for 4 hours under reflux to carry out the reaction. .
  • the mixture was cooled in an ice bath, the reaction solution was concentrated, and the precipitated solid was filtered and dried to obtain 26.5 g of a brown solid resin (Al-R1-XBisN-1).
  • the obtained resin (Al-R1-XBisN-1) was Mn: 2076, Mw: 3540, and Mw / Mn :.
  • CMS-P vinylbenzyl chloride
  • the obtained resin (AlOH-R1-XBisN-1) was Mn: 2121, Mw: 3640, and Mw / Mn :.
  • the obtained resin (Al-R2-XBisN-1) was Mn: 2116, Mw: 3160, and Mw / Mn: 1.62.
  • Synthesis of AlOH-R2-XBisN-1 instead of the above formula (Al-R1-XBisN-1) obtained in Synthesis Example 14-1, it was obtained in Synthesis Example 15-1.
  • the reaction was conducted in the same manner as in Synthesis Example 14-2 except that 40.5 g of the compound represented by the above formula (Al-R2-XBisN-1) was used, and a light gray solid (AlOH-R2-XBisN-1 36.8 g of a resin represented by
  • the obtained resin (AlOH-R2-XBisN-1) was Mn: 2244, Mw: 3215, and Mw / Mn :.
  • 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 under 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 raised to 220 ° C. and reacted for 2 hours.
  • the obtained resin (CR-1) was Mn: 885, Mw: 2220, and Mw / Mn: 4.17.
  • the carbon concentration was 89.1% by mass, and the oxygen concentration was 4.5% by mass.
  • materials for forming a lower layer film for lithography having the compositions shown in Table 6 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.
  • DTDDPI Ditertiary butyl diphenyliodonium nonafluoromethanesulfonate
  • Crosslinking agent Nikalac MX270 (Nikalac) manufactured by Sanwa Chemical Co., Ltd.
  • Organic solvent Propylene glycol monomethyl ether acetate (PGMEA) ⁇ Novolac: PSM4357 manufactured by Gunei Chemical
  • 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. / cm 2, and is cured by irradiation time of 20 seconds to produce each an underlying film having a thickness of 200 nm.
  • the following were used for the photoacid generator, crosslinking agent and organic solvent.
  • -Radical polymerization initiator IRGACURE184 manufactured by BASF ⁇
  • 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.
  • n is an integer of 1 to 4.
  • Etching device 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, a novolac underlayer film was produced under the same conditions as in Example 1 except that novolak (PSM4357 manufactured by Gunei Chemical Co., Ltd.) was used instead of the compound (AlOH-XBisN-1). Then, the above-described etching test was performed on this novolac lower layer film, and the etching rate at that time was measured. Next, the above-described etching test was similarly performed on the lower layer films of Examples 1-1 and 2 and Comparative Example 1, 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.
  • Etching rate is less than ⁇ 10% compared to the novolac lower layer film
  • B Etching rate from ⁇ 10% to + 5% compared to the novolac lower layer film
  • C Etching rate is more than + 5% compared to the novolak underlayer
  • each solution of the underlayer film forming material for lithography containing AlOH-XBisN-1 or AlOH-BisF-1 obtained in Examples 1-1 and 2-1 was applied to a 300 nm-thick SiO 2 substrate. Then, baking was performed 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. On this lower layer film, 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 formula (11) is 4.15 g of 2-methyl-2-methacryloyloxyadamantane, 3.00 g of methacryloyloxy- ⁇ -butyrolactone, 2.08 g of 3-hydroxy-1-adamantyl methacrylate, azobisisobutyronitrile. 0.38 g was dissolved in 80 mL of tetrahydrofuran to obtain a reaction solution. 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 resulting 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 and defects of the obtained 55 nm L / S (1: 1) and 80 nm L / S (1: 1) resist patterns 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 set as “sensitivity” and used as an evaluation index.
  • Table 8 The evaluation results are shown in Table 8.
  • Examples 40 to 41> A solution of a material for forming a lower layer film for lithography of Examples 1-1 and 2-1 using AlOH-XBisN-1 or AlOH-BisF-1 was applied on a SiO 2 substrate having a film thickness of 300 nm, and a solution of 60 ° C. at 240 ° C. was obtained. The film was baked at 400 ° C. for 120 seconds for a second to form an underlayer film having a thickness of 80 nm. 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 the 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, the silicon atom-containing polymer obtained below 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.
  • the prepared film was evaluated as “A” when the refractive index was 1.65 or more, “B” when it was 1.6 or more and less than 1.65, and “C” when it was less than 1.6. .
  • a resist composition was prepared with the formulation shown in Table 10 below. Of the components of the resist composition in Table 10, the following were used for the radical generator, radical diffusion inhibitor, and solvent.
  • -Radical polymerization initiator IRGACURE184 manufactured by BASF
  • -Radical diffusion control agent IRGACURE1010 manufactured by BASF
  • Organic solvent Propylene glycol monomethyl ether acetate acetate (PGMEA)
  • 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 observed with an SEM (Scanning Electron Microscope) And evaluated according to the following.
  • C When a non-rectangular pattern is obtained
  • the compound and resin according to the present invention are highly soluble in a safe solvent, have good heat resistance and etching resistance, and the resist composition according to the present invention gives 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. Furthermore, when the lower layer film is formed, the adhesion with the resist layer is also excellent, so that an excellent resist pattern can be formed.
  • the refractive index is high and the coloring is suppressed by low-temperature to high-temperature treatment, it is useful as a composition for forming various optical parts.
  • 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 for semiconductor resist 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 has industrial applicability in the fields of lithography resist, lithography underlayer film, multilayer resist underlayer film and optical components.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Architecture (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Pyrane Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

L'invention fournit un composé représenté par la formule (0). (Dans la formule (0), ＲＹ représente un atome d'hydrogène, ＲＺ représente une liaison simple ou un groupe de valence N de 1 à 60 atomes de carbone, ＲＴ représentent, chacun de manière indépendante, un groupe alkyle de 1 à 30 atomes de carbone ayant facultativement un substituant, un groupe aryle de 6 à 30 atomes de carbone ayant facultativement un substituant, un groupe alcényle de 2 à 30 atomes de carbone ayant facultativement un substituant, un groupe alcoxy de 1 à 30 atomes de carbone ayant facultativement un substituant, un atome d'halogène, un groupe nitro, un groupe amino, un groupe acide carboxylique, un groupe thiol ou un groupe hydroxyle, lesdits groupe alkyle, groupe aryle, groupe alcényle et groupe alcoxy pouvant inclure une liaison éther, une liaison cétone ou une liaison esther, au moins un ＲＴ représente un groupe hydroxyle, et au moins un ＲＴ représente un groupe alcényle de 2 à 30 atomes de carbone, X représente un atome d'oxygène, un atome de soufre, une liaison simple ou n'est pas réticulé, m représentent, chacun de manière indépendante, un nombre entier de 0 à 9, au moins un m représentant un nombre entier de 2 à 9, ou au moins deux m représentant un nombre entier de 1 à 9, N représente un nombre entier de 1 à 4, les formules structurales à l'intérieur de N paires de crochets pouvant être identiques ou différentes lorsque N est un nombre entier supérieur ou égal à 2, et r représentent, chacun de manière indépendante, un nombre entier de 0 à 2.)
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JP2022130463A (ja) * 2016-09-13 2022-09-06 三菱瓦斯化学株式会社 化合物、樹脂、組成物、並びにレジストパターン形成方法及び回路パターン形成方法

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