WO2021039843A1 - Composition permettant de former un film pour la lithographie, procédé de formation de motif de réserve, procédé de formation de motif de circuit et procédé de purification - Google Patents

Composition permettant de former un film pour la lithographie, procédé de formation de motif de réserve, procédé de formation de motif de circuit et procédé de purification Download PDF

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WO2021039843A1
WO2021039843A1 PCT/JP2020/032187 JP2020032187W WO2021039843A1 WO 2021039843 A1 WO2021039843 A1 WO 2021039843A1 JP 2020032187 W JP2020032187 W JP 2020032187W WO 2021039843 A1 WO2021039843 A1 WO 2021039843A1
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group
substituent
carbon atoms
film
resist
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PCT/JP2020/032187
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English (en)
Japanese (ja)
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越後　雅敏
牧野嶋　高史
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三菱瓦斯化学株式会社
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Priority to CN202080059349.6A priority Critical patent/CN114303096A/zh
Priority to JP2021542965A priority patent/JPWO2021039843A1/ja
Publication of WO2021039843A1 publication Critical patent/WO2021039843A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • the present invention relates to a film forming composition for lithography, a resist pattern forming method, a circuit pattern forming method, and a purification method.
  • Non-Patent Document 2 a polyphenol compound as a base compound of a resist material can impart high heat resistance while having a low molecular weight and is useful for improving the resolution and roughness of a resist pattern
  • the present inventors have excellent etching resistance, and as a material that is soluble in a solvent and to which a wet process can be applied, a resist composition containing a compound having a specific structure and an organic solvent (see Patent Document 4). Is proposing.
  • the resist pattern becomes finer, there arises a problem of resolution or a problem that the resist pattern collapses after development, so that it is desired to reduce the thickness of the resist.
  • the resist is simply thinned, it becomes difficult to obtain a resist pattern film thickness sufficient for substrate processing. Therefore, not only the resist pattern but also a process of forming a resist underlayer film between the resist and the semiconductor substrate to be processed and giving the resist underlayer film a function as a mask at the time of substrate processing is required.
  • Patent Document 13 describes an optical lens sheet containing an ionic liquid, a compound having a predetermined polyalkylene oxide structure and a (meth) acryloyl group, a predetermined (meth) acrylate monomer, and a photopolymerization initiator.
  • An energy ray-curable resin composition is disclosed.
  • Patent Document 14 describes that a resin composition containing a copolymer having a specific structural unit, a specific curing acceleration catalyst, and a solvent is suitably used for a microlens or a flattening film. Has been done.
  • It may have a bridging group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, and a substituent having 0 to 30 carbon atoms. If it is any of the amino group, carboxyl group, thiol group, and hydroxyl group of 30, and R 1A is any of the alkyl group, the aryl group, the cross-linking group, and the alkoxy group, an ether bond and a ketone. It may contain at least one bond selected from the group consisting of a bond and an ester bond, and at least one of R 1A is an amino group having 0 to 30 carbon atoms which may have a substituent.
  • X is an oxygen atom or a sulfur atom, and X does not have to be present.
  • R independently represents any of a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, and a pyrene ring.
  • m is an integer from 0 to 9 independently, where at least one of m is an integer from 1 to 9.
  • n A is an integer of 1 to 4.
  • R 4A is the alkyl group or acyl group.
  • the aryl group, and the cross-linking group may contain at least one bond selected from the group consisting of ether bonds, ketone bonds, and ester bonds.
  • m 6A is an integer of 0 to 5 independently of each other.
  • R X, X, R, and n A are as defined above.
  • RY is any one of a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent.
  • R Z is an n A- valent group or a single bond having 1 to 60 carbon atoms, and the total number of carbon atoms of RY and R Z is 69 or less.
  • X, R, n A , R 3A , R 4A , and m 6A are synonymous with the above.
  • L is a linear or branched linking group or a single bond having 1 to 30 carbon atoms.
  • RX , R 1A , X, R, m, and n A are as defined in [1].
  • [14] The lithography according to [13], which comprises at least one selected from the group consisting of the compounds represented by the formulas (BiA-1) to (BiA-35) and the polyamine resin having a structural unit derived from the compound. Membrane forming composition.
  • the film forming composition for lithography according to [15] which further contains an acid generator.
  • a method for forming a resist pattern including. [27] A lower layer film forming step of forming a lower layer film on a substrate using the lithography film forming composition according to [19], and An intermediate layer film forming step of forming an intermediate layer film on the lower layer film formed by the lower layer film forming step, A photoresist layer forming step of forming at least one photoresist layer on the interlayer film formed by the intermediate layer film forming step.
  • R X is 2n A-valent group or a single bond, it is preferred that 2n A-valent group.
  • the carbon number of the 2n A- valent group is 1 to 70, preferably 3 to 50, and more preferably 6 to 30.
  • R x1 examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, and a neopentyl group.
  • the aryl group is not particularly limited, but is, for example, a phenyl group, a naphthyl group (for example, 1-naphthyl group and 2-naphthyl group), an anthryl group (for example, 1-anthryl group), and a phenanthryl group (for example, 1-).
  • Aryl groups having 6 to 30 carbon atoms such as phenanthryl group) can be mentioned, and from the viewpoint of more effectively and surely exerting the action and effect of the present invention, the aryl group has 6 to 10 carbon atoms such as phenyl group and naphthyl group. Is preferable, and a phenyl group is more preferable.
  • Examples of the alicyclic hydrocarbon ring include a monocyclic aliphatic hydrocarbon ring and a polycyclic aliphatic hydrocarbon ring.
  • the group represented by the above formula (R 4 ) 2 N- is an amino group; one R 4 is a hydrogen atom and the other R 4 is from the viewpoint of more effectively and surely exerting the action and effect of the present invention.
  • Alkyl group for example, linear or branched alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, n-butyl group
  • alkylcarbonyl group for example, methylcarbonyl group, ethyl) carbonyl group, n- propyl group, and n- butyl carbonyl monosubstituted amino group is a linear or branched alkyl group) having 2 to 5 carbon atoms, such groups
  • two R 4 is an alkyl group ( For example, a linear or branched alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an n-buty
  • At least one of R 1A represents an amino group having 0 to 30 carbon atoms which may have a substituent.
  • the number of the amino groups is not particularly limited as long as it is one or more, but from the viewpoint of more effectively and surely exerting the action and effect of the present invention, it is preferably 1 to 3, and more preferably 1 or 2. preferable.
  • the amino groups of each other may be substituted with the same aromatic ring or may be substituted with different aromatic rings.
  • X represents an oxygen atom or a sulfur atom, and X may not be present, but from the viewpoint of further excellent structure forming ability, it is preferably an oxygen atom or a sulfur atom, and oxygen is preferable. It is more preferably an atom.
  • the compound represented by the formula (0) in which X represents an oxygen atom is represented by the following formula (0-1). (In the above formula (0-1), RX , R 1A , R, m, and n A have the same meanings as described above.)
  • m is an integer of 0 to 9 independently. However, at least one of m is an integer of 1 to 9. From the viewpoint of more effectively and surely exerting the action and effect of the present invention, m is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and preferably an integer of 1 or 2. More preferred.
  • the compound represented by the above formula (0) has a high refractive index due to its high aromatic ring density, and its coloring is suppressed even by a wide range of heat treatment from low temperature to high temperature. Therefore, various optical component forming materials. It is also useful as.
  • the compound represented by the above formula (0) is preferably a compound having quaternary carbon from the viewpoint of suppressing oxidative decomposition of the compound, suppressing coloring, and improving heat resistance and solvent solubility.
  • the optical component may be in the form of a film or a sheet, for example, a plastic lens (for example, a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast improving lens, etc.), a position, and the like.
  • a plastic lens for example, a prism lens, a lenticular lens, a microlens, a Fresnel lens, a viewing angle control lens, a contrast improving lens, etc.
  • the compound represented by the formula (0) includes an embedded film and a flattening film on a photodiode, which is a member of a solid-state image sensor for which a high refractive index is particularly required, a flattening film before and after a color filter, a microlens, and a micro. It is suitably used as a material for forming a flattening film and a conformal film on a lens.
  • the (poly) amine compound represented by the formula (0) is preferably a compound represented by the following formula (1) from the viewpoint of further excellent structure forming ability.
  • Each of R 3A 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, and a substituent.
  • R 4A has a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an acyl group having 1 to 30 carbon atoms which may have a substituent, and a substituent. It is either an aryl group having 6 to 30 carbon atoms which may have a substituent, and a bridging group having 2 to 30 carbon atoms which may have a substituent, and R 4A is the alkyl group or acyl group. , The aryl group, and the cross-linking group, may contain at least one bond selected from the group consisting of ether bonds, ketone bonds, and ester bonds.
  • m 6A is an integer of 0 to 5 independently of each other.
  • R X, X, R, and n A are as defined above.
  • R 3A Each of R 3A 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, and a substituent.
  • Examples of the alkyl group having 1 to 30 carbon atoms which may have a substituent include the alkyl group exemplified as the alkyl group in (1-1-1a.
  • R X1 The aryl group which may having 6 to 30 carbon atoms which may have a substituent, for example, in (1-1-1a.R X1), be mentioned exemplified aryl group as the aryl group.
  • Examples of the cross-linking group having 2 to 30 carbon atoms which may have a substituent include the cross-linking group exemplified as the cross-linking group in (2.R 1A).
  • Examples of the alkoxy group having 1 to 30 carbon atoms which may have a substituent include the alkoxy group exemplified as the alkoxy group in (2. R 1A).
  • R 3A is a linear or branched alkyl group having 1 to 30 carbon atoms and a substituent which may have a substituent from the viewpoint of more effectively and surely exerting the action and effect of the present invention. It is preferably an aryl group having 6 to 30 carbon atoms which may have.
  • the linear or branched alkyl group having 1 to 30 carbon atoms which may have a substituent is preferable in (2.R 1A) of [(poly) amine compound represented by the formula (0)]. It is preferably an alkyl group exemplified as an alkyl group which may have a substituent.
  • the aryl group having 6 to 30 carbon atoms which may have a substituent is preferably the aryl group exemplified as the aryl group which may have a preferable substituent in (2. R 1A).
  • R 4A has a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an acyl group having 1 to 30 carbon atoms which may have a substituent, and a substituent. Indicates either an aryl group having 6 to 30 carbon atoms which may have a substituent and a bridging group having 2 to 30 carbon atoms which may have a substituent, and R 4A is the alkyl group or acyl group.
  • the aryl group, and the cross-linking group, at least one bond selected from the group consisting of an ether bond, a ketone bond, and an ester bond may be contained.
  • a hydrogen atom a linear or branched alkyl group having 1 to 30 carbon atoms which may have a substituent, and a ketone bond
  • the alkyl group contains (for example, an alkylcarbonyl group).
  • m 6A is an integer of 0 to 5 independently, and is preferably an integer of 1 to 3 from the viewpoint of more effectively and surely performing the effects of the present invention, and is an integer of 1 or 2. Is more preferable.
  • R X, R , n A, R 3A, R 4A, and m 6A are as defined above.
  • the (poly) amine compound represented by formula (2) is more preferably a (poly) amine compound represented by the following formula (2) from the viewpoint of further improving the solubility in an organic solvent.
  • (1. RY ) RY represents any one of a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, and an aryl group having 6 to 30 carbon atoms which may have a substituent.
  • Examples of the alkyl group having 1 to 30 carbon atoms which may have a substituent, for example, in (1-1-1a.R X1) include exemplified alkyl group as an alkyl group, effects of the present invention As a preferable alkyl group from the viewpoint of more effectively and surely playing the above, an alkyl group exemplified as a preferable alkyl group in (1-1-1a. R X1) can be mentioned.
  • the aryl group which may having 6 to 30 carbon atoms which may have a substituent, for example, in (1-1-1a.R X1) include exemplified aryl group as the aryl group, effects of the present invention in view to achieve the more efficient and reliable, preferred aryl groups in (1-1-1a.R X1), be mentioned exemplified aryl groups as preferred aryl group.
  • RY is preferably an aryl group having 6 to 30 carbon atoms which may have a hydrogen atom, a methyl group or a substituent, more preferably a hydrogen atom or a methyl group, and hydrogen. Most preferably it is an atom. ..
  • R Z is preferably a group having an n A valence of 1 to 60 carbon atoms from the viewpoint of more effectively and surely exerting the action and effect of the present invention.
  • the n A-valent group having 1 to 60 carbon atoms for example, include n A-valent group exemplified in (1-1-1b.R X2), as preferable groups, (1-1-1b.
  • Examples of the preferred n- A- valent group in RX2 ) include n- A- valent groups.
  • R, n A , R 3A , R 4A , m 6A , RY , and R Z have the same meanings as described above.
  • the (poly) amine compound represented by the formula (2) is represented by the following formula (3) from the viewpoint of further improving the solubility in an organic solvent and further improving the heat resistance and the refractive index (3). It is more preferably a poly) amine compound.
  • R 3A' may have an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, and a substituent. It is any of an amino group, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a bridging group, a hydroxyl group and a cyano group which may have a substituent and have 2 to 30 carbon atoms.
  • R 1 is a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, and a heterocycle containing at least one of an oxygen atom, a sulfur atom, and a nitrogen atom as a hetero atom (for example, a furan ring, an imidazole ring, a carbazole ring, etc.
  • R 3A' may have an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, and a substituent. It is any of an amino group, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a bridging group, a hydroxyl group and a cyano group which may have a substituent and may have 2 to 30 carbon atoms.
  • R 3A' has an alkyl group having 1 to 30 carbon atoms which may have a substituent and an alkyl group having 1 to 30 carbon atoms which may have a substituent. Any of an alkoxy group, an aryl group having 6 to 30 carbon atoms which may have a substituent, and a bridging group, a hydroxyl group and a cyano group which may have a substituent and have 2 to 30 carbon atoms. Is preferable.
  • Each R 3A' 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, and a substituent. It is preferable to indicate any of a cross-linking group having 2 to 30 carbon atoms and a cyano group.
  • the alkyl group having 1 to 30 carbon atoms which may have a substituent for example, in (1-1-1a.R X1), include alkyl groups exemplified as alkyl groups.
  • the aryl group having 6 to 30 carbon atoms which may have a substituent for example, in (1-1-1a.R X1), be mentioned exemplified aryl group as the aryl group.
  • Examples of the cross-linking group having 2 to 30 carbon atoms which may have a substituent include the cross-linking group exemplified as the cross-linking group in (2.R 1A).
  • R 3A' is a linear or branched alkyl group having 1 to 30 carbon atoms which may have a substituent and a substitution from the viewpoint of more effectively and surely exerting the action and effect of the present invention. It is preferably an aryl group having 6 to 30 carbon atoms which may have a group.
  • the linear or branched alkyl group having 1 to 30 carbon atoms which may have a substituent is preferable in (2.R 1A) of [(poly) amine compound represented by the formula (0)]. It is preferably an alkyl group exemplified as an alkyl group which may have a substituent.
  • the aryl group having 6 to 30 carbon atoms which may have a substituent is preferably the aryl group exemplified as the aryl group which may have a preferable substituent in (2. R 1A).
  • m 6A' is an integer of 0 to 5, and is preferably an integer of 1 to 3 and more preferably an integer of 1 or 2 from the viewpoint of more effectively and surely performing the effects of the present invention. ..
  • R 1 independently represents any one of a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, and so on.
  • R 1 when R 1 is a benzene ring, it indicates that one or more R 3A'is substituted on the benzene ring, and the substitution position of each R 3A'with the benzene ring is not particularly limited. ..
  • R 1 when R 1 is a naphthalene ring, it indicates that one or more R 3A'is substituted on the naphthalene ring, and the substitution position of each R 3A'with the naphthalene ring is not particularly limited.
  • R 1 when R 1 is an anthracene ring, it indicates that one or more R 3A'is substituted on the anthracene ring, and the substitution position of each R 3A'with the anthracene ring is not particularly limited. .. R 1 is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring, from the viewpoint of more effectively and surely exerting the effects of the present invention.
  • the (poly) amine compound represented by the formula (3) has R 3A , R 4A , m 6A , R, X, RY , R 3A ', from the viewpoint of more effectively and surely exerting the action and effect of the present invention. It is preferable that m 6A'and R 1 simultaneously satisfy the following conditions (i) to (ix), respectively.
  • R 3A is an independent alkyl group (particularly methyl group and ethyl group), haloalkyl group (particularly trichloromethyl group and trifluoromethyl group), hydroxyl group, phenyl group, and phenyl group substituted with amino group.
  • R 4A which is one of (particularly aminophenyl group), independently indicates any of hydrogen atom, alkyl group, and alkylcarbonyl group, and (iii) m 6A is 0 or 1.
  • R is a benzene ring or a naphthalene ring
  • X indicates an oxygen atom or does not exist
  • RY indicates a methyl group or a phenyl group
  • R 3A' is methyl group, ethyl group, n- propyl group, n- butyl group, any one of a cyclohexyl group and a hydroxyl group
  • R 1 is a benzene ring
  • the (poly) amine compound represented by the formula (3) is preferably a compound represented by the following formula (0a) from the viewpoint of further improving solubility and heat resistance, and is preferably represented by the following formula (0b). It is more preferably the compound represented.
  • R 4A' may have 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, and a substituent. Indicates either a cross-linking group having 2 to 30 carbon atoms or a cyano group.
  • m 5A represents an integer from 0 to 5.
  • R 4A' 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, and a carbon which may have a substituent. Indicates any of the number 2 to 30 cross-linking groups and cyano groups.
  • m 5A represents an integer from 0 to 5.
  • the (poly) amine compound represented by the formula (3) is preferably a compound represented by the following formula (0a-1) from the viewpoint of further improving the solubility, and is preferably represented by the following formula (0b-1). It is more preferably the compound represented.
  • R, R 3A , R 4A , m 6A , R 4A' , m 5A and RY have the same meanings as described above.
  • R, R 3A , R 4A , m 6A , R 4A' , and m 5A have the same meanings as described above.
  • the (poly) amine compound represented by the formula (0b-1) is more preferably a compound represented by the following formula (0b-2) from the viewpoint of further improving the fluidity during film formation.
  • R, R 3A , R 4A , R 4A' , and m 5A are synonymous with the above.
  • m 5A' is an integer of 1 to 5 independently.
  • the (poly) amine compound represented by the formula (0a-1) is more preferably a compound represented by the following formula (0a-2) from the viewpoint of further improving the solubility.
  • R, R 3A , R 4A , R 4A' , m 6A , and m 5A are synonymous with the above.
  • R Y ' is either a aryl group of the alkyl group and carbon atoms 6 may have a substituent to 30, having 1 to 30 carbon atoms which may have a substituent.
  • the (poly) amine compound represented by the formula (0b-1) is more preferably a compound represented by the following formula (0b-3) from the viewpoint of further improving the fluidity during film formation.
  • R, R 3A , R 4A , m 6A , and m 5A are synonymous with the above.
  • R 5A represents an alkyl group having 5 to 30 carbon atoms which may have a substituent.
  • the (poly) amine compound represented by the formula (3) is a compound represented by the following formula (1a) from the viewpoint of being more excellent in the supply of raw materials and further improving the solubility and heat resistance. Is preferable, and the compound represented by the following formula (1b) is more preferable.
  • the (poly) amine compound represented by the formula (3) is preferably a compound represented by the following formula (3a) from the viewpoint of further improving heat resistance, and is represented by the following formula (3b). More preferably, it is a compound.
  • R, X, R 3A , R 4A , m 6A , RY , R 1 , R 3A' , and m 6A' are synonymous with the above.
  • n A' is an integer of 2-4.
  • R, X, R 3A , R 4A , m 6A , R 1 , R 3A' , and m 6A' are synonymous with the above.
  • n A' is an integer of 2-4.
  • the compound represented by the above formula (3) preferably has X as an oxygen atom from the viewpoint of further improving the solubility in an organic solvent and further improving the heat resistance and the refractive index.
  • the (poly) amine compound in which X is an oxygen atom is represented by the compound represented by the following formula (0-4).
  • R, n A , R 3A , R 4A , m 6A , RY , R 1 , R 3A' , and m 6A' have the same meanings as described above.
  • the compound represented by the above formula (0-4) is a compound represented by the following formula (1a-1) from the viewpoint of being excellent in the supply of raw materials and further improving the solubility and heat resistance. It is preferable that the compound is represented by the following formula (1b-1), and more preferably.
  • R, R 3A , R 4A , m 6A , and RY have the same meanings as described above.
  • R, R 3A , R 4A , and m 6A have the same meanings as described above.
  • R 4A in the above formula is a hydrogen atom from the viewpoint of improving the curing performance by the reactive functional group.
  • Representative (poly) amine compounds of the present embodiment include (poly) amine compounds represented by the formulas (p1) to (p55) and (p61) to (p509).
  • R 4 is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotoriacontyl group, norbonyl group, adamantyl group, naphthyl group, anthracene group, heptaxen Examples include a group, a triacontenyl group, a methoxy
  • R 5 is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, triacontyl group, cyclopropyl group, cyclobutyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotoriacontyl group, norbonyl group, adamantyl group, naphthyl group, anthracene group, heptaxen Examples include a group, a triacontenyl group, a methoxy
  • R 6 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, cyclotoriacontyl group, norbonyl group, adamantyl group, naphthyl group, anthracene group, heptaxen Examples include a group, a triacontenyl group, a methoxy group, an ethoxy group, a triacontixi group and the like, and each example contains an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • the number of R 6 may be 1 or more.
  • R 7 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, cyclotoriacontyl group, norbonyl group, adamantyl group, naphthyl group, anthracene group, heptasen Examples include a group, a triacontenyl group, a methoxy group, an ethoxy group, a triacontixi group and the like, and each example contains an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • the number of R 7 may be 1 or more.
  • R 8 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, cyclotoriacontyl group, norbonyl group, adamantyl group, naphthyl group, anthracene group, heptaxen Examples include a group, a triacontenyl group, a methoxy group, an ethoxy group, a triacontixi group and the like, and each example contains an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • the number of R 8 may be 1 or more.
  • R 9 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, cyclotoriacontyl group, norbonyl group, adamantyl group, naphthyl group, anthracene group, heptaxen Examples include a group, a triacontenyl group, a methoxy group, an ethoxy group, a triacontixi group and the like, and each example contains an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • the number of R 9 may be 1 or more.
  • R 10 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, cyclotoriacontyl group, norbonyl group, adamantyl group, naphthyl group, anthracene group, heptaxen Examples include a group, a triacontenyl group, a methoxy group, an ethoxy group, a triacontixi group and the like, and each example contains an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • the number of R 10 may be 1 or more.
  • R 11 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, cyclotoriacontyl group, norbonyl group, adamantyl group, naphthyl group, anthracene group, heptaxen Examples include a group, a triacontenyl group, a methoxy group, an ethoxy group, a triacontixi group and the like, and each example contains an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • the number of R 11 may be 1 or more.
  • R 12 or R 13 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.
  • cyclobutyl group cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundesyl group, cyclododecyl group, cyclotoriacontyl group, norbonyl group, adamantyl group, naphthyl group, anthracene
  • Examples thereof include a group, a heptasen group, a triacontenyl group, a methoxy group, an ethoxy group, a triacontixi group and the like, and each example contains an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • the number of R 12 or R 13 may be 1 or more.
  • R 9 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, cyclotoriacontyl group, norbonyl group, adamantyl group, naphthyl group, anthracene group, heptaxen Examples include a group, a triacontenyl group, a methoxy group, an ethoxy group, a triacontixi group and the like, and each example contains an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • the number of R 9 may be 1 or more.
  • cyclopentyl group cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, cyclotoriacontyl group, norbonyl group, adamantyl group, naphthyl group, anthracene group, heptaxen Examples include a group, a triacontenyl group, a methoxy group, an ethoxy group, a triacontixi group and the like, and each example contains an isomer.
  • the butyl group includes an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • the number of R 13 may be 1 or more.
  • aldehydes examples include compounds represented by the following formula (0-b), and compounds represented by the following formula (3-a) are preferable.
  • R 3A ', m 6A' , R 1, and n A is, R 3A in the formula (3) ', m 6A' , the same meanings as R 1, and n A.
  • benzaldehyde ethylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarbaldehyde, phenanthrencarbaldehyde, pyrenecarbaldehyde, and furfural (poly).
  • a higher etching resistance can be imparted to the amine compound.
  • an aldehyde having an aromatic ring from
  • ketones examples include ketones represented by the following formula (0-c).
  • the amount of the acid catalyst used can be appropriately set according to the raw material to be used, the type of catalyst, the reaction conditions, and the like, and may be, for example, about 0.01 to 100 parts by mass with respect to 100 parts by mass of the entire reaction raw material. Just do it.
  • the reaction raw materials may be reacted in a solvent.
  • the solvent may be any solvent that can sufficiently proceed the reaction between the anilines used as the reaction raw material and the aldehydes and / or the ketones.
  • the solvent include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, or a mixed solvent thereof.
  • the solvent one type can be used alone, or two or more types can be used in combination.
  • the (poly) amine compound may be isolated by a known method.
  • an isolation method for example, first, the reaction solution is concentrated and pure water is added to precipitate the reaction product. Next, the precipitated reaction product is cooled to room temperature and then separated by filtration. The solid obtained by separation is further filtered and dried. The dried reaction product is separated and purified into a product and a by-product by column chromatography. Further, the separated and purified reaction product is subjected to solvent distillation, filtration, and further drying to obtain the target (poly) amine compound of the present embodiment.
  • the compound for introducing the crosslinkable group is dissolved or suspended in the aprotic solvent of an aprotic solvent (for example, acetone, tetrahydrofuran (THF), and propylene glycol monomethyl ether acetate).
  • an aprotic solvent for example, acetone, tetrahydrofuran (THF), and propylene glycol monomethyl ether acetate.
  • epichlorohydrin eg, epichlorohydrin and epibromohydrin
  • the reaction is carried out under normal pressure at a reaction temperature of 0 to 60 ° C. and a reaction time of 6 to 72 hours.
  • a (poly) amine compound having a specific functional group is dissolved or suspended in an aprotic solvent.
  • allyl halides eg, allyl chloride and allyl bromide
  • methacrylic acid halides eg, methacrylic acid chloride and methacrylic acid bromide
  • Vinyl benzyl halide eg, vinyl benzyl chloride and vinyl benzyl bromide
  • alkaline catalysts eg, sodium hydroxide, triethylamine, and potassium carbonate
  • the reaction is carried out at ⁇ 110 ° C. and a reaction time of 6 to 72 hours.
  • the reaction solution is neutralized with an acid such as hydrochloric acid, and distilled water is added to the reaction solution to precipitate a white solid.
  • the separated white solid is washed with distilled water and dried to obtain a (poly) amine compound in which the hydrogen atom of a specific functional group is replaced with an acid crosslinkable group.
  • the timing of introducing the acid crosslinkable group may be before or after the polycondensation reaction between anilines and aldehydes and / or ketones. Further, it may be after the resin described later is manufactured.
  • the acid crosslinkable group reacts in the presence or absence of a radical or an acid or alkali, and has a refractive index, heat resistance, mechanical strength, and the like. Permeability and solubility in acids or alkalis or organic solvents used in coating solvents or developing solutions can be improved.
  • Examples of the acid-crosslinkable group include an allyl group, a (meth) acryloyl group, a vinyl group, an epoxy group, an alkoxymethyl group, and a cyanato group.
  • the resin of the present embodiment may be composed of only the above-mentioned monomer unit of the present embodiment, may contain other monomer units copolymerizable with the (poly) amine compound, and is a unit derived from a compound having crosslink reactivity. May include.
  • linking group examples include a group (residue) derived from a compound capable of oligomerizing or polymerizing the (poly) amine compound of the present embodiment. Groups derived from compounds that can be oligomerized or polymerized will be described later.
  • X, R, R 3A , R 4A , m 6A , RY , and L have the same meanings as described above, and R 4A'may have a substituent and has 1 to 1 to carbon atoms. It indicates any one of 30 alkyl groups, aryl groups having 6 to 30 carbon atoms which may have a substituent, bridging groups having 2 to 30 carbon atoms which may have substituents, and cyano groups. Further, m 5A represents an integer of 0 to 5.
  • the monomer unit constituting the (poly) amine resin represented by the formula (7) is preferably the monomer unit represented by the following formula (7a-1) from the viewpoint of further improving the solubility, and is preferably the monomer unit represented by the following formula (7a-1). It is more preferably a monomer unit represented by (7b-1).
  • R, R 3A , R 4A , m 6A , R 4A' , m 5A , RY , and L have the same meanings as described above.
  • R, R 3A , R 4A , m 6A , R 4A' , m 5A , and L have the same meanings as described above.
  • the monomer unit constituting the (poly) amine resin represented by the formula (7a-1) is more preferably the monomer unit represented by the following formula (7a-2) from the viewpoint of further improving the solubility. ..
  • R, R 3A, R 4A, m 6A, R 4A ', m 5A, L is are the same as defined above, R Y' may have a substituent It is either an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms which may have a substituent.
  • the monomer unit constituting the (poly) amine resin represented by the formula (7b-1) is a monomer unit represented by the following formula (7b-3) from the viewpoint of further improving the fluidity during film formation. Is even more preferable.
  • R, R 3A , R 4A , m 6A , m 5A , and L are synonymous with the above, and R 5A may have a substituent and has 5 to 30 carbon atoms. Indicates the alkyl group of.
  • the monomer unit constituting the (poly) amine resin represented by the formula (7) is represented by the following formula (7a-3) from the viewpoint of further improving the supply of raw materials and further improving the solubility and heat resistance. It is preferably a monomer unit represented by the following formula (7b-4), and more preferably a monomer unit represented by the following formula (7b-4).
  • the monomer unit constituting the (poly) amine resin represented by the formula (7) is preferably a monomer unit represented by the following formula (7a') from the viewpoint of further improving heat resistance, and is preferably the following formula. It is more preferably a monomer unit represented by (7b').
  • R, X, R 3A, R 4A, m 6A, R Y, R 1, R 3A above formula (7a)', m 6A ' , L are as defined above, n A' 2-4 Is an integer of.
  • the monomer units represented by the above formulas (4), (5), (6) and (7) have the following formulas (0-5) and (0-6), respectively, from the viewpoint of further improving the structure forming ability. ), (0-7), and (0-8) are preferably monomer units.
  • R X, R 1A, R, m, n A, and L are as defined above.
  • R X, R , n A, R 3A, R 4A, m 6A, and L have the same meanings as defined above.
  • R, n A , R 3A , R 4A , m 6A , RY , R Z , and L have the same meanings as described above.
  • R, n A , R 3A , R 4A , m 6A , RY , R 1 , R 3A' , m 6A' , and L are synonymous with the above.
  • the resin of the present embodiment is obtained by reacting the compound of the present embodiment with a compound having a cross-linking reactivity, if necessary.
  • the cross-linking reactive compound is not particularly limited as long as it is a compound capable of oligomerizing or polymerizing the (poly) amine compound of the present embodiment. Specific examples thereof include aldehydes, ketones, carboxylic acids, carboxylic acid anhydrides, carboxylic acid halides, halogen-containing compounds, isocyanates, unsaturated hydrocarbon group-containing compounds and the like.
  • L is a linking group
  • the linking group corresponds to a group derived from these compounds.
  • examples of the aldehydes for novolacification include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, hydroxybenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde and ethylbenzaldehyde.
  • ketones for novolacization include ketones exemplified as a reaction raw material. Among these, formaldehydes are preferable. In addition, these aldehydes and / or ketones can be used individually by 1 type or in combination of 2 or more type.
  • a catalyst can also be used in the condensation reaction of the (poly) amine compound of the present embodiment with an aldehyde and / or a ketone.
  • Examples of the acid catalyst used here include the acid catalyst exemplified in the section of the condensation step.
  • the (poly) amine compound of the present embodiment can be used as indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna-2- Aldehydes and / or ketones are not always required when performing a copolymerization reaction with a compound having a non-conjugated double bond such as indene, ⁇ -pinene, ⁇ -pinene, and limonene.
  • a reaction solvent can also be used in the condensation reaction of the (poly) amine compound of the present embodiment with an aldehyde and / or a ketone.
  • the reaction solvent exemplified in the section in the polycondensation step can be exemplified.
  • the amount of solvent used, reaction temperature, reaction time, isolation method after reaction, etc. can also be exemplified by the amount of solvent used, reaction temperature, reaction time, isolation method after reaction, etc. exemplified in the section of polycondensation step. ..
  • the resin of the present embodiment may be copolymerized with a polymerizable monomer in addition to the other phenols described above.
  • the copolymerization monomer include naphthol, methylnaphthol, methoxynaphthol, dihydroxynaphthalene, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, and the like.
  • Examples include norbornadiene, vinyl norbornadiene, pinen, and limonene.
  • the resin of the present embodiment may be a binary or higher (for example, 2 to quaternary) copolymer of the (poly) amine compound of the present embodiment and the above-mentioned phenols. It may be a binary or more (for example, 2 to quaternary) copolymer of the (poly) amine compound of the present embodiment and the above-mentioned copolymerization monomer. It may be a ternary or more (for example, 3 to quaternary) copolymer of the (poly) amine compound of the present embodiment, the above-mentioned phenols, and the above-mentioned copolymerization monomer.
  • the compound of the present embodiment and / or the resin of the present embodiment described above are preferably highly soluble in a solvent from the viewpoint of facilitating the application of a wet process and the like. More specifically, these compounds and / or resins use cyclohexanone (CHN), cyclopentanone (CPN), 1-methoxy-2-propanol (PGME) and / or propylene glycol monomethyl ether acetate (PGMEA) as a solvent. If so, the solubility in the solvent is preferably 10% by mass or more.
  • the solubility in CHN, CPN, PGME and / or PGMEA is defined as "mass of resin ⁇ (mass of resin + mass of solvent) x 100 (mass%)".
  • composition of the present embodiment contains one or more selected from the group consisting of the compound of the present embodiment and a resin obtained by using the compound of the present embodiment as a monomer.
  • composition of the present embodiment contains the compound and / or resin of the present embodiment, a wet process can be applied, and a composition for forming a lithography film having excellent heat resistance and etching resistance (that is, It is useful as a "film forming composition for lithography"). Since the composition of the present embodiment contains a compound or resin having a specific structure having high heat resistance and solvent solubility, deterioration of the film during high-temperature baking is suppressed, and the composition is resistant to plasma etching and the like as compared with the photoresist layer. A lithography film having excellent etching resistance can be formed.
  • the composition of the present embodiment is also excellent in adhesion to the resist layer when the underlayer film is formed, so that an excellent resist pattern can be formed. Further, since the aromatic ring density is high, the refractive index is high, and coloring due to a wide range of heat treatment from low temperature to high temperature is suppressed, so that it is suitably used for forming optical components.
  • the film forming composition for lithography used for forming the photoresist layer may be referred to as "resist composition”. Further, a film forming composition for lithography used for forming a resist underlayer film may be referred to as a "lower layer film forming composition for lithography”.
  • the film-forming composition for lithography in the present embodiment can be suitably used as a resist composition, an underlayer film-forming composition for lithography, and a permanent resist film-forming composition.
  • the resist composition of the present embodiment contains one or more components (hereinafter, also referred to as "component (A)”) selected from the group consisting of the compound of the present embodiment and a resin obtained by using the compound as a monomer. ..
  • the resist composition of the present embodiment preferably contains a solvent.
  • the solvent is not particularly limited, and examples thereof include those described in International Publication No. 2013/024778. These solvents can be used alone or in combination of two or more.
  • 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. It is a species, 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 mass of the solid component and 20 to 99% by mass of the solvent are relative to 100% by mass of the total mass of the amount of the solid component and the solvent. %, More preferably 1 to 50% by mass of the solid component and 50 to 99% by mass of the solvent, still more preferably 2 to 40% by mass of the solid component and 60 to 98% by mass of the solvent, and particularly preferably the solid component. It is 2 to 10% by mass and 90 to 98% by mass of the solvent.
  • the resist composition of the present embodiment may contain other components such as an acid generator and a cross-linking agent, if necessary, in addition to the above-mentioned component (A) and solvent.
  • these optional components will be described.
  • acid generator (C) In the resist composition of the present embodiment, acid is directly or indirectly generated by irradiation with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet (EUV), X-ray and ion beam. It is preferable to contain one or more acid generators (C).
  • the acid generator (C) is not particularly limited, but for example, the acid generator (C) described in International Publication No. 2013/024778 can be used.
  • the acid generator (C) may be used alone or in combination of two or more.
  • the amount of the acid generator (C) used is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, further preferably 3 to 30% by mass, and 10 to 25% by mass based on the total weight of the solid component. Especially preferable.
  • the acid generator (C) within the above range, a pattern profile with high sensitivity and low edge roughness can be obtained.
  • the method of generating the acid is not limited. Finer processing is possible by using an excimer laser instead of ultraviolet rays such as g-rays and i-rays, and further fine processing is possible by using electron beams, extreme ultraviolet rays, X-rays, and ion beams as high-energy rays. Is possible.
  • the acid cross-linking agent (G) is a compound capable of intramolecularly or intermolecularly cross-linking the component (A) in the presence of an acid generated from the acid generator (C).
  • Examples of such an acid cross-linking agent (G) include compounds having one or more groups (hereinafter, referred to as “cross-linking groups”) capable of cross-linking the component (A).
  • Such a crosslinkable group is not particularly limited, but for example, (i) hydroxy (C1-C6 alkyl group), C1-C6 alkoxy (C1-C6 alkyl group), acetoxy (C1-C6 alkyl group) and the like.
  • crosslinkable group of the acid cross-linking
  • the acid cross-linking agent (G) having a cross-linking group is not particularly limited, but for example, the one described in International Publication No. 2013/024778 can be used.
  • the acid cross-linking agent (G) can be used alone or in combination of two or more.
  • the amount of the acid cross-linking agent (G) used is preferably 0.5 to 49% by mass, more preferably 0.5 to 40% by mass, still more preferably 1 to 30% by mass, based on the total weight of the solid components. 2 to 20% by mass is particularly preferable.
  • the amount of the acid cross-linking agent (G) is preferably 0.5% by mass or more, the effect of suppressing the solubility of the resist film in the alkaline developer is improved, the residual film ratio is lowered, and the pattern is swollen. There is a tendency that the occurrence of meandering can be suppressed, while a decrease in heat resistance as a resist can be suppressed by setting the content to 49% by mass or less.
  • the acid diffusion control agent (E) having an action of controlling the diffusion of the acid generated from the acid generator in the resist film by irradiation to prevent an unfavorable chemical reaction in the unexposed region and the like. May be blended into the resist composition.
  • an acid diffusion control agent (E) By using such an acid diffusion control agent (E), the storage stability of the resist composition is improved. In addition, the resolution is improved, and changes in the line width of the resist pattern due to fluctuations in the retention time before irradiation and the retention time after irradiation can be suppressed, resulting in extremely excellent process stability.
  • the acid diffusion control agent (E) is not particularly limited, and examples thereof include radiodegradable basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds.
  • the acid diffusion control agent (E) is not particularly limited, but for example, the one described in International Publication No. 2013/024778 can be used.
  • the acid diffusion control agent (E) may be used alone or in combination of two or more.
  • the storage stability of the resist composition is improved, the resolution is improved, and the retention time before irradiation and the retention time after irradiation fluctuate.
  • the change in line width of the resist pattern can be suppressed, and the process stability tends to be extremely excellent.
  • the low molecular weight dissolution accelerator enhances the solubility and appropriately increases the dissolution rate of the component (A) during development. It is a component having the above, and can be used as needed.
  • the dissolution accelerator include low molecular weight phenolic compounds, and examples thereof include bisphenols and tris (hydroxyphenyl) methane. These dissolution accelerators can be used alone or in combination of two or more.
  • the blending amount of the dissolution accelerator is appropriately adjusted according to the type of the component (A) to be used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0-1 by mass of the total weight of the solid component. Mass% is more preferable, and 0% by mass is particularly preferable.
  • the dissolution control agent is a component having an action of controlling the solubility of the component (A) of the present embodiment when the solubility in the developing solution is too high and appropriately reducing the dissolution rate during development.
  • a dissolution control agent one that does not chemically change in steps such as firing of the resist film, irradiation, and development is preferable.
  • the dissolution control agent is not particularly limited, and for example, aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthylketone; and methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Sulfones and the like can be mentioned. These dissolution control agents may be used alone or in combination of two or more.
  • the blending amount of the dissolution control agent is appropriately adjusted according to the type of the component (A) to be used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0-1 by mass of the total weight of the solid component. Mass% is more preferable, and 0% by mass is particularly preferable.
  • the sensitizer has the effect of absorbing the energy of the irradiated radiation and transferring that energy to the acid generator (C), thereby increasing the amount of acid produced, improving the apparent sensitivity of the resist. It is an ingredient to make.
  • a sensitizer include benzophenones, biacetyls, pyrenes, phenothiazines, fluorenes, and the like, but are not particularly limited. These sensitizers can be used alone or in combination of two or more.
  • the blending amount of the sensitizer is appropriately adjusted according to the type of the component (A) used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, and 0-1% by mass of the total weight of the solid component. % Is more preferable, and 0% by mass is particularly preferable.
  • the resist composition of the present embodiment contains an organic carboxylic acid or a phosphorus oxo acid or a derivative thereof as an optional component for the purpose of preventing sensitivity deterioration or improving the resist pattern shape, retention stability, and the like. Can be done.
  • the organic carboxylic acid or the oxo acid of phosphorus or a derivative thereof can be used in combination with an acid diffusion control agent, or may be used alone.
  • the organic carboxylic acid for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.
  • Examples of phosphorus oxo acids or derivatives thereof include phosphoric acids such as phosphoric acid, di-n-butyl ester of phosphoric acid, and diphenyl ester of phosphoric acid, or derivatives of their esters, phosphonic acid, dimethyl phosphonic acid ester, and di-phosphonic acid.
  • Examples include phosphonic acids such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester and phosphonic acid dibenzyl ester or derivatives such as their esters, phosphinic acid such as phosphinic acid and phenylphosphinic acid and derivatives such as their esters. Of these, phosphonic acid is particularly preferable.
  • the organic carboxylic acid or phosphorus oxo acid or its derivative can be used alone or in combination of two or more.
  • the blending amount of the organic carboxylic acid or the oxo acid of phosphorus or a derivative thereof is appropriately adjusted according to the type of the component (A) used, but is preferably 0 to 49% by mass, preferably 0 to 5% by mass, based on the total weight of the solid component. % Is more preferable, 0 to 1% by mass is further preferable, and 0% by mass is particularly preferable.
  • the resist composition of the present embodiment contains, if necessary, one or more additives other than the above-mentioned dissolution control agent, sensitizer, surfactant, and organic carboxylic acid or phosphorus oxo acid or a derivative thereof. Two or more types can be blended. Examples of such additives include dyes, pigments, adhesion aids and the like.
  • the other additive is not particularly limited, and examples thereof include an anti-halation agent, a storage stabilizer, an antifoaming agent, a shape improver, and specifically 4-hydroxy-4'-methylchalcone. Can be done.
  • the total amount of the optional component (F) is 0 to 99% by mass, preferably 0 to 49% by mass, more preferably 0 to 10% by mass, and 0, based on the total weight of the solid components. It is more preferably from 5% by mass, further preferably from 0 to 1% by mass, and particularly preferably from 0% by mass.
  • the content of the component (A) of the present embodiment is not particularly limited, but the total mass of the solid component (component (A), acid generator (C), acid cross-linking agent (G). ), Acid diffusion control agent (E) and other components (F) (also referred to as "arbitrary component (F)"), total of solid components including optionally used components, the same shall apply hereinafter) 50 to 99. It is preferably .4% by mass, more preferably 55 to 90% by mass, still more preferably 60 to 80% by mass, and particularly preferably 60 to 70% by mass. In the case of the above content, the resolution tends to be further improved and the line edge roughness (LER) tends to be further reduced. When both the compound and the resin of the present embodiment are contained, the above content is the total amount of the compound and the resin of the present embodiment.
  • the compound and / or resin of the present embodiment (component (A)), acid generator (C), acid cross-linking agent (G), acid diffusion control agent (E), optional component (
  • the content ratio of F) is 100% by mass of solid content of the resist composition. With respect to%, it is preferably 50 to 99.4% by mass / 0.001 to 49% by mass / 0.5 to 49% by mass / 0.001 to 49% by mass / 0 to 49% by mass, and more preferably.
  • the blending ratio of the components is selected from each range so that the total of the components is 100% by mass. With the above formulation, performance such as sensitivity, resolution, and developability tends to be further excellent.
  • the "solid content” means a component excluding the solvent, and the "solid content 100% by mass” means that the component excluding the solvent is 100% by mass.
  • the resist composition of the present embodiment is usually prepared by dissolving each component in a solvent at the time of use to obtain a uniform solution, and then, if necessary, filtering with a filter having a pore size of about 0.2 ⁇ m or the like. To.
  • the resist composition of the present embodiment may contain a resin other than the resin of the present embodiment, if necessary.
  • the other resin is not particularly limited, and for example, novolak resin, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and acrylic acid, vinyl alcohol, or vinylphenol as a monomer unit. Examples thereof include polymers containing the same or derivatives thereof.
  • the content of the resin is not particularly limited and is appropriately adjusted according to the type of the component (A) used, but is preferably 30 parts by mass or less, more preferably 30 parts by mass with respect to 100 parts by mass of the component (A). It is 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 0 parts by mass.
  • the resist composition of the present embodiment can form an amorphous film by spin coating. It can also be applied to general semiconductor manufacturing processes. Either a positive resist pattern or a negative resist pattern can be created depending on the type of developer used.
  • 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 5 ⁇ / sec or less, more preferably 0.05 to 5 ⁇ / sec. It is preferable, 0.0005 to 5 ⁇ / sec is more preferable. When the dissolution rate is 5 ⁇ / sec or less, it is insoluble in the developing solution and can be easily used as a resist. Further, when the dissolution rate is 0.0005 ⁇ / sec or more, the resolution tends to 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 ⁇ / sec or more, it is easily dissolved in a developing solution and is more suitable as a resist.
  • the dissolution rate is 10 ⁇ / sec or more, the resolution tends to be improved. It is presumed that this is because the micro surface portion of the component (A) is dissolved and the LER is reduced. In addition, the effect of reducing defects can be easily obtained.
  • the dissolution rate is determined by immersing the amorphous film in a developer for a predetermined time at 23 ° C. and measuring the film thickness before and after the immersion by a known method such as visual inspection, cross-sectional observation with an ellipsometer or a scanning electron microscope. it can.
  • the dissolution rate is preferably 10 ⁇ / sec or more. When the dissolution rate is 10 ⁇ / sec or more, it is easily dissolved in a developing solution and is more suitable as a resist. Further, when the dissolution rate is 10 ⁇ / sec or more, the resolution tends to be improved. It is presumed that this is because the micro surface portion of the component (A) is dissolved and the LER is reduced. In addition, the effect of reducing defects can be easily obtained.
  • the dissolution rate is preferably 5 ⁇ / sec or less, more preferably 0.05 to 5 ⁇ / sec, and even more preferably 0.0005 to 5 ⁇ / sec.
  • the dissolution rate is 5 ⁇ / sec or less, it is insoluble in the developing solution and can be easily used as a resist. Further, when the dissolution rate is 0.0005 ⁇ / sec or more, the resolution tends to be improved.
  • the radiation-sensitive composition of the present embodiment contains the component (A) of the present embodiment, the diazonaphthoquinone photoactive compound (B), and a solvent, and the content of the solvent is the radiation-sensitive composition. It is preferably 20 to 99% by mass with respect to 100% by mass of the total amount of the substance, and the content of the components other than the solvent is preferably 1 to 80% with respect to 100% by mass of the total amount of the radiation-sensitive composition. It is mass%.
  • the component (A) contained in the radiation-sensitive composition of the present embodiment is used in combination with the diazonaphthoquinone photoactive compound (B) described later, and g-ray, h-ray, i-ray, KrF excimer laser, ArF excimer laser, extreme. It is useful as a base material for positive resist, which becomes a compound easily soluble in a developing solution by irradiating with ultraviolet rays, electron beams, or X-rays.
  • a resist pattern can be formed by the developing step.
  • 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 obtained resist pattern is very small.
  • 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, still more preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. ..
  • the upper limit of the glass transition temperature of the component (A) is not particularly limited, but is, for example, 400 ° C. When the glass transition temperature of the component (A) is within the above range, it has heat resistance capable of maintaining the pattern shape in the semiconductor lithography process, and performance such as high resolution is improved.
  • the amount of calorific value for crystallization determined by differential scanning calorimetry 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.
  • (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.
  • the calorific value for crystallization is less than 20 J / g, or when (crystallization temperature)-(glass transition temperature) is within the above range, an amorphous film can be easily formed by spin coating the radiation-sensitive composition.
  • the film-forming property required for the resist can be maintained for a long period of time, and the resolution tends to be improved.
  • the crystallization calorific value, 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 the sample is placed in an aluminum unsealed container, and the temperature is raised to the melting point or higher at a heating rate of 20 ° C./min in a nitrogen gas stream (50 mL / min). After quenching, the temperature is raised to the melting point or higher again in a nitrogen gas stream (30 mL / min) at a heating rate of 20 ° C./min. After further quenching, the temperature is raised to 400 ° C.
  • the temperature at the midpoint of the stepped baseline step (where the specific heat changes in half) is the glass transition temperature (Tg), and the temperature of the exothermic peak that appears after that is the crystallization temperature.
  • Tg glass transition temperature
  • the calorific value is calculated from the area of the region surrounded by the exothermic peak and the baseline, and is used as the crystallization calorific value.
  • the component (A) contained in the radiation-sensitive composition of the present embodiment is 100 ° C. or lower, preferably 120 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 140 ° C. or lower, and particularly preferably 150 ° C. or lower under normal pressure. It is preferable that the sublimation property 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, still more preferably 1% or less, particularly preferably. Indicates 0.1% or less. Due to the low sublimation property, it is possible to prevent contamination of the exposure apparatus due to outgas during exposure. Further, there is a tendency that a good pattern shape can be obtained with low roughness.
  • the 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. , Anisol, butyl acetate, ethyl propionate and ethyl lactate, and in a solvent having the highest dissolving ability with respect to the component (A), at 23 ° C., preferably 1% by mass or more, more preferably 5% by mass.
  • % Or more more preferably 10% by mass or more, and even more preferably, in a solvent selected from PGMEA, PGME, CHN and showing the highest solubility in the component (A) at 23 ° C., 20 It dissolves in an amount of 20% by mass or more, particularly preferably in PGMEA 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, and is generally used in a positive resist composition.
  • a photosensitive component photosensitizer
  • Such a photosensitizer was obtained by reacting naphthoquinone diazide sulfonic acid chloride, benzoquinone diazido sulfonic acid chloride, or the like with a low molecular weight compound or a high molecular weight compound having a functional group capable of condensing with these acid chlorides.
  • Compounds are preferred.
  • the functional group capable of condensing with acid chloride is not particularly limited, and examples thereof include a hydroxyl group and an amino group, and a hydroxyl group is particularly preferable.
  • the compound capable of condensing with the acid chloride containing a hydroxyl group is not particularly limited, and for example, 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, hydroxyphenyl alkanes such as bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) propane , 4,4', 3 ", 4" -tetrahydroxy-3,5,3', 5'-tetramethyltriphenylmethane, 4,4', 2 ", 3", 4 "-pent
  • acid chloride such as naphthoquinone diazide sulfonic acid chloride and benzoquinone diazido sulfonic acid chloride
  • 1,2-naphthoquinone diazide-5-sulfonyl chloride, 1,2-naphthoquinone diazido-4-sulfonyl chloride and the like are preferable.
  • the radiation-sensitive composition of the present embodiment is prepared, for example, by dissolving each component in a solvent at the time of use to obtain a uniform solution, and then, if necessary, filtering with a filter having a pore size of about 0.2 ⁇ m or the like. It is preferable to be done.
  • the solvent that can be used in the radiation-sensitive composition of the present embodiment is not particularly limited, but for example, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, cyclopentanone, 2-heptanone, anisole, butyl acetate. , Ethyl propionate, and ethyl lactate.
  • propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone are preferable, and the solvent may be used alone or in combination of two or more.
  • the content of the solvent is 20 to 99% by mass, preferably 50 to 99% by mass, more preferably 60 to 98% by mass, particularly based on 100% by mass of the total amount of the radiation-sensitive composition. It is preferably 90 to 98% by mass.
  • the content of the component (solid component) other than the solvent is 1 to 80% by mass, preferably 1 to 50% by mass, more preferably 1 to 50% by mass, based on 100% by mass of the total amount of the radiation-sensitive composition. It is 2 to 40% by mass, and particularly preferably 2 to 10% by mass.
  • the radiation-sensitive composition of the present embodiment can form an amorphous film by spin coating. It can also be applied to general semiconductor manufacturing processes. Either a positive resist pattern or a negative resist pattern can be produced depending on the type of developer used.
  • the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment in a developing solution at 23 ° C. is preferably 5 ⁇ / sec or less, preferably 0.05 to 5 ⁇ / sec. Is more preferable, and 0.0005 to 5 ⁇ / sec is even more preferable.
  • the dissolution rate is 5 ⁇ / sec or less, it is insoluble in the developing solution and can be easily used as a resist. Further, when the dissolution rate is 0.0005 ⁇ / sec or more, the resolution tends to be improved.
  • the dissolution rate of the amorphous film formed by spin-coating the radiation-sensitive composition of the present embodiment in a developing solution at 23 ° C. is preferably 10 ⁇ / sec or more.
  • the dissolution rate is 10 ⁇ / sec or more, it is easily dissolved in a developing solution and is more suitable as a resist.
  • the dissolution rate is 10 ⁇ / sec or more, the resolution tends to be improved. It is presumed that this is because the micro surface portion of the component (A) is dissolved and the LER is reduced. In addition, the effect of reducing defects can be easily obtained.
  • the dissolution rate can be determined by immersing the amorphous film in a developing solution at 23 ° C. and measuring the film thickness before and after the immersion by a known method such as visual inspection, ellipsometer or QCM method.
  • the dissolution rate of the exposed portion after heating at 500 ° C. in the developing solution at 23 ° C. is preferably 10 ⁇ / sec or more, more preferably 10 to 10000 ⁇ / sec, still more preferably 100 to 1000 ⁇ / sec.
  • the dissolution rate is 10 ⁇ / sec or more, it is easily dissolved in a developing solution and is more suitable as a resist. Further, when the dissolution rate is 10,000 ⁇ / sec or less, the resolution tends to be improved.
  • the micro surface portion of the component (A) is dissolved and the LER is reduced.
  • the effect of reducing defects can be easily obtained.
  • the dissolution rate of the exposed portion after heating at 500 ° C. in the developing solution at 23 ° C. is preferably 5 ⁇ / sec or less, more preferably 0.05 to 5 ⁇ / sec, still more preferably 0.0005 to 5 ⁇ / sec. ..
  • the dissolution rate When the dissolution rate is 5 ⁇ / sec or less, it is insoluble in the developing solution and can be easily used as a resist. Further, when the dissolution rate is 0.0005 ⁇ / sec or more, the resolution tends to be improved. It is presumed that this is because the contrast between the unexposed portion dissolved in the developing solution and the exposed portion not dissolved in the developing solution increases due to the change in the solubility of the component (A) before and after exposure. In addition, the effects of reducing LER and reducing defects can be easily obtained.
  • the content of the component (A) is arbitrarily used such as the total weight of the solid component (component (A), diazonaphthoquinone photoactive compound (B) and other component (D)). It 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, based on the total amount of the solid components to be produced (the same applies hereinafter). %.
  • the content of the component (A) is within the above range, the radiation-sensitive composition of the present embodiment tends to be able to obtain a pattern having high sensitivity and small roughness.
  • the content of the diazonaphthoquinone photoactive compound (B) is the total weight of the solid component (component (A), diazonaphthoquinone photoactive compound (B) and other components (D), etc. It is preferably 1 to 99% by weight, more preferably 5 to 95% by weight, still more preferably 10 to 90% by weight, and particularly preferably 10 to 90% by weight, based on the total of the solid components arbitrarily used in the above. It is 25 to 75% by weight.
  • the content of the diazonaphthoquinone photoactive compound (B) in the radiation-sensitive composition of the present embodiment is within the above range, it tends to be possible to obtain a pattern having high sensitivity and small roughness.
  • [Other components (D)] In the radiation-sensitive composition of the present embodiment, if necessary, as components other than the component (A) and the diazonaphthoquinone photoactive compound (B), the above-mentioned acid generator, acid cross-linking agent, acid diffusion control agent, etc. One or two or more kinds of additives such as a dissolution accelerator, a dissolution control agent, a sensitizer, a surfactant, an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be added.
  • the other component (D) may be referred to as an optional component (D).
  • Content ratio of component (A), diazonaphthoquinone photoactive compound (B), and other optional component (D) that can be optionally contained in the radiation-sensitive composition is preferably 1 to 99% by mass / 99 to 1% by mass / 0 to 98% by mass, and more preferably 5 to 95% by mass with respect to 100% by mass of the solid content of the radiation-sensitive composition.
  • the blending ratio of each component is selected from each range so that the total sum is 100% by mass.
  • the radiation-sensitive composition of the present embodiment tends to be excellent in performance such as sensitivity and resolution in addition to roughness when the blending ratio of each component is within the above range.
  • the radiation-sensitive composition of the present embodiment may contain a resin other than the present embodiment.
  • resins include novolak resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resin, and polymers containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units, or polymers thereof. Examples include derivatives.
  • the blending amount of these resins is appropriately adjusted according to the type of the component (A) used, but is preferably 30 parts by mass or less, and more preferably 10 parts by mass or less with respect to 100 parts by mass of the component (A). , More preferably 5 parts by mass or less, and particularly preferably 0 parts by mass.
  • the method for producing an amorphous film of the present embodiment includes a step of forming an amorphous film on a substrate by using the above-mentioned radiation-sensitive composition.
  • the resist pattern forming method using the radiation-sensitive composition of the present embodiment includes a step of forming a resist film on a substrate using the radiation-sensitive composition and at least a part of the formed resist film. It includes a step of exposing and a step of developing the exposed resist film to form a resist pattern. In detail, the same operation as the following resist pattern forming method using the resist composition can be performed.
  • the method for forming a resist pattern using the resist composition of the present embodiment includes a step of forming a resist film on a substrate using the resist composition of the present embodiment described above, and at least a part of the formed resist film. It includes a step of exposing and a step of developing the exposed resist film to form a resist pattern.
  • the resist pattern in this embodiment can also be formed as an upper resist in a multilayer process. Further, the resist pattern forming method of the present embodiment can also be applied as a resist permanent film forming method described later.
  • the method for forming the resist pattern is not particularly limited, and examples thereof include the following methods.
  • a resist film is formed by applying the resist composition of the present embodiment on a conventionally known substrate by coating means such as rotary coating, casting coating, and roll coating.
  • 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, although not particularly limited, examples thereof include a silicon wafer, a metal substrate such as copper, chromium, iron, and aluminum, and a glass substrate.
  • the material of the wiring pattern is not particularly limited, and examples thereof include copper, aluminum, nickel, and gold. Further, if necessary, an inorganic and / or organic film may be provided on the above-mentioned substrate.
  • the inorganic film is not particularly limited, and examples thereof include an inorganic antireflection film (inorganic BARC).
  • the organic film is not particularly limited, and examples thereof include an organic antireflection film (organic BARC). Surface treatment with hexamethylene disilazane or the like may be performed.
  • the heating conditions vary depending on the composition of the resist composition and the like, but are preferably 20 to 250 ° C, more preferably 20 to 150 ° C. By heating, the adhesion of the resist to the substrate may be improved, which is preferable.
  • the resist film is then exposed to a desired pattern with any radiation selected from the group consisting of visible light, ultraviolet light, excimer lasers, electron beams, extreme ultraviolet light (EUV), X-rays, and ion beams.
  • the exposure conditions and the like are appropriately selected according to the compounding composition of the resist composition and the like. In the present embodiment, it is preferable to heat after irradiation in order to stably form a fine pattern with high accuracy in exposure.
  • a predetermined resist pattern is formed by developing the exposed resist film with a developing solution.
  • a solvent having a solubility parameter (SP value) close to that of the component (A) it is preferable to select a solvent having a solubility parameter (SP value) close to that of the component (A) to be used.
  • SP value solubility parameter
  • a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, a hydrocarbon solvent or an alkaline aqueous solution described in International Publication No. 2013/024778 can be used. ..
  • a plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water as long as the solvent has performance.
  • 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. It is more preferably present, more preferably less than 10% by mass, and particularly preferably substantially free of water. That is, the content of the organic solvent in the developing solution is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, based on the total amount of the developing solution. It is more preferably mass% or more and 100 mass% or less, further preferably 90 mass% or more and 100 mass% or less, and particularly preferably 95 mass% or more and 100 mass% or less.
  • a developing solution containing at least one solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent is used for the resolution and roughness of the resist pattern. It is preferable because it improves the resist performance such as.
  • the surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and / or silicon-based surfactant can be used.
  • fluorine and / or silicon-based surfactants include Japanese Patent Application Laid-Open No. 62-36663, Japanese Patent Application Laid-Open No. 61-226746, Japanese Patent Application Laid-Open No. 61-226745, and Japanese Patent Application Laid-Open No. 62-170950. , JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat.
  • the surfactants described in the same 5360692, 5529881, 5296330, 5436598, 5576143, 5294511, and 5824451 can be mentioned. It is possible, preferably a nonionic surfactant.
  • the nonionic surfactant is not particularly limited, but it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.
  • 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 developing solution.
  • the developing method is not particularly limited, but for example, a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), or a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time.
  • Development method (paddle method), method of spraying developer on the surface of the substrate (spray method), continuous application of developer on the substrate rotating at a constant speed while scanning the developer application nozzle at a constant speed.
  • a method (dynamic dispense method) or the like can be applied.
  • the time for developing the pattern is not particularly limited, but is preferably 10 seconds to 90 seconds.
  • a step of stopping the development may be carried out while substituting with another solvent.
  • the rinsing solution 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 containing a general organic solvent or water can be used.
  • a rinsing solution it is preferable to use a rinsing solution containing at least one organic solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent and an ether solvent. .. More preferably, after the development, a step of washing with a rinsing solution containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent and an amide solvent is performed.
  • a step of washing with a rinsing solution containing an alcohol solvent or an ester solvent is performed. Even more preferably, after development, a step of washing with a rinse solution containing a monohydric alcohol is performed. Particularly preferably, after the development, a step of washing with a rinsing solution containing a monohydric alcohol having 5 or more carbon atoms is performed.
  • the time for rinsing the pattern is not particularly limited, but is preferably 10 to 90 seconds.
  • examples of the monohydric alcohol used in the rinsing step after development include linear, branched, and cyclic monohydric alcohols, and are not particularly limited, but are described in, for example, International Publication No. 2013/024778. Things can be used.
  • a particularly preferable monohydric alcohol having 5 or more carbon atoms 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and the like can be used.
  • Each of the above components may be mixed in a plurality or mixed with an organic solvent other than the above.
  • the water content in the rinse solution is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics tend to be obtained.
  • An appropriate amount of surfactant can be added to the rinse solution before use.
  • the developed wafer is cleaned with a rinsing solution containing the above organic solvent.
  • the cleaning treatment method is not particularly limited, but for example, a method of continuously coating the rinse liquid on a substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time.
  • a method (dip method), a method of spraying a rinse solution on the surface of the substrate (spray method), etc. can be applied.
  • the cleaning treatment is performed by the rotary coating method, and after cleaning, the substrate is rotated at a rotation speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.
  • a pattern wiring board can be obtained by etching after forming a resist pattern.
  • the etching method can be a known method such as dry etching using plasma gas and wet etching with an alkaline solution, a cupric chloride solution, a ferric chloride solution or the like.
  • plating can also be performed.
  • the plating method include copper plating, solder plating, nickel plating, gold plating and the like.
  • the residual resist pattern after etching can be peeled off with an organic solvent.
  • the organic solvent is not particularly limited, and examples thereof include PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), and EL (ethyl lactate).
  • the peeling method is not particularly limited, and examples thereof 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 obtained in the present embodiment can also be formed by a method of forming a resist pattern, depositing a metal in a vacuum, and then dissolving the resist pattern with a solution, that is, a lift-off method.
  • a method of forming a resist pattern depositing a metal in a vacuum, and then dissolving the resist pattern with a solution, that is, a lift-off method.
  • the underlayer film forming composition for lithography in the present embodiment may contain a solvent.
  • the solvent is not particularly limited as long as it is a solvent that can dissolve the compound or resin of the present embodiment.
  • the compound or resin of the present embodiment has excellent solubility in an organic solvent, and therefore various organic solvents are preferably used.
  • the solvent is not particularly limited, and examples thereof include those described in International Publication No. 2013/024779. These solvents may be used alone or in combination of two or more.
  • one or more selected from the group consisting of cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate, and anisole is preferable.
  • the underlayer film forming composition for lithography of the present embodiment may contain a cross-linking agent from the viewpoint of suppressing intermixing and the like.
  • the cross-linking agent is not particularly limited, and for example, those described in International Publication No. 2013/024779 and International Publication No. 2018/016614 can be used.
  • the cross-linking agent is not particularly limited, and for example, a phenol compound, an epoxy compound, a cyanate compound, an amino compound, a benzoxazine compound, an acrylate compound, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, an isocyanate compound, an azide compound and the like. Can be mentioned.
  • These cross-linking agents may be used alone or in combination of two or more. Among these, one or more selected from the group consisting of benzoxazine compounds, epoxy compounds and cyanate compounds is preferable, and benzoxazine compounds are more preferable from the viewpoint of improving etching resistance.
  • a cross-linking agent having at least one allyl group may be used from the viewpoint of improving the cross-linking property.
  • the cross-linking agent having at least one allyl group is not particularly limited, and examples thereof include those described in International Publication No. 2018/016614. These cross-linking agents may be used alone or in combination of two or more.
  • Allylphenols such as propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide, and bis (3-allyl-4-hydroxyphenyl) ether. Is preferable.
  • the content of the cross-linking agent is not particularly limited, but is preferably 0.1 to 100 parts by mass and 5 to 50 parts by mass with respect to 100 parts by mass of the film forming material for lithography. Is more preferable, and more preferably 10 to 40 parts by mass.
  • the content of the cross-linking agent is within the above range, the occurrence of the mixing phenomenon with the resist layer tends to be suppressed, the antireflection effect is enhanced, and the film-forming property after cross-linking tends to be enhanced. is there.
  • the underlayer film forming composition for lithography of the present embodiment may contain a cross-linking accelerator in order to promote a cross-linking reaction (curing reaction), if necessary.
  • a cross-linking accelerator include a radical polymerization initiator.
  • the radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization by light, or a thermal polymerization initiator that initiates radical polymerization by heat.
  • the radical polymerization initiator include at least one selected from the group consisting of a ketone-based photopolymerization initiator, an organic peroxide-based polymerization initiator, and an azo-based polymerization initiator.
  • the radical polymerization initiator is not particularly limited, and examples thereof include those described in International Publication No. 2018/016614.
  • radical polymerization initiators are used alone or in combination of two or more.
  • the underlayer film forming composition for lithography of the present embodiment may contain an acid generator from the viewpoint of further promoting the cross-linking reaction by heat.
  • an acid generator those that generate acid by thermal decomposition, those that generate acid by light irradiation, and the like are known, and any of them can be used.
  • the acid generator for example, those described in International Publication No. 2013/024779 can be used.
  • the content of the acid generator in the film forming composition for lithography is not particularly limited, but is preferably 0.1 to 50 parts by mass, more preferably 0, with respect to 100 parts by mass of the film forming material for lithography. .5 to 40 parts by mass.
  • the content of the acid generator is within the above range, the cross-linking reaction tends to be enhanced, and the occurrence of the mixing phenomenon with the resist layer tends to be suppressed.
  • the underlayer film forming composition for lithography of the present embodiment may contain a basic compound from the viewpoint of improving storage stability and the like.
  • the basic compound plays a role of preventing the acid generated in a small amount from the acid generator from advancing the cross-linking reaction, that is, a role of quenching against the acid.
  • Such basic compounds are not particularly limited, and examples thereof include those described in International Publication No. 2013/024779.
  • the content of the basic compound in the underlayer film forming composition for lithography of the present embodiment is not particularly limited, but is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the film forming material for lithography. , More preferably 0.01 to 1 part by mass.
  • the content of the basic compound is within the above range, the storage stability tends to be enhanced without excessively impairing the cross-linking reaction.
  • the underlayer film forming composition for lithography of 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 are not particularly limited, and for example, naphthol resin, xylene resin, naphthalene-modified resin, phenol-modified resin of naphthalene resin; polyhydroxystyrene, dicyclopentadiene resin, (meth) acrylate, and the like.
  • Non-resin examples thereof include resins or compounds containing an alicyclic structure such as rosin-based resins, cyclodextrines, adamantane (poly) all, tricyclodecane (poly) all and derivatives thereof.
  • the underlayer film forming composition for lithography of the present embodiment may contain a known additive.
  • additives include, but are not limited to, heat and / or photocurable catalysts, polymerization inhibitors, flame retardants, fillers, coupling agents, thermosetting resins, photocurable resins, dyes, pigments. , Thickeners, lubricants, defoaming agents, leveling agents, ultraviolet absorbers, surfactants, colorants, nonionic surfactants and the like.
  • the underlayer film for lithography of the present embodiment is formed from the film-forming composition for lithography of the present embodiment.
  • the forming method is not particularly limited, and a known method can be applied.
  • the film-forming composition for lithography of the present embodiment is applied onto a substrate by a known coating method such as spin coating or screen printing, a printing method, or the like, and then removed by volatilizing an organic solvent to remove the lower layer.
  • a film can be formed.
  • the baking temperature is not particularly limited, but is preferably in the range of 80 to 450 ° C, and more preferably 200 to 400 ° C.
  • the baking time is also not particularly limited, but is preferably in the range of 10 to 300 seconds.
  • the thickness of the underlayer film can be appropriately selected according to the required performance, and is not particularly limited, but is preferably 30 to 20,000 nm, more preferably 50 to 15,000 nm.
  • the lower layer film After preparing the lower layer film, in the case of a two-layer process, it is preferable to prepare a silicon-containing resist layer or a single-layer resist composed of hydrocarbons on the lower layer film, and in the case of a three-layer process, it is preferably on the lower layer film. It is preferable to prepare a silicon-containing intermediate layer and further prepare a silicon-free single-layer resist layer on the silicon-containing intermediate layer. In this case, a known photoresist material can be used to form the resist layer.
  • a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative is used as the base polymer from the viewpoint of oxygen gas etching resistance, and further, an organic solvent, an acid generator, and the like. If necessary, a positive photoresist material containing a basic compound or the like is preferably used.
  • the silicon atom-containing polymer a known polymer used in this type of resist material can be used.
  • a polysilsesquioxane-based intermediate layer is preferably used as the silicon-containing intermediate layer for the three-layer process.
  • the intermediate layer By giving the intermediate layer an effect as an antireflection film, reflection tends to be effectively suppressed.
  • the k value tends to be high and the substrate reflection tends to be high, but the reflection is suppressed by 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 polysilseski cross-linked with an acid or heat into which a phenyl group or an absorption group having a silicon-silicon bond is introduced. Oxane is preferably used.
  • an intermediate layer formed by the Chemical Vapor Deposition (CVD) method It is also possible to use an intermediate layer formed by the Chemical Vapor Deposition (CVD) method.
  • the intermediate layer produced by the CVD method and having a high effect as an antireflection film is not limited to the following, and 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 the present 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 underlayer film has excellent etching resistance for base processing, it can be expected to function as a hard mask for base processing.
  • a wet process such as a spin coating method or screen printing is preferably used as in the case of forming the underlayer film.
  • prebaking is usually performed, and 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 developing according to a conventional method.
  • 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 used.
  • high-energy rays having a wavelength of 300 nm or less specifically, excimer lasers having a wavelength of 248 nm, 193 nm, and 157 nm, soft X-rays having a wavelength of 3 to 20 nm, electron beams, X-rays, and the like can be mentioned.
  • the resist pattern formed by the above-mentioned method has the pattern collapse suppressed by the underlayer film. Therefore, by using the lower layer film in the present embodiment, a finer pattern can be obtained, and the exposure amount required to obtain the resist pattern can be reduced.
  • gas etching is preferably used as the etching of the underlayer film in the two-layer process.
  • gas etching etching using oxygen gas is preferable.
  • oxygen gas it is also possible to add an inert gas such as He or Ar, or CO, CO 2 , NH 3 , SO 2 , N 2 , NO 2 , or H 2 gas.
  • inert gas such as He or Ar, or CO, CO 2 , NH 3 , SO 2 , N 2 , NO 2 , or H 2 gas.
  • the latter gas is preferably used for side wall protection to prevent undercutting of the pattern side wall.
  • gas etching is also preferably used for etching the intermediate layer in the three-layer process.
  • 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 by using a chlorofluorocarbon-based gas and masking the resist pattern.
  • the lower layer film can be processed by performing, for example, oxygen gas etching using the intermediate layer pattern as a mask as described above.
  • a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film are formed by a CVD method, an ALD method, or the like.
  • the method for forming the nitride film is not limited to the following, and for example, the method described in JP-A-2002-334869 and WO2004 / 0666377 can be used.
  • a photoresist film can be formed directly on such an intermediate layer film, but an organic antireflection film (BARC) is formed on the intermediate layer film by spin coating, and a photoresist film is formed on the organic antireflection film (BARC). You may.
  • a polysilsesquioxane-based intermediate layer is also preferably used.
  • the resist intermediate layer film By giving the resist intermediate layer film an effect as an antireflection film, reflection tends to be effectively suppressed.
  • the specific material of the polysilsesquioxane-based intermediate layer is not limited to the following, and for example, those described in JP-A-2007-226170 and JP-A-2007-226204 can be used.
  • the next etching of the substrate can also be performed by a conventional method.
  • the etching is mainly composed of chlorofluorocarbons
  • the substrate is p—Si, Al, or W, chlorine or bromine is used.
  • Etching mainly composed of gas can be performed.
  • the silicon-containing resist layer or the silicon-containing intermediate layer is separately peeled off, and generally, dry etching peeling with a chlorofluorocarbon-based gas is performed after the substrate is processed. ..
  • the underlayer film in the present embodiment has a feature of being excellent in etching resistance of the substrate.
  • a known substrate can be appropriately selected and used, and the substrate is not particularly limited, and examples thereof include Si, ⁇ -Si, p-Si, SiO 2 , SiN, SiON, W, TiN, and Al. Be done.
  • the substrate may be a laminate having a film to be processed (substrate to be processed) on a base material (support).
  • various Low-k films such as Si, SiO 2 , SiON, SiN, p-Si, ⁇ -Si, W, W-Si, Al, Cu, Al-Si and the like and their stoppers are used.
  • Examples include a film, and usually a material different from the base material (support) is used.
  • the thickness of the substrate or the film to be processed is not particularly limited, but is usually preferably about 50 to 1,000,000 nm, and more preferably 75 to 50,000 nm.
  • the resist pattern forming method of the present embodiment includes a lower layer film forming step of forming a lower layer film using the composition of the present embodiment on a substrate and at least one layer on the lower layer film formed by the lower layer film forming step. It includes a photoresist layer forming step of forming a photoresist layer and a step of irradiating a predetermined region of the photoresist layer formed by the photoresist layer forming step with radiation to develop the photoresist layer.
  • the resist pattern forming method of the present embodiment can be used for forming various patterns, and is preferably an insulating film pattern forming method.
  • circuit pattern formation method In the circuit pattern forming method of the present embodiment, an intermediate layer film is formed on a substrate by a lower layer film forming step of forming a lower layer film using the composition of the present embodiment and an intermediate layer film formed by the lower layer film forming step.
  • the intermediate layer film pattern forming step the lower layer film pattern forming step of etching the lower layer film using the intermediate layer film pattern formed by the intermediate layer film pattern forming step as a mask, and the lower layer film pattern forming step of forming the lower layer film pattern.
  • the resist permanent film of the present embodiment contains the composition of the present embodiment.
  • the resist permanent film formed by applying the composition of the present embodiment is suitable as a permanent film that remains in the final product after forming a resist pattern, if necessary.
  • Specific examples of permanent films include package adhesive layers such as solder resists, package materials, underfill materials, and circuit elements for semiconductor device cans, adhesive layers for integrated circuit elements and circuit boards, and thin film transistor protection for thin displays. Examples include a film, a liquid crystal color filter protective film, a black matrix, and a spacer.
  • the resist permanent film containing the composition of the present embodiment has an extremely excellent advantage that it is excellent in heat resistance and moisture resistance and is less contaminated by sublimation components. Especially in the display material, it is a material having high sensitivity, high heat resistance, and moisture absorption reliability with little deterioration of image quality due to important contamination.
  • composition of the present embodiment is used for a permanent resist film
  • various additions such as a curing agent and other resins, surfactants and dyes, fillers, cross-linking agents, dissolution accelerators and the like are added as necessary.
  • a composition for a permanent resist film can be obtained by adding an agent and dissolving it in an organic solvent.
  • composition of the present embodiment can be adjusted by blending each of the above components and mixing them using a stirrer or the like.
  • a disperser such as a dissolver, a homogenizer, or a three-roll mill.
  • the method for purifying a compound or resin of the present embodiment includes an extraction step of bringing the compound or resin of the present embodiment into contact with an acidic aqueous solution and extracting the solution containing an organic solvent that is not optionally mixed with water. More specifically, in the purification method of the present embodiment, the compound or resin of the present embodiment and the organic solvent are subjected to extraction treatment by dissolving the solution in an organic solvent that is not arbitrarily mixed with water and contacting the solution with an acidic aqueous solution. After the metal content contained in the solution (A) containing the above is transferred to the aqueous phase, the organic phase and the aqueous phase are separated and purified.
  • the purification method of the present embodiment can significantly reduce the content of various metals in the compound or resin of the present embodiment.
  • the "organic solvent immiscible with water” means that the solubility in water at 20 to 90 ° C. is less than 50% by mass, and from the viewpoint of productivity, it is less than 25% by mass. Is preferable.
  • the organic solvent that is not arbitrarily miscible with water is not particularly limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferable.
  • the amount of the organic solvent used is usually about 1 to 100 times by weight with respect to the compound or resin of the present embodiment.
  • solvent used examples include those described in International Publication WO2015 / 080240. These solvents may be used alone or in combination of two or more. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, and cyclohexanone and propylene glycol monomethyl ether acetate are particularly preferable.
  • the acidic aqueous solution to be used is appropriately selected from a generally known aqueous solution in which an organic or inorganic compound is dissolved in water.
  • aqueous solutions may be used alone or in combination of two or more.
  • aqueous solutions of sulfuric acid, nitric acid, and carboxylic acids such as acetic acid, tartaric acid, tartaric acid, and citric acid are preferable, and aqueous solutions of sulfuric acid, oxalic acid, tartaric acid, and citric acid are preferable, and an aqueous solution of citric acid is particularly preferable.
  • polyvalent carboxylic acids such as oxalic acid, tartaric acid, and citric acid can remove more metals because they coordinate with metal ions and produce a chelating effect.
  • water having a low metal content for example, ion-exchanged water or the like is preferably used according to the object of the present invention.
  • the pH of the acidic aqueous solution used in the present embodiment is not particularly limited, but if the acidity of the aqueous solution becomes too large, the compound of the present embodiment or the resin obtained by using the compound as a monomer may be adversely affected, which is not preferable.
  • the pH range is about 0 to 5, and more preferably about pH 0 to 3.
  • the amount of the acidic aqueous solution used in the present embodiment is not particularly limited, but if the amount is too small, it is necessary to increase the number of extractions for removing the metal, and conversely, if the amount of the aqueous solution is too large, the whole liquid is used. The amount may increase and cause operational problems.
  • the amount of the aqueous solution used is usually 10 to 200% by mass, preferably 20 to 100% by mass, based on the solution of the compound or resin of the present embodiment dissolved in an organic solvent.
  • the metal component is extracted by contacting the above-mentioned acidic aqueous solution with the solution (A) containing the compound or resin of the present embodiment and an organic solvent that is arbitrarily immiscible with water.
  • the temperature at which the extraction process is performed is usually 20 to 90 ° C, preferably 30 to 80 ° C.
  • the extraction operation is performed by, for example, stirring well and then allowing the mixture to stand.
  • the metal component contained in the solution containing the compound or resin of the present embodiment and the organic solvent is transferred to the aqueous phase. Further, by this operation, the acidity of the solution is lowered, and the alteration of the compound or resin of the present embodiment can be suppressed.
  • the solution containing the compound or resin of the present embodiment and an organic solvent is recovered by decantation or the like.
  • the standing time is not particularly limited, but if the standing time is too short, the separation between the solution phase containing the organic solvent and the aqueous phase becomes poor, which is not preferable.
  • the standing time is 1 minute or more, more preferably 10 minutes or more, and further preferably 30 minutes or more.
  • the extraction process may be performed only once, it is also effective to repeat the operations of mixing, standing, and separating a plurality of times.
  • the solution (A) containing the compound or resin of the present embodiment and an organic solvent extracted and recovered from the aqueous solution after the treatment is Further, it is preferable to carry out an extraction treatment with water.
  • the extraction operation is performed by mixing well by stirring or the like and then allowing the mixture to stand. Then, since the obtained solution is separated into a solution phase containing the compound or resin of the present embodiment and an organic solvent and an aqueous phase, the solution phase containing the compound or resin of the present embodiment and an organic solvent is recovered by decantation or the like.
  • the water used here is preferably water having a low metal content, for example, ion-exchanged water, for the purpose of the present invention.
  • the extraction process may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times. Further, the conditions such as the ratio of use of both in the extraction treatment, temperature, and time are not particularly limited, but the same as in the case of the contact treatment with the acidic aqueous solution may be used.
  • the water mixed in the solution containing the compound or resin of the present embodiment thus obtained and the organic solvent can be easily removed by performing an operation such as vacuum distillation. Further, if necessary, an organic solvent can be added to adjust the concentration of the compound or resin of the present embodiment to an arbitrary concentration.
  • the method for obtaining only the compound or resin of the present embodiment from the obtained solution containing the compound or resin of the present embodiment and an organic solvent shall be carried out by a known method such as removal under reduced pressure, separation by reprecipitation, and a combination thereof. Can be done. If necessary, known treatments such as concentration operation, filtration operation, centrifugation operation, and drying operation can be performed.
  • the obtained crude compound was purified by column chromatography to obtain 0.9 g of a (poly) amino compound (BiA-27) represented by the following formula (BiA-27).
  • the molecular weight of the obtained compound (BiA-27) was measured and found to be 364. Further, when 1 H-NMR measurement of the obtained compound (BiA-27) was performed, the following peaks were found, and it was confirmed that the compound (BiA-27) had a chemical structure of the following formula (BiA-27).
  • Synthesis Example 1-1 Synthesis of CBiA-1
  • the crude compound obtained in Synthesis Example 1 was not isolated as it was, but was dried in a vacuum dryer to obtain a compound represented by the above formula (BiA-1). 3.0 g of the reaction product (CBiA-1) as a main component was obtained.
  • ethylbenzene (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added to the reaction solution as a diluting solvent, and after standing, the aqueous phase of the lower phase was removed. Further, the mixture was neutralized and washed with water, 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.
  • 100 g (0.51 mol) of dimethylnaphthalene formaldehyde resin obtained as described above and 0.05 g of p-toluenesulfonic acid were charged under a nitrogen stream, and the temperature was raised to 190 ° C. 2 After heating for hours, it was stirred. After that, 52.0 g (0.36 mol) of 1-naphthol was further added, the temperature was further raised to 220 ° C., and the reaction was carried out for 2 hours.
  • the obtained resin (CR-1) was Mn: 885, Mw: 2220, and Mw / Mn: 4.17.
  • the carbon concentration of the obtained resin (CR-1) was 89.1% by mass, and the oxygen concentration was 4.5% by mass.
  • the Mn, Mw and Mw / Mn of the resin (CR-1) were determined by gel permeation chromatography (GPC) analysis in terms of polystyrene under the following measurement conditions.
  • GPC gel permeation chromatography
  • Acid generator Midori Kagaku Co., Ltd. product "Jitter Charlie Butyl Diphenyliodonium Nonafluoromethane Sulfonate” (described as “DTDPI” in the table)
  • Cross-linking agent Nippon Kayaku Co., Ltd. product "Epoxy resin NC-3000 (described as” NC3000 “in the table)
  • Organic solvent "Propylene glycol monomethyl ether acetate (described as” PGMEA “in the table)” manufactured by Kanto Chemical Co., Inc., “Cyclohexanone (described as” CHN “in the table)” manufactured by Kanto Chemical Co., Inc.
  • the etching test was performed on the underlayer film containing the phenol novolac resin, and the etching rate (etching rate) at that time was measured.
  • the etching test was performed on the lower film of each Example and Comparative Example, and the etching rate at that time was measured.
  • the etching resistance of each Example and Comparative Example was evaluated according to the following evaluation criteria.
  • Evaluation A Etching rate is less than -10% compared to the lower layer film of Novolac Evaluation B: Etching rate is -10% to + 5% compared to the lower layer film of Novolac Evaluation C: Etching rate is over + 5% compared to the underlayer film of Novolac
  • Examples 37-1 to 44-2, Examples 1B-1 and 1B-2 Each solution of the underlayer film forming material for lithography prepared in each of the above examples was applied onto a SiO 2 substrate having a film thickness of 300 nm, and baked at 240 ° C. for 60 seconds and then at 400 ° C. for 120 seconds to obtain a film thickness. A 70 nm underlayer film was formed. A resist solution for ArF was applied onto the underlayer film and baked at 130 ° C. for 60 seconds to form a photoresist layer having a film thickness of 140 nm.
  • a compound represented by the following formula (11) 5 parts by mass, triphenylsulfonium nonafluoromethanesulfonate: 1 part by mass, tributylamine: 2 parts by mass, and PGMEA: 92 parts by mass.
  • the one prepared by blending was used.
  • the compounds represented by the following formula (11) are 2-methyl-2-methacryloyloxyadamantane 4.15 g, methacrylloyloxy- ⁇ -butyrolactone 3.00 g, 3-hydroxy-1-adamantyl methacrylate 2.08 g, and azobis.
  • the photoresist layer was exposed using an electron beam drawing apparatus (ELS-7500, 50 keV) and baked (PEB) at 115 ° C. for 90 seconds to obtain 2.38 mass% tetramethylammonium hydroxide (2.38 mass% tetramethylammonium hydroxide).
  • ELS-7500 electron beam drawing apparatus
  • PEB baked
  • a positive resist pattern was obtained by developing with an aqueous solution of TMAH) for 60 seconds.
  • Table 5 shows the results of observing the defects of the obtained resist patterns of 55 nm L / S (1: 1) and 80 nm L / S (1: 1).
  • "good” means that no large defects were found in the formed resist pattern
  • “poor” means that no large defects were found in the formed resist pattern.
  • a rectangular shape with a good resist pattern shape is formed, and the minimum line width (the finest pattern) with no defects is measured by a scanning electron microscope (S-4800 manufactured by Hitachi High-Technology Co., Ltd.). Shows the measured value.
  • the sensitivity the exposure intensity when the minimum line width is given is shown, and the smaller the exposure intensity, the higher the sensitivity.
  • Examples 37-1 to 44-2 and Examples 1B-1 and 1B-2 using either the compound or the resin of the present embodiment the resist pattern shape after development It was confirmed that the results were good and no major defects were observed. Furthermore, each of Examples 37-1 to 44-2, Examples 1B-1 and 1B-2 are significantly in terms of both resolution and sensitivity as compared with Comparative Example 2 in which the underlayer film is not formed. It was confirmed to be excellent.
  • the fact that the resist pattern shape after development is good means that the underlayer film forming material for lithography used in Examples 37-1 to 44-2 and Examples 1B-1 and 1B-2 is a resist material (photolithography). It shows that the adhesion with resist material etc.) is good.
  • Example 45-1 to 52-2 A solution of the underlayer film forming material for lithography of each example was applied onto a SiO 2 substrate having a film thickness of 300 nm, and baked at 240 ° C. for 60 seconds and then at 400 ° C. for 120 seconds to obtain an underlayer film having a film thickness of 80 nm. Formed. A silicon-containing intermediate layer material was applied onto the lower layer film and baked at 200 ° C. for 60 seconds to form an intermediate layer film having a film thickness of 35 nm. Further, the above resist solution for ArF was applied onto the intermediate layer film and baked at 130 ° C. for 60 seconds to form a photoresist layer having a film thickness of 150 nm.
  • the silicon-containing intermediate layer material As the silicon-containing intermediate layer material, the silicon atom-containing polymer described in ⁇ Synthesis Example 1> of JP-A-2007-226170 was used. Next, the photoresist layer was mask-exposed using an electron beam drawing apparatus (ELS-7500, 50 keV), baked (PEB) at 115 ° C. for 90 seconds, and 2.38 mass% tetramethylammonium hydroxide was used. By developing with an aqueous solution of (TMAH) for 60 seconds, a positive resist pattern of 55 nm L / S (1: 1) was obtained.
  • ELS-7500 electron beam drawing apparatus
  • PEB baked
  • TMAH aqueous solution of
  • the silicon-containing intermediate layer film (SOG) is dry-etched using the obtained resist pattern as a mask, and then the obtained silicon-containing intermediate layer film pattern is obtained.
  • the dry etching process of the lower layer film used as a mask and the dry etching process of the SiO 2 film using the obtained lower layer film pattern as a mask were sequentially performed.
  • the pattern cross section (that is, the shape of the SiO 2 film after etching) obtained as described above was observed using an "electron microscope (S-4800)" manufactured by Hitachi, Ltd. The observation results are shown in Table 6. In the table, “good” means that no large defect was found in the formed pattern cross section, and “poor” means that no large defect was found in the formed pattern cross section.
  • Example 53 to 60 An optical component forming composition solution having the same composition as the solution of the underlayer film forming material for lithography prepared in each of the above examples is applied onto a SiO 2 substrate having a film thickness of 300 nm and baked at 260 ° C. for 300 seconds. An optical component forming film having a thickness of 100 nm was formed. Next, a refractive index and transparency test at a wavelength of 633 nm were performed using a vacuum ultraviolet multi-incident angle spectroscopic ellipsometer (VUV-VASE) manufactured by JA Woolam Japan, and the refractive index and transparency were tested according to the following criteria. Gender was evaluated. The evaluation results are shown in Table 7.
  • VUV-VASE vacuum ultraviolet multi-incident angle spectroscopic ellipsometer
  • a resist composition was prepared according to the formulation shown in Table 8. Among the components of the resist composition in Table 8, the following were used as the acid generator (C), the acid diffusion control agent (E), and the solvent.
  • Acid generator (C) P-1 Triphenylbenzene sulfonium Trifluoromethanesulfonate (Midori Chemical Co., Ltd.)
  • Acid diffusion control agent (E) Q-1 Trioctylamine (Tokyo Chemical Industry Co., Ltd.)
  • Solvent S-1 Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)
  • a uniform resist composition was spin-coated on a clean silicon wafer and then pre-exposed baked (PB) in an oven at 110 ° C. to form a resist film with a thickness of 60 nm.
  • the obtained resist film was irradiated with an electron beam having a 1: 1 line and space setting at 50 nm intervals using an electron beam drawing apparatus (ELS-7500, manufactured by Elionix Inc.). After the irradiation, each resist film was heated at a predetermined temperature for 90 seconds and immersed in a TMAH 2.38 mass% alkaline developer for 60 seconds for development. Then, the resist film was washed with ultrapure water for 30 seconds and dried to form a positive resist pattern.
  • ELS-7500 electron beam drawing apparatus
  • the line and space of the formed resist pattern was observed with a scanning electron microscope (S-4800 manufactured by Hitachi High-Technology Co., Ltd.), and the reactivity of the resist composition by electron beam irradiation was evaluated.
  • S-4800 manufactured by Hitachi High-Technology Co., Ltd.
  • the compound or resin satisfying the requirements of the present invention has higher heat resistance than the comparative compound (CR-1) and can impart a good resist pattern shape. As long as the above-mentioned requirements of the present invention are satisfied, the same effect is exhibited with respect to the resins other than those described in the examples.
  • the following resist base material was used as the resist base material in Comparative Example 4.
  • B-1 Naftquinone diazide-based photosensitizer of the following chemical structural formula (G) (4NT-300, Toyo Gosei Co., Ltd.) The following solvents were used.
  • S-1 Propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.)
  • the radiation-sensitive composition obtained above was rotationally coated on a clean silicon wafer and then pre-exposed baked (PB) in an oven at 110 ° C. to form a resist film having a thickness of 200 nm.
  • the resist film was exposed to ultraviolet rays using an ultraviolet exposure device (Mikasa Mask Aligner MA-10).
  • the resist film was heated at 110 ° C. for 90 seconds and immersed in TMAH 2.38 mass% alkaline developer for 60 seconds for development. Then, the resist film was washed with ultrapure water for 30 seconds and dried to form a 5 ⁇ m positive resist pattern.
  • the obtained line and space was observed with a scanning electron microscope (S-4800 manufactured by Hitachi High-Technology Co., Ltd.).
  • the line edge roughness was good when the unevenness of the pattern was less than 50 nm.
  • the radiation-sensitive compositions of Examples 68 to 74 can form a resist pattern having a smaller roughness and a better shape than the radiation-sensitive compositions of Comparative Example 4. I found out. As long as the above-mentioned requirements of the present invention are satisfied, radiation-sensitive compositions other than those described in Examples show the same effect.
  • the underlayer film forming material for lithography using this has relatively low embedding characteristics and flatness of the film surface. Can be enhanced in favor of. Further, since the pyrolysis temperature is 150 ° C. or higher (evaluation A) and has high heat resistance, it can be used even under high temperature baking conditions.
  • Example 75 Purification of BiA-1 with acid 150 g of a solution (10% by mass) of BiA-1 obtained in Synthesis Example 1 dissolved in PGMEA in a 1000 mL volume four-necked flask (bottom punching type). It was charged and heated to 80 ° C. with stirring. Then, 37.5 g of an aqueous oxalic acid solution (pH 1.3) was added, and the mixture was stirred for 5 minutes and allowed to stand for 30 minutes. As a result, the oil phase and the aqueous phase were separated, and the aqueous phase was removed.
  • aqueous oxalic acid solution pH 1.3
  • Example 76-1 to 105-2 The solubility of the resin obtained in the above synthetic example was evaluated. The results are shown in Table 11. Further, the underlayer film forming material for lithography (underlayer film forming composition for lithography) having the composition shown in Table 11 was prepared. Next, these lithographic underlayer film forming materials were rotationally coated on a silicon substrate, and then baked at 240 ° C. for 60 seconds and further at 400 ° C. for 120 seconds to prepare underlayer films having a film thickness of 200 nm. The following were used as the acid generator, the cross-linking agent and the organic solvent. Acid generator: Midori Kagaku Co., Ltd.
  • Each of the obtained underlayer films was subjected to an etching test to evaluate the etching resistance.
  • the evaluation results are shown in Tables 11-1 to 11-3.
  • the content of the etching test is as described in Example 1-1 and the like.
  • Example B1-1 to Example B1-2> The composition for forming an underlayer film for lithography prepared in Examples 36-1 and 36-2 was spin-coated on a silicon substrate and baked at 150 ° C. for 60 seconds to form a film and remove a solvent. Then, high temperature heat resistance was evaluated using a lamp annealing furnace as shown below.
  • Example B2-1 to Example B31-2, Comparative Example B1> The high temperature heat resistance evaluation was carried out in the same manner as in Example B1-1 except that the composition for forming the underlayer film for lithography used was changed to the composition shown in Table 11.
  • Example C1-1 to Example C1-2> A 12-inch silicon wafer is subjected to thermal oxidation treatment to prepare a substrate having a silicon oxide film, and the same composition is used on the substrate for forming a film for lithography of Examples 36-1 and 36-2.
  • a resin film having a thickness of 100 nm was prepared by the method.
  • a silicon oxide film and a SiN film were formed on the resin film as described later, and the PE-CVD film forming property was evaluated.
  • Example C2-1 to Example C11-2 and Comparative Example C1> A film was formed and evaluated in the same manner as in Example C1-1 except that the composition for forming a film for lithography used was changed to the composition shown in Table 11.
  • TELINDY manufactured by Tokyo Electron Limited
  • TEOS tetraethylsiloxane
  • a wafer with a cured film on which this silicon oxide film is laminated is inspected for defects using KLA-Tencor SP-5, and the number of defects in the film-formed oxide film is evaluated using the number of defects having a diameter of 21 nm or more as an index. It was.
  • SiN film evaluation A cured film is formed on a substrate having a 100 nm-thick silicon oxide film formed by thermal oxidation treatment on a 12-inch silicon wafer by the same method as described above, and further, a film-forming device TELINDY (manufactured by Tokyo Electron).
  • TELINDY manufactured by Tokyo Electron
  • a SiN film having a film thickness of 40 nm, a refractive index of 1.94, and a film stress of ⁇ 54 MPa was formed at a substrate temperature of 350 ° C. using SiN 4 (monosilane) and ammonia as raw materials.
  • a wafer with a cured film on which a SiN film is laminated is inspected for defects using KLA-Tencor SP-5, and as described above, the number of defects in the film-formed oxide film is evaluated using the number of defects having a diameter of 21 nm or more as an index. Was done. These results are shown in Table 13.
  • the silicon oxide film or SiN film formed on the resin films of Examples C1-1 to C11-2 has 50 or less defects (B evaluation or more) having a diameter of 21 nm or more, and the number of defects in Comparative Example C1. It was shown to be less than.
  • Example D1-1 The composition solution for forming a film for lithography obtained in Example 36-1 was applied onto a substrate on which a 12-inch silicon wafer was subjected to thermal oxidation treatment to form a silicon oxide film by the same method as in Example C1-1.
  • a resin film was prepared with a thickness of 100 nm.
  • the resin film was further subjected to an annealing treatment by heating under the condition of 600 ° C. for 4 minutes using a hot plate capable of high temperature treatment in a nitrogen atmosphere to prepare a wafer on which the annealed resin film was laminated.
  • Etching evaluation was performed on the substrate as follows.
  • the substrate was etched using an etching apparatus TELIUS (manufactured by Tokyo Electron Limited) under the condition that CF 4 / Ar was used as the etching gas, and the etching rate was evaluated.
  • the etching rate is evaluated by using a resin film having a thickness of 200 nm prepared by annealing SU8 (manufactured by Nippon Kayaku Co., Ltd.) at 250 ° C. for 1 minute as a reference, and obtaining the rate ratio of the etching rate to SU8 as a relative value. did.
  • Example D1-2 to Example D31-2 Comparative Example D1> Etching evaluation after high temperature treatment was carried out in the same manner as in Example D1-1 except that the composition for forming a film for lithography used was changed to the composition shown in Table 11.
  • the compound and resin of the present invention have high heat resistance and high solvent solubility, and a wet process can be applied. Therefore, the lithographic film forming material using the compound or resin of the present invention and the lithographic film can be widely and effectively used in various applications in which these performances are required.
  • the present invention relates to, for example, electrical insulating materials, resist resins, semiconductor encapsulation resins, printed wiring board adhesives, electrical laminates mounted on electrical equipment, electronic equipment, industrial equipment, etc., and electrical equipment.
  • Prepreg matrix resin mounted on electronic equipment, industrial equipment, etc. build-up laminate material, fiber-reinforced plastic resin, liquid crystal display panel sealing resin, paint, various coating agents, adhesives, coatings for semiconductors It can be widely and effectively used in agents, resins for resists for semiconductors, resins for forming underlayer films, and the like. In particular, the present invention can be particularly effectively used in the field of lithographic films.

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Abstract

La présente invention aborde le problème de la fourniture : d'une (poly)amine qui est particulièrement utile en tant que matériau pour la formation de film pour lithographie ou en tant que matériau pour la formation d'un composant optique ; une résine obtenue à l'aide de ce composé en tant que monomère ; une composition ; un procédé de formation de motif de réserve ; un procédé de formation d'un film isolant ; un procédé de formation de motif de circuit ; et un procédé de purification du composé ou de la résine ci-dessus. La solution selon l'invention concerne : une composition permettant de former un film pour lithographie, ladite composition contenant une (poly)amine représentée par la formule (0) et/ou une résine polyamine ayant une unité constitutive dérivée de (poly)amine ; et similaire.
PCT/JP2020/032187 2019-08-27 2020-08-26 Composition permettant de former un film pour la lithographie, procédé de formation de motif de réserve, procédé de formation de motif de circuit et procédé de purification WO2021039843A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005099138A (ja) * 2003-09-22 2005-04-14 Fuji Photo Film Co Ltd 感光性組成物
JP2006088582A (ja) * 2004-09-24 2006-04-06 Fuji Photo Film Co Ltd 平版印刷版原版及びそれを用いた平版印刷方法
JP2006220863A (ja) * 2005-02-09 2006-08-24 Fuji Photo Film Co Ltd パターン形成材料、並びにパターン形成装置及びパターン形成方法
JP5498170B2 (ja) * 2007-12-26 2014-05-21 旭化成イーマテリアルズ株式会社 耐熱性樹脂前駆体及びそれを用いた感光性樹脂組成物
WO2015098594A1 (fr) * 2013-12-26 2015-07-02 日産化学工業株式会社 Composition filmogène de sous-couche de réserve contenant un polymère novolaque ayant un groupe amine secondaire
WO2019151400A1 (fr) * 2018-01-31 2019-08-08 三菱瓦斯化学株式会社 Composé, résine, composition, procédé de formation de motif de photorésine, procédé de formation de motif de circuit, et procédé de purification de résine

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005099138A (ja) * 2003-09-22 2005-04-14 Fuji Photo Film Co Ltd 感光性組成物
JP2006088582A (ja) * 2004-09-24 2006-04-06 Fuji Photo Film Co Ltd 平版印刷版原版及びそれを用いた平版印刷方法
JP2006220863A (ja) * 2005-02-09 2006-08-24 Fuji Photo Film Co Ltd パターン形成材料、並びにパターン形成装置及びパターン形成方法
JP5498170B2 (ja) * 2007-12-26 2014-05-21 旭化成イーマテリアルズ株式会社 耐熱性樹脂前駆体及びそれを用いた感光性樹脂組成物
WO2015098594A1 (fr) * 2013-12-26 2015-07-02 日産化学工業株式会社 Composition filmogène de sous-couche de réserve contenant un polymère novolaque ayant un groupe amine secondaire
WO2019151400A1 (fr) * 2018-01-31 2019-08-08 三菱瓦斯化学株式会社 Composé, résine, composition, procédé de formation de motif de photorésine, procédé de formation de motif de circuit, et procédé de purification de résine

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