Film-forming material for semiconductor, member-forming material for semiconductor, process member-forming material for semiconductor, underlayer film-forming material, underlayer film, and semiconductor device

Abstract

The purpose of the present invention is to provide a film-forming material for a semiconductor which yields a film having excellent heat resistance and solvent resistance.　The present invention is a film-forming material for a semiconductor including: a compound represented by general formula (I) and having one or more reactive groups in the molecule thereof, or a polymer in which the compound represented by general formula (I) and having one or more reactive groups in the molecule thereof serves as a monomer; and a solvent. In the formula, A represents a hydrocarbon ring having six carbon atoms, X1 and X2 each represent a reactive group or an aryl group or the like having 6-30 carbon atoms and in which a group having a reactive group may be substituted, R1, R2, R3, R4, R6, R7, R8, and R9 each represent a hydrogen atom, a reactive group, or a hydrocarbon group or the like having 1-20 carbon atoms and in which a reactive group may be substituted, and R5 and R10 each represent a hydrogen atom or a hydrocarbon group or the like having 1-20 carbon atoms and in which a reactive group may be substituted.

Description

Semiconductor film forming materials, semiconductor member forming materials, semiconductor process member forming materials, underlayer film forming materials, underlayer films and semiconductor devices

[0001] The present invention relates to a film-forming material for semiconductors, which contains a compound having a specific skeleton.

[0002] With the recent increase in capacity, integration density, and speed of integrated circuits, further improvements in performance, such as high heat resistance and high durability, are being demanded of materials used to form semiconductor components, such as encapsulants, insulating films, materials for multilayer substrates, barrier films, insulating films for through-silicon vias, etc. Patent Document 1 describes an oxazine compound having an aromatic ring structure and a plurality of specified carbon-carbon triple bond structures as a compound that has excellent heat resistance, low thermal expansion, and also excellent adhesion and moisture resistance and solder resistance.

[0003] Furthermore, as semiconductor patterns become finer, photoresist layers are becoming thinner to address issues such as maintaining the rectangular shape of the photoresist pattern and preventing collapse. However, as the photoresist layers become thinner, the etching resistance of the photoresist pattern becomes insufficient, making it difficult to sufficiently etch the substrate to be processed. To achieve a good pattern shape, multi-layer resist materials consisting of photoresist, an intermediate film, an underlayer film, etc. are used in the semiconductor manufacturing process.

[0004] An example of a semiconductor manufacturing process using a multilayer resist material is shown below. A common example of a multilayer resist material is a three-layer resist method, which has two layers underneath a photoresist layer. Specifically, the process is as follows: First, an underlayer film-forming material is applied to a substrate to be processed, such as a silicon wafer, and then heated to form an underlayer film. After an intermediate film is formed on the underlayer film, a photoresist is applied, and a pattern is formed by exposure and development. Using the formed pattern as a mask, the intermediate film and then the underlayer film are etched under appropriate dry etching conditions. Using the resulting underlayer film pattern as a mask, the substrate to be processed is etched under appropriate dry etching conditions, and the remaining mask is ashed to obtain a substrate with the desired structure.

[0005] Materials for forming the underlayer film must be heat-resistant and solvent-resistant so that they do not deform due to heat or solvents during the formation of the intermediate film or photoresist layer, and must also be etch-resistant so that transfer by etching can be performed accurately. They must also be able to fill in the irregularities on the substrate and have flatness properties so that the film can be formed evenly. Known underlayer film materials include vinyl derivatives having an aromatic hydrocarbon ring (Patent Document 2) and aromatic compounds having a carbon-carbon triple bond structure (Patent Document 3).

[0006] JP 2018-002612 A JP 2018-140972 A US 2020 / 0142309 A1

[0007] An object of the present invention is to provide a film-forming material for semiconductors which gives a film having excellent heat resistance and solvent resistance.

[0008] As a result of extensive research, the present inventors have found that a semiconductor film-forming material containing a compound having a specific skeleton and one or more reactive groups in the molecule, or a polymer having such a compound as a monomer, and a solvent, can provide a film that is excellent in heat resistance and solvent resistance, and have thus completed the present invention.

[0009] That is, the present invention provides a semiconductor film-forming material containing a compound represented by the following general formula (I) and having one or more reactive groups in the molecule (hereinafter also referred to as “compound (I)”) or a polymer containing compound (I) as a monomer (hereinafter also referred to as “polymer (I)”), and a solvent:

[0010] In the formula, A represents a hydrocarbon ring having 6 carbon atoms; １ and X ２ each independently represents an aryl group having 6 to 30 carbon atoms which may be substituted with a reactive group or a group having a reactive group, a heterocyclic group having 2 to 30 carbon atoms which may be substituted with a reactive group or a group having a reactive group, or a heterocyclic-containing group having 3 to 30 carbon atoms which may be substituted with a reactive group or a group having a reactive group, １ , R ２ , R ３ , R ４ , R ６ , R ７ , R ８ and R９ each independently represents a hydrogen atom, a halogen atom, a reactive group, a nitro group, a hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a reactive group, a heterocyclic group of 2 to 10 carbon atoms which may be substituted with a reactive group, or a heterocyclic group containing 3 to 30 carbon atoms which may be substituted with a reactive group, or a group in which one or more methylene groups in the hydrocarbon group of 1 to 20 carbon atoms have been substituted with a divalent group selected from the following <Group A>, or a group in which one or more methylene groups in the heterocyclic group containing 3 to 30 carbon atoms have been substituted with a divalent group selected from the following <Group A>, R ５ and R １０ each independently represents a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a reactive group, a heterocyclic group of 2 to 10 carbon atoms which may be substituted with a reactive group, or a heterocyclic ring-containing group of 3 to 30 carbon atoms which may be substituted with a reactive group, or a group in which one or more methylene groups in the hydrocarbon group of 1 to 20 carbon atoms have been substituted with a divalent group selected from <Group A> below, or a group in which one or more methylene groups in the heterocyclic ring-containing group of 3 to 30 carbon atoms have been substituted with a divalent group selected from <Group A> below. <Group A>: -O-, -CO-, -COO-, -OCO-, -NR １１ -, -NR １２ CO-, -S-R １１ and R １２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0011] The semiconductor film-forming material of the present invention can provide a semiconductor film having excellent heat resistance and solvent resistance.

[0012] Semiconductor film-forming materials are materials necessary for forming semiconductor films, and consist of semiconductor member-forming materials necessary for forming semiconductor members and semiconductor process member-forming materials necessary for forming semiconductor process members.

[0013] The semiconductor member-forming material includes materials suitable for each application, such as insulating film-forming materials, barrier film-forming materials, encapsulant-forming materials, gap fill material-forming materials, mounting films, mounting adhesives, and circuit connection materials.

[0014] The materials for forming semiconductor process members include materials suitable for the respective applications, such as materials for forming underlayer films, photoresists, anti-reflection films, and intermediate films.

[0015] The semiconductor film is a film used in the production of semiconductors. Specifically, it is a general term for a solid layer formed by applying a semiconductor film-forming material and then evaporating the solvent, or a cured product formed by curing the solid layer through a polymerization reaction or the like.

[0016] The semiconductor film is made up of a semiconductor material and a semiconductor process material. The semiconductor material refers to a material that remains on a semiconductor device as a permanent film, and the semiconductor process material refers to a material that is used in a semiconductor manufacturing process as a sacrificial film but does not remain on the semiconductor device.

[0017] Examples of the semiconductor member include an insulating film, a barrier film, a sealing material, a gap fill material, a mounting film, a mounting adhesive, and a circuit connecting material.

[0018] Examples of the semiconductor processing members include photoresists, intermediate films, underlayer films, anti-reflective films, etc. Photoresists, intermediate films, and underlayer films are semiconductor processing members used for the purpose of obtaining good patterns, and can be used as multi-layer resists in which an underlayer film, an intermediate film, and a photoresist are laminated in this order on a substrate to be processed such as a silicon wafer.

[0019] The semiconductor device means an electronic component equipped with a semiconductor, and examples thereof include discrete devices (individual semiconductors) each having a single function, such as a transistor or a diode; ICs (integrated circuits) each having multiple functional devices mounted on a single chip; and CPUs such as memories, microprocessors (MPUs), and logic ICs.

[0020] The compound (I) used in the present invention is a compound having a specific skeleton and is characterized by having one or more reactive groups in the molecule.

[0021] The reactive group possessed by the compound (I) refers to a group capable of forming a covalent bond with another reactive group. Here, the other reactive group may be the same type of reactive group or a different type of reactive group. In the present invention, the reactive group refers to a carbon-carbon double bond, a carbon-carbon triple bond, a nitrile group, an epoxy group, an isocyanate group, a hydroxyl group, an amino group, or a thiol group. That is, the reactive group in the general formula (I) is a vinyl group, an ethynyl group, a nitrile group, an epoxy group, an isocyanate group, a hydroxyl group, an amino group, or a thiol group. The nitrile group is included in the reactive group because it can form a triazine ring by a trimerization reaction. Preferred reactive groups are a carbon-carbon triple bond, a carbon-carbon double bond, a hydroxyl group, and an epoxy group; more preferred are a carbon-carbon triple bond, a carbon-carbon double bond, and a phenolic hydroxyl group; and most preferred are a carbon-carbon triple bond and a phenolic hydroxyl group. The reactive group being one of the above groups improves the heat resistance of the resulting film.

[0022] The group having a reactive group in the general formula (I) represents a group in which one or more hydrogen atoms of a group that can be taken in the general formula (I) are substituted with the above-mentioned reactive group, and examples thereof include alkenyl groups having 2 to 10 carbon atoms such as an allyl group; alkenyloxy groups having 2 to 10 carbon atoms such as a vinyloxy group and an allyloxy group; alkynyl groups having 2 to 10 carbon atoms such as a propargyl group; alkynyloxy groups having 2 to 10 carbon atoms such as a propargyloxy group; acryloyl, methacryloyl, glycidyl, glycidyloxy, and oxetanyl groups.

[0023] Examples of the hydrocarbon ring having 6 carbon atoms represented by A in the general formula (I) include a benzene ring, a cyclohexadiene ring, a cyclohexene ring, and a cyclohexane ring.

[0024] X in the general formula (I) １ and X ２The aryl group having 6 to 30 carbon atoms and represented by the formula (I) may have a monocyclic structure, a fused ring structure, or may further have two aromatic hydrocarbon rings linked together. Examples of the aryl group having a fused ring structure having 6 to 30 carbon atoms include hydrocarbon-type aromatic fused ring groups having 7 to 30 carbon atoms, which have a structure in which two or more aromatic hydrocarbon rings are fused together.

[0025] Examples of the aryl group having a monocyclic structure and having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, 2,4,6-trimethylphenyl, etc. Examples of the hydrocarbon-type aromatic fused ring group having 7 to 30 carbon atoms include naphthyl, anthracenyl, phenanthryl, pyrenyl, fluorenyl, and indenofluorenyl.

[0026] The aryl group in which two aromatic hydrocarbon rings are linked may be one in which two aromatic hydrocarbon rings of a monocyclic structure are linked, one in which an aromatic hydrocarbon ring of a monocyclic structure is linked to an aromatic hydrocarbon ring of a fused ring structure, or one in which an aromatic hydrocarbon ring of a fused ring structure is linked to an aromatic hydrocarbon ring of a fused ring structure. Examples of the linking group linking the two aromatic hydrocarbon rings include a single bond, a sulfide group (-S-), and a carbonyl group. Examples of the aryl group in which two aromatic hydrocarbon rings of a monocyclic structure are linked to each other include biphenyl, diphenyl sulfide, and benzoylphenyl.

[0027] The aryl group having 6 to 30 carbon atoms may be substituted with a reactive group or a group having a reactive group. An aryl group having 6 to 30 carbon atoms and substituted with a reactive group or a group having a reactive group refers to an aryl group having 6 to 30 carbon atoms in which one or more hydrogen atoms have been substituted with a reactive group or a group having a reactive group. The aryl group having 6 to 30 carbon atoms may also have other substituents. Examples of other substituents include halogen atoms and nitro groups.

[0028] X in the general formula (I) １ and X ２A heterocyclic group having 2 to 30 carbon atoms represented by the formula (I) is a group in which one hydrogen atom has been removed from a heterocyclic compound, but an epoxy group is included in the category of reactive groups and is therefore not included in the heterocyclic group. The heterocyclic group may have a monocyclic structure or a fused ring structure. Examples of heterocyclic groups having a fused ring structure and having 2 to 30 carbon atoms include heterocycle-containing fused ring groups having 3 to 30 carbon atoms, which have a structure in which a heterocycle and a heterocycle or a hydrocarbon ring are fused together. Specific examples of heterocyclic groups include pyridyl, quinolyl, thiazolyl, tetrahydrofuranyl, dioxolanyl, tetrahydropyranyl, methylthiophenyl, hexylthiophenyl, benzothiophenyl, pyrrolyl, pyrrolidinyl, imidazolyl, imidazolidinyl, imidazolinyl, pyrazolyl, pyrazolidinyl, piperidinyl, piperazinyl, pyrimidinyl, furyl, thienyl, benzoxazol-2-yl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, morpholinyl, and the like.

[0029] The heterocyclic group having 2 to 30 carbon atoms may be substituted with a reactive group or a group having a reactive group. A heterocyclic group having 2 to 30 carbon atoms substituted with a reactive group or a group having a reactive group means a group having 2 to 30 carbon atoms in which one or more hydrogen atoms in the heterocyclic group have been substituted with a reactive group or a group having a reactive group. The heterocyclic group having 2 to 30 carbon atoms may also have other substituents. Examples of the substituents include a halogen atom and a nitro group.

[0030] X in the general formula (I) １ and X ２ The heterocyclic ring-containing group having 3 to 30 carbon atoms represented by the formula (I) means a group having 3 to 30 carbon atoms in which one or more hydrogen atoms in a hydrocarbon group have been substituted with a heterocyclic group. Examples of the heterocyclic group include the groups exemplified above as the heterocyclic group having 2 to 30 carbon atoms. Examples of the hydrocarbon group include hydrocarbon groups having 1 to 20 carbon atoms. Hydrocarbon groups having 1 to 20 carbon atoms will be described later.

[0031] The heterocyclic ring-containing group having 3 to 30 carbon atoms may be substituted with a reactive group or a group having a reactive group. A heterocyclic ring-containing group having 3 to 30 carbon atoms and substituted with a reactive group or a group having a reactive group refers to a group having 3 to 30 carbon atoms in which one or more hydrogen atoms in the heterocyclic ring-containing group have been substituted with a reactive group or a group having a reactive group. The heterocyclic ring-containing group having 3 to 30 carbon atoms may also have other substituents. Examples of the substituents include a halogen atom and a nitro group.

[0032] R in the general formula (I) １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ and R １０ (Hereinafter referred to as “R １ The hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) is a group having 1 to 20 carbon atoms and consisting of carbon atoms and hydrogen atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon ring-containing groups having 6 to 20 carbon atoms. However, reactive groups or groups having reactive groups, i.e., vinyl groups, ethynyl groups, and groups having these groups, are not included in the hydrocarbon group.

[0033] Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkylalkyl group having 4 to 20 carbon atoms.

[0034] The alkyl group having 1 to 20 carbon atoms may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, iso-amyl, tert-amyl, hexyl, heptyl, and octyl. Examples of branched alkyl groups include iso-propyl, sec-butyl, tert-butyl, iso-butyl, iso-pentyl, tert-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, iso-octyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebrotadecyl, and octadecyl.

[0035] Examples of cycloalkyl groups having 3 to 20 carbon atoms include saturated monocyclic alkyl groups having 3 to 20 carbon atoms, saturated polycyclic alkyl groups having 3 to 20 carbon atoms, and groups having 4 to 20 carbon atoms in which one or more hydrogen atoms in the ring of these groups have been substituted with an alkyl group. Examples of saturated monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Examples of saturated polycyclic alkyl groups include adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo[1.1.1]pentanyl. Examples of alkyl groups substituting hydrogen atoms in the ring of saturated monocyclic or saturated polycyclic alkyl groups include the groups exemplified above as alkyl groups having 1 to 20 carbon atoms. Examples of groups in which one or more hydrogen atoms in the ring of a saturated polycyclic alkyl group have been substituted with an alkyl group include bornyl.

[0036] A cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of an alkyl group is substituted with a cycloalkyl group. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms and in which the cycloalkyl group is monocyclic include cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, and 2-cyclodecylethyl. Examples of cycloalkylalkyl groups having 4 to 20 carbon atoms and in which the cycloalkyl group is polycyclic include 3-3-adamantylpropyl and decahydronaphthylpropyl.

[0037] The aromatic hydrocarbon ring-containing group having 6 to 20 carbon atoms is a hydrocarbon group that contains an aromatic hydrocarbon ring but does not contain a heterocycle, and may have an aliphatic hydrocarbon group. Examples of the aromatic hydrocarbon ring-containing group include an aryl group having 6 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms.

[0038] Examples of the aryl group having 6 to 20 carbon atoms include X １ and X ２ Examples of the aryl group having 6 to 30 carbon atoms include the groups exemplified as the aryl group represented by the following formula:

[0039] An arylalkyl group having 7 to 20 carbon atoms means a group in which one or more hydrogen atoms in an alkyl group are substituted with an aryl group. Examples of the arylalkyl group having 7 to 20 carbon atoms include benzyl, fluorenyl, indenyl, 9-fluorenylmethyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl, and naphthylpropyl groups.

[0040] R in the general formula (I) １ The hydrocarbon group having 1 to 20 carbon atoms, represented by the following formula (I) or (II), may have a substituent. Examples of the substituent include a halogen atom and a nitro group. When the hydrocarbon group has a substituent, the number of carbon atoms indicates the total number of carbon atoms in the group.

[0041] R in the general formula (I)１ and the like may be a group in which one or more methylene groups in the hydrocarbon group having 1 to 20 carbon atoms are substituted with a divalent group selected from the above <Group A>, or a group in which one or more methylene groups in the heterocycle-containing group having 3 to 30 carbon atoms are substituted with a divalent group selected from the above <Group A>. The number of carbon atoms in these groups represents the number of carbon atoms in the hydrocarbon group and the heterocycle-containing group before the methylene groups are substituted.

[0042] R in the general formula (I) １１ and R １２ The hydrocarbon group having 1 to 20 carbon atoms represented by R in general formula (I) １ and the like.

[0043] In the present invention, a compound in which A in the general formula (I) is a benzene ring, a cyclohexadiene ring, or a cyclohexane ring is preferred because it has excellent solvent solubility and the resulting film has excellent heat resistance and solvent resistance. That is, the compound (I) is preferably a compound represented by the following general formula (Ia), (Ib), or (Ic):

[0044] Each symbol in the formula is the same as in the general formula (I).

[0045] Each symbol in the formula is the same as in the general formula (I).

[0046] Each symbol in the formula is the same as in the general formula (I).

[0047] Among these, the compound represented by the general formula (Ia) in which A in the general formula (I) is a benzene ring is preferred because the resulting film has better heat resistance and solvent resistance.

[0048] X in the general formula (I) １ and X ２However, a compound which is an aryl group having a monocyclic structure and having 6 to 30 carbon atoms, a hydrocarbon-type aromatic fused ring group having 7 to 30 carbon atoms, or a heterocycle-containing fused ring group having 3 to 30 carbon atoms, which may be substituted with a reactive group or a group having a reactive group, is preferred because it allows the formation of a film with better heat resistance, and a phenyl group is particularly preferred as the aryl group having a monocyclic structure and having 6 to 30 carbon atoms because of its high solubility in solvents.

[0049] The hydrocarbon-type aromatic fused ring group having 7 to 30 carbon atoms is a fused ring containing an aromatic ring consisting only of carbon atoms and hydrogen atoms, and the atoms constituting the ring structure of the fused ring are only carbon atoms. Examples of the hydrocarbon-type aromatic fused ring having 7 to 30 carbon atoms include a naphthyl group, an anthracenyl group, a pyrenyl group, a tetracenyl group, a triphenylenyl group, an azulenyl group, a phenanthrenyl group, a tetracenyl group, a perylenyl group, and a fluorenyl group, with the naphthyl group and the fluorenyl group being preferred due to their high solubility in solvents.

[0050] The C3-C30 heterocycle-containing fused ring group is a C3-C30 fused ring containing a heterocycle. Examples of the C3-C30 heterocycle-containing fused ring group include an indolyl group, a carbazolyl group, a benzofuranyl group, a benzothiophenyl group, a benzopyrazoyl group, a julolidinyl group, and a benzoquinolinyl group, and the indolyl group, a carbazolyl group, and a benzothiophenyl group are preferred because of their high solubility in solvents.

[0051] In the present invention, X in the general formula (I) １ and X ２ However, compounds each independently being a reactive group or a group which may be substituted with a group having a reactive group are preferred because they can provide a film with excellent heat resistance, and １ and X ２ However, a compound in which each of the groups is independently substituted with a reactive group or a group having a reactive group is more preferred, and a compound in which each of the groups is an aryl group having 6 to 30 carbon atoms substituted with a reactive group or a group having a reactive group is particularly preferred.

[0052] X １ and X ２However, when the aryl group is an aryl group having 6 to 30 carbon atoms substituted with a reactive group or a group having a reactive group, the aryl group is preferably a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a pyrenyl group, or a fluorenyl group, since a film having excellent heat resistance can be obtained.

[0053] X １ or X ２ When the aryl group is an aryl group having 6 to 30 carbon atoms substituted with a reactive group or a group having a reactive group, the number of reactive groups or groups having a reactive group is preferably one or two, respectively.

[0054] X １ and X ２ When the compound (I) has a reactive group or a group having a reactive group, the reactive group is preferably a carbon-carbon triple bond, since a film having excellent heat resistance can be obtained. As the group having a carbon-carbon triple bond, an alkynyl group having 2 to 10 carbon atoms and an alkynyloxy group having 2 to 10 carbon atoms are preferred, and a propargyl group and a propargyloxy group are more preferred.

[0055] Also, X １ and X ２ When X has a reactive group, a film having excellent heat resistance can be obtained, and therefore, it is also preferable that the reactive group is a hydroxyl group. １ and X ２ However, a compound in which the aryl group is an aryl group having 6 to 30 carbon atoms substituted with a hydroxyl group, that is, an aryl group having 6 to 30 carbon atoms and a phenolic hydroxyl group, is more preferred.

[0056] X １ and X ２ may be the same group or different groups, but are preferably the same group from the viewpoint of compound synthesis.

[0057] In the present invention, R in the general formula (I) ５ and R １０ It is also preferable that R is a hydrocarbon group having 1 to 20 carbon atoms substituted with a reactive group. ５ and R １０When is a group having a reactive group, the reactive group is preferably a carbon-carbon triple bond or a carbon-carbon double bond, and a carbon-carbon triple bond is particularly preferred, since a film having excellent heat resistance can be obtained. As the hydrocarbon group having 1 to 20 carbon atoms substituted with a carbon-carbon triple bond, an alkynyl group having 3 to 10 carbon atoms is preferred, and a propargyl group is more preferred.

[0058] Also, R １ , R ２ , R ３ , R ４ , R ６ , R ７ , R ８ and R ９ is preferably a hydrogen atom from the viewpoint of compound synthesis.

[0059] The compound of the present invention preferably has three or more reactive groups in the molecule, since this allows for the production of a film with excellent heat resistance, and more preferably has four to six reactive groups. When the compound has three or more reactive groups in the molecule, X １ and X ２ When each of X has two reactive groups, １ and X ２ each having two reactive groups, and R ５ and R １０ When X has a reactive group, １ and X ２ each having one reactive group, and further R ５ and R １０ has a reactive group.

[0060] In the present invention, X in the general formula (I) １ and X ２ is preferably a group having a reactive group. １ , X ２ , R ５ and R １０ It is also preferred that is a group having a reactive group.

[0061] Specific examples of the compound (I) include the following compounds (1) to (215).

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] The compound (I) can be produced by a known method. Specifically, a tetrahydroindolocarbazole compound corresponding to the compound in which A in the general formula (I) is a cyclohexadiene ring can be produced by condensing indole and an aldehyde compound using an acid catalyst. Furthermore, a dihydroindolocarbazole compound corresponding to the compound in which A in the general formula (I) is a benzene ring can be produced by oxidizing the tetrahydroindolocarbazole compound with an oxidizing agent such as iodine and chloranil. Thereafter, the compound (I) can be produced by introducing a reactive group into the amino group in these indolocarbazole compounds. For example, １ and X２ is a phenyl group, and R ５ and R １０ is a reactive group R, and R １ , R ２ , R ３ , R ４ , R ６ , R ７ , R ８ and R ９ The compound in which is a hydrogen atom can be prepared as follows.

[0080]

[0081] In addition, for example, by using an aldehyde compound having a hydroxyl group, X in the general formula (I) can be １ and X ２ is a hydroxyphenyl group. Furthermore, by introducing reactive groups R into the hydroxyl group and amino group of this compound, it is possible to produce a compound having three or more reactive groups R in the molecule.

[0082]

[0083] The polymer (I) used in the present invention may be a homopolymer of the compound (I) or a copolymer with other monomers.

[0084] In the present invention, the polymer (I) is preferably a polymer (hereinafter also referred to as "polymer (II)") that is represented by the following general formula (II) and contains a structural unit (hereinafter also referred to as "structural unit (II)") having one or more reactive groups. １ and X ２ is preferably a group having a reactive group. １ , X ２ , R ５ and R １０ It is also preferred that is a group having a reactive group.

[0085] A and X in the formula １ , X ２ , R ５ and R １０is the same as in the general formula (I), ２１ and R ２２ each independently represents a halogen atom, a reactive group, a nitro group, a cyano group, a hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a reactive group, a heterocyclic group of 2 to 10 carbon atoms which may be substituted with a reactive group, or a heterocyclic group containing 3 to 30 carbon atoms which may be substituted with a reactive group, or a group in which one or more methylene groups in the hydrocarbon group of 1 to 20 carbon atoms are substituted with a divalent group selected from <Group B> below, or a group in which one or more methylene groups in the heterocyclic group containing 3 to 30 carbon atoms are substituted with a divalent group selected from <Group B> below, R ２３ and R ２４ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a hydrocarbon group of 1 to 20 carbon atoms which may have a substituent, a heterocyclic group of 2 to 10 carbon atoms which may have a substituent, or a heterocyclic group containing 3 to 30 carbon atoms which may have a substituent, or a group in which one or more methylene groups in the hydrocarbon group of 1 to 20 carbon atoms have been substituted with a divalent group selected from <Group B> below, or a group in which one or more methylene groups in the heterocyclic group containing 3 to 30 carbon atoms have been substituted with a divalent group selected from <Group B> below, R ２３ and R ２４ may be bonded to each other directly or via a methylene group, —O— or —S— to form a ring, a represents an integer of 0 to 3, and b represents an integer of 0 to 3. <Group B>: —O—, —CO—, —COO—, —OCO—, —NR ２５ -, -NR ２６ CO-, -S-R ２５ and R ２６ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0086] R in the general formula (II) ２１ , R ２２ , R ２３ , R ２４ , R ２５ and R ２６ The hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) is R １The R in the general formula (II) is exemplified as a hydrocarbon group having 1 to 20 carbon atoms. ２１ , R ２２ , R ２３ and R ２４ The heterocyclic group having 2 to 10 carbon atoms and the heterocyclic group containing 3 to 30 carbon atoms represented by the formula (I) are １ and the like, which are exemplified as heterocyclic groups having 2 to 10 carbon atoms and heterocyclic ring-containing groups having 3 to 30 carbon atoms.

[0087] In the present invention, a polymer in which A in the general formula (II) is a benzene ring, a cyclohexadiene ring, or a cyclohexane ring is preferred because the resulting film has excellent heat resistance. That is, the structural unit (II) is preferably a structural unit represented by the following general formula (IIa), (IIb), or (IIc) and having one or more reactive groups:

[0088] Each symbol in the formula is the same as in the general formula (II).

[0089] Each symbol in the formula is the same as in the general formula (II).

[0090] Each symbol in the formula is the same as in the general formula (II).

[0091] In the structural unit (II), A and X in general formula (II) １ , X ２ , R ５ and R １０ The preferred embodiments of the compound (I) can be the same as those described above in the description of the compound (I).

[0092] In the general formula (II), a and b are preferably 0, since a film having excellent heat resistance can be obtained. １ , R ２ , R ３ , R ４ , R ６ , R ７ , R ８ and R ９ is equivalent to being a hydrogen atom.

[0093] In the present invention, the weight average molecular weight of the polymer is preferably 500 or more and less than 30,000, since a film having excellent solubility in solvents and excellent heat resistance can be obtained, more preferably 700 or more and less than 15,000, and particularly preferably 1,000 or more and less than 10,000, since the solubility in solvents and film formability are good. In the present invention, the weight average molecular weight is a molecular weight measured by gel permeation chromatography (GPC) in terms of polystyrene.

[0094] The weight average molecular weight (Mw) can be measured, for example, using a GPC (LC-2000plus series) manufactured by JASCO Corporation, using tetrahydrofuran as the elution solvent, using polystyrene standards for calibration curves of Mw 1,110,000, 707,000, 397,000, 189,000, 98,900, 37,200, 15,700, 9,490, 5,430, 3,120, 1,010, and 589 (TSKgel standard polystyrene manufactured by Tosoh Corporation), and using KF-804, KF-803, and KF-802 (manufactured by Showa Denko K.K.) as measurement columns.

[0095] Specific examples of the structural unit (II) include the following structural units (u1) to (u101).

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] The polymer (II) can be produced by condensing the compound (I) with an aldehyde or a ketone in the presence of an acid catalyst.

[0105] Examples of the acid catalyst used in the condensation reaction include inorganic acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, phosphoric acid, and heteropolyacids; organic acids such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, formic acid, oxalic acid, oxalic acid dihydrate, and trifluoromethanesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, titanium tetrachloride, titanium tetrabromide, and titanium oxide.

[0106] R in the structural unit (II) ２３ and R ２４ is a group derived from an aldehyde or ketone, which is a raw material for the polymer. For example, when formaldehyde is used, R ２３ and R ２４ In addition, when benzaldehyde is used, a polymer in which R is a hydrogen atom can be obtained. ２３ is a phenyl group, and R ２４ Similarly, when naphthaldehyde, anthracenecarboxaldehyde, pyrenecarboxaldehyde, or fluorenecarboxaldehyde is used, a polymer in which R ２３ are respectively a naphthyl group, an anthracenyl group, a pyrenyl group, or a fluorenyl group, and R ２４ is a hydrogen atom.

[0107] R in the structural unit (II) ２３ and R ２４ However, polymers in which none of the atoms is a hydrogen atom can be obtained by using a ketone. Examples of ketones include diaryl ketones and alkylaryl ketones. For example, when diphenyl ketone is used, R ２３ and R ２４ is a phenyl group, and when methyl phenyl ketone is used, a polymer in which R ２３ is a methyl group, and R ２４ is a phenyl group.

[0108] R in the general formula (I) ２３ and R ２４A polymer in which R are directly bonded to each other to form a ring can be obtained by using a cyclic ketone. For example, when fluorenone is used, R ２３ and R ２４ are phenyl groups, and a polymer is obtained in which these are directly bonded to each other to form a ring.

[0109] The amounts of the aldehyde and ketone used may be adjusted so that the resulting polymer has a desired molecular weight and copolymerization ratio, and are preferably 0.05 to 1.1 mol, and more preferably 0.3 to 1.0 mol, relative to 1 mol of the compound (I).

[0110] The condensation reaction may be carried out without a solvent, but is usually carried out using a solvent. Any solvent can be used as long as it does not inhibit the reaction. Examples of solvents include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ethers such as diethylene glycol dimethyl ether, 1,4-dioxane, and tetrahydrofuran; halogenated solvents such as methylene chloride, chloroform, and dichloroethane; hydrocarbons such as toluene and xylene; ketones such as ethyl methyl ketone and isobutyl methyl ketone; esters such as ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, dimethylacetamide, N,N-dimethylformamide, and N-methylpyrrolidone. These can be used alone or in combination of two or more.

[0111] The reaction temperature for the condensation reaction is usually 50 to 200° C., preferably 100 to 200° C. in terms of reaction time. The reaction time may be adjusted by the amount of catalyst, the reaction temperature, etc., but is usually 30 minutes to 50 hours.

[0112] The solvent used in the present invention may be any solvent capable of dissolving or dispersing the compound (I) and the polymer (I), and examples thereof include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether-based solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and Texanol; cellosolve-based solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, and amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ... ether ester solvents such as butyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, and ethoxyethyl ether propionate; BTX solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; paraffin solvents such as mineral spirits, Swazol #310 (Cosmo Matsuyama Oil Co., Ltd.), and Solvesso #100 (Exxon Chemical Co., Ltd.). halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol-based solvents; aniline; triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N,N-dimethylformamide; N,N-dimethylacetamide (DMAc); N-methylpyrrolidone; dimethyl sulfoxide; water, and the like can be used alone or in combination.

[0113] Among these, ketones, ether ester solvents, and particularly propylene glycol monomethyl ether acetate and cyclohexanone are preferred because they have good solubility for the compound (I) and the polymer (I).

[0114] The content of the solvent is preferably 50 parts by mass or more and 99 parts by mass or less, and more preferably 70 parts by mass or more and 95 parts by mass or less, per 100 parts by mass of the semiconductor film-forming material.

[0115] The semiconductor film-forming material of the present invention is characterized by containing the compound (I) or the polymer (I). By containing the compound (I) or the polymer (I), a semiconductor film having excellent heat resistance can be obtained.

[0116] A semiconductor film-forming material containing the compound (I) and the polymer (I) in a total amount of 20 to 100 mass% in the solid content is preferred because it can produce a film with excellent heat resistance. The content in the solid content is more preferably 40 to 100 mass%, and particularly preferably 60 to 100 mass%. The solid content here refers to the components in the semiconductor film-forming material excluding the solvent.

[0117] The semiconductor film-forming material of the present invention may contain compounds other than the compound (I). Examples include fused ring compounds such as fluorene compounds, bisphenol compounds, xanthene compounds, naphthalene compounds, and anthracene compounds, as well as biphenyl compounds. Among these, particularly preferred compounds include the following compounds (a) to (s). The content of the other compounds is preferably 20 mass% or less of the solid content.

[0118]

[0119] The semiconductor film-forming material of the present invention may also contain a polymer other than the polymer (I). Examples include polymers whose monomers are fused ring compounds such as fluorene compounds, bisphenol compounds, xanthene compounds, naphthalene compounds, and anthracene compounds, and biphenyl compounds. Particularly preferred among these are polymers containing the following structural units (u201) to (u210). The content of the other polymer is preferably 20% by mass or less of the solid content.

[0120]

[0121] The semiconductor film-forming material of the present invention may contain a crosslinking agent. The crosslinking agent refers to a compound that reacts with a reactive group in the compound (I) or the polymer (I), linking multiple molecules through a chemical bond, and is incorporated into the polymer after the polymerization reaction, changing its physical and chemical properties. By including a crosslinking agent, a cured product with superior heat resistance can be obtained. Examples of crosslinking agents include phenolic compounds, epoxy compounds, cyanate compounds, amine compounds, benzoxazine compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds, and azide compounds.

[0122] Examples of the phenol compound include alkylphenols such as phenol, cresols, and xylenols; bisphenols such as bisphenol A, bisphenol F, bis(3-methyl-4-hydroxyphenyl)propane, and bis(4-hydroxyphenyl)-1-phenylethane; trisphenols such as α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene; phenol resins such as phenol novolac resin and phenol aralkyl resin; and resinous phenol derivatives such as linear trisphenols, methane-type trisphenols, linear tetrakisphenols, and radial hexanuclear compounds represented by the following general formulas.

[0123] In the formula, R １３ represents an alkyl group having 1 to 4 carbon atoms, n represents an integer of 0 to 2, and m represents an integer of 0 to 1.

[0124] Examples of the epoxy compound include glycidyl ethers of the above-mentioned phenol compounds, tris(2,3-epoxypropyl)isocyanurate, trimethylolmethane triglycidyl ether, and trimethylolpropane triglycidyl ether.

[0125] Examples of cyanate resins include compounds in which the hydroxyl groups of the above-mentioned phenol compounds are substituted with cyanate groups.

[0126] Examples of the amine compound include aromatic amines such as m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, and 1,3-bis(4-aminophenoxy)benzene; alicyclic amines such as diaminocyclohexane, diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo[2.2.1]heptane, and isophoronediamine; and aliphatic amines such as ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, diethylenetriamine, and triethylenetetramine.

[0127] Examples of the benzoxazine compound include Pd-type benzoxazine obtained from a diamine compound and a monofunctional phenol compound, and Fa-type benzoxazine obtained from an amine compound and a bifunctional phenol compound.

[0128] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine have been acyloxymethylated, or a mixture thereof.

[0129] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated, or a mixture thereof; tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated, or a mixture thereof; and the like.

[0130] Examples of glycoluril compounds include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, tetramethylol glycoluril compounds in which 1 to 4 methylol groups have been methoxymethylated or mixtures thereof, and tetramethylol glycoluril compounds in which 1 to 4 methylol groups have been acyloxymethylated or mixtures thereof.

[0131] Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, tetramethylol urea compounds in which one to four methylol groups are methoxymethylated, or mixtures thereof, and tetramethoxyethyl urea.

[0132] Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, etc. Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidene bisazide, 4,4'-oxybisazide, etc.

[0133] The crosslinking agent is preferably a compound having a hydroxyl group or a thiol group, since a cured product having excellent heat resistance can be obtained, and examples thereof include the phenol compounds and glycoluril compounds.

[0134] The content of the crosslinking agent is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total of Compound (I) and Polymer (I). If the content is less than the above range, the effect of improving heat resistance may not be sufficiently exhibited.

[0135] The semiconductor film-forming material of the present invention may contain a polymerization initiator. The polymerization initiator refers to a compound that generates active species by heating or irradiation with active energy rays, etc., and can initiate polymerization, and known polymerization initiators can be used. Examples of polymerization initiators include acid generators, base generators, and radical polymerization initiators. The inclusion of a polymerization initiator is expected to promote curing of the semiconductor film-forming material.

[0136] Polymerization initiators can be classified into photopolymerization initiators that generate active species upon irradiation with active energy rays and thermal polymerization initiators that generate active species upon heating. Photopolymerization initiators include photoacid generators, photobase generators, and photoradical polymerization initiators, while thermal polymerization initiators include thermal acid generators, thermal base generators, and thermal radical polymerization initiators.

[0137] The semiconductor film-forming material of the present invention may contain an acid generator as a polymerization initiator to promote the curing reaction of the crosslinking agent. The acid generator may be any compound capable of generating an acid under predetermined conditions, and examples thereof include onium salts such as sulfonium salts, iodonium salts, and ammonium salts. The acid generator may be either a thermal acid generator that generates an acid by heat or a photoacid generator that generates an acid by light, but a thermal acid generator that generates an acid by heat is particularly preferred due to its good curability.

[0138] Specific examples of the thermal acid generator include bis(4-tert-butylphenyl)iodonium Nonafluorobutanesulfonate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium nonafluorobutanesulfonate, triethylammonium nonafluorobutanesulfonate, pyridinium nonafluorobutanesulfonate, triethylammonium camphorsulfonate, pyridinium camphorsulfonate, tetra-n-butylammonium nonafluorobutanesulfonate, tetraphenylammonium nonafluorobutanesulfonate, tetramethylammonium p-toluenesulfonate, diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, (p-tert-butoxyphenyl)phenyliodonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, bis(p-tert-butoxyphenyl)trifluoromethanesulfonate tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium p-toluenesulfonate, bis(p-tert-butoxyphenyl)phenylsulfonium p-toluenesulfonate, tris(p-tert-butoxyphenyl)sulfonium p-toluenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium butanesulfonate phenylsulfonium, trimethylsulfonium trifluoromethanesulfonate, trimethylsulfonium p-toluenesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium p-toluenesulfonate, dimethylphenylsulfonium trifluoromethanesulfonate, dimethylphenylsulfonium p-toluenesulfonate, dicyclohexylphenylsulfonium trifluoromethanesulfonate,Examples of onium salts include dicyclohexylphenylsulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, (2-norbornyl)methyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate, ethylenebis[methyl(2-oxocyclopentyl)sulfonium trifluoromethanesulfonate], and 1,2'-naphthylcarbonylmethyltetrahydrothiophenium triflate.

[0139] A photoacid generator is a compound that generates an acid when irradiated with light. Examples of the photoacid generator include compounds that generate an acid when exposed to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Specific examples of the photoacid generator include known compounds such as onium salt compounds, sulfone compounds, sulfonic acid ester compounds, quinone diazide compounds, sulfonimide compounds, and diazomethane compounds. Among these, the photoacid generator is preferably at least one selected from the group consisting of onium salt compounds, sulfonimide compounds, and diazomethane compounds, more preferably an onium salt compound, and even more preferably a triarylsulfonium salt.

[0140] Examples of the onium salt compound include diaryliodonium salts, triarylsulfonium salts, and triarylphosphonium salts.

[0141] Specific examples of the diaryliodonium salts include diphenyliodonium salts such as diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, and diphenyliodonium-p-toluenesulfonate; 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroantimonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, and 4- 4-methoxyphenylphenyl iodonium salts such as methoxyphenylphenyl iodonium trifluoroacetate and 4-methoxyphenylphenyl iodonium-p-toluenesulfonate; bis(4-tert-butylphenyl) iodonium tetrafluoroborate, bis(4-tert-butylphenyl) iodonium hexafluorophosphonate, bis(4-tert-butylphenyl) iodonium hexafluoroantimonate, bis(4-tert-butylphenyl) iodonium hexafluoroarsenate, bis(4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl) iodonium trifluoroacetate, bis(4-tert-butylphenyl) iodonium-p-toluenesulfonate and other bis(4-tert-butylphenyl) iodonium salts.

[0142] Examples of the triarylsulfonium salts include triphenylsulfonium salts such as triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, and triphenylsulfonium-p-toluenesulfonate; 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, and 4-methoxyphenyldiphenylsulfonium trifluoromethane sulfonate, 4-methoxyphenyldiphenylsulfonium salts such as 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate; and 4-phenylthiophenyldiphenylsulfonium salts such as 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium-p-toluenesulfonate.

[0143] Examples of the triarylphosphonium salts include triphenylphosphonium salts such as triphenylphosphonium tetrafluoroborate, triphenylphosphonium hexafluorophosphonate, triphenylphosphonium hexafluoroantimonate, triphenylphosphonium hexafluoroarsenate, triphenylphosphonium trifluoromethanesulfonate, triphenylphosphonium trifluoroacetate, and triphenylphosphonium-p-toluenesulfonate; 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphonate, 4-methoxyphenyldiphenylphosphonium hexafluoroantimonate, 4-methoxyphenyldiphenylphosphonium hexafluoroarsenate, and 4-methoxyphenyldiphenylphosphonium tetrafluoroborate. tris(4-methoxyphenyl)phosphonium salts such as tris(4-methoxyphenyl)phosphonium tetrafluoroborate, tris(4-methoxyphenyl)phosphonium hexafluorophosphonate, tris(4-methoxyphenyl)phosphonium hexafluoroantimonate, tris(4-methoxyphenyl)phosphonium hexafluoroarsenate, tris(4-methoxyphenyl)phosphonium trifluoromethanesulfonate, tris(4-methoxyphenyl)phosphonium trifluoroacetate, tris(4-methoxyphenyl)phosphonium-p-toluenesulfonate, and the like.

[0144] Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, and N-(trifluoromethylsulfonyloxy) Sulfonimide compounds having an N-(trifluoromethylsulfonyloxy) group, such as bicyclo-[2,2,1]-heptane-5,6-oxy-2,3-dicarboximide and N-(trifluoromethylsulfonyloxy)naphthylimide; N-(camphanylsulfonyloxy)succinimide, N-(camphanylsulfonyloxy)phthalimide, N-(camphanylsulfonyloxy)diphenylmaleimide, N-(camphanylsulfonyloxy)bicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(camphanylsulfonyloxy) sulfonimide compounds having an N-(camphanylsulfonyloxy) group such as N-(camphanylsulfonyloxy)-7-oxabicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(camphanylsulfonyloxy)bicyclo-[2,2,1]-heptane-5,6-oxy-2,3-dicarboximide, and N-(camphanylsulfonyloxy)naphthylimide; N-(4-methylphenylsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)phthalimide, and N-(4-methylphenylsulfonyloxy)diphenylmethane; sulfonimide compounds having an N-(4-methylphenylsulfonyloxy) group, such as naphthylimide, N-(4-methylphenylsulfonyloxy)bicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)bicyclo-[2,2,1]-heptane-5,6-oxy-2,3-dicarboximide, and N-(4-methylphenylsulfonyloxy)naphthylimide;Examples of sulfonimide compounds having an N-(2-trifluoromethylphenylsulfonyloxy) group include N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo-[2,2,1]-hept-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo-[2,2,1]-heptane-5,6-oxy-2,3-dicarboximide, and N-(2-trifluoromethylphenylsulfonyloxy)naphthylimide;

[0145] Examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-1,1-dimethylethylsulfonyl)diazomethane, and bis(1,1-dimethylethylsulfonyl)diazomethane.

[0146] Commercially available photo-acid generators can also be used. Commercially available photo-cationic polymerization initiators include, for example, "Kayarad (registered trademark) PCI-220" and "Kayarad (registered trademark) PCI-620" manufactured by Nippon Kayaku Co., Ltd.; "UVI-6990" manufactured by The Dow Chemical Company; "ADEKA ARCLES (registered trademark) SP-150", "ADEKA ARCLES (registered trademark) SP-170", "ADEKA ARCLES (registered trademark) SP-500", and "ADEKA ARCLES (registered trademark) SP-606" manufactured by ADEKA Corporation; and "CI-5102", "CIT-1370", "CIT-1682", "CIP-1866S", and "CIP-20" manufactured by Nippon Soda Co., Ltd. 48S", "CIP-2064S"; "DPI-101", "DPI-102", "DPI-103", "DPI-105", "MPI-103", "MPI-105", "BBI-101", "BBI-102", "BBI-103", "BBI-105", "TPS-101", "TPS-102", "TPS-103", "TPS-105", "MDS-103", "MDS-105", "DTS-102", "DTS-103" manufactured by Midori Chemical Co., Ltd.; "PI-2074" manufactured by Solvay Japan Co., Ltd.; and CPI-100P manufactured by San-Apro Ltd.

[0147] The content of the acid generator is preferably 0.001 to 50 parts by mass, and more preferably 0.01 to 20 parts by mass, per 100 parts by mass of the total solid content. When the content is within this range, a composition with excellent curability can be obtained, and a cured product with excellent heat resistance and solvent resistance can be obtained.

[0148] The composition of the present invention may contain a base generator as a polymerization initiator to promote the curing reaction of the crosslinking agent. The base generator may be any compound capable of generating a base under predetermined conditions, and may be either a thermal base generator that generates a base by heat or a photobase generator that generates a base by light, but a thermal base generator that generates a base by heat is particularly preferred because of its good curability.

[0149] Examples of the thermal base generator include carbamate derivatives such as 2-(4-biphenyl)-2-propyl carbamate and 1,1-dimethyl-2-cyanoethyl carbamate, urea derivatives such as urea and N,N,N'-trimethylurea, dihydropyridine derivatives such as 1,4-dihydronicotinamide, dicyandiamide, and salts of acids and bases such as organic salts and inorganic salts.

[0150] Examples of the photobase generator include carbamate compounds, α-aminoketone compounds, quaternary ammonium compounds, O-acyloxime compounds, and aminocyclopropenone compounds.

[0151] Examples of the carbamate compound include 1-(2-anthraquinonyl)ethyl 1-piperidinecarboxylate, 1-(2-anthraquinonyl)ethyl 1H-2-ethylimidazole-1-carboxylate, 9-anthrylmethyl 1-piperidinecarboxylate, 9-anthrylmethyl N,N-diethylcarbamate, 9-anthrylmethyl N-propylcarbamate, 9-anthrylmethyl N-cyclohexylcarbamate, 9-anthrylmethyl 1H-imidazole-1-carboxylate, 9-anthrylmethyl N,N-dioctylcarbamate, 9-anthrylmethyl 1-(4-hydroxypiperidine)carboxylate, 1-pyrenylmethyl 1-piperidinecarboxylate, bis[1-(2-anthraquinonyl)ethyl]1,6-hexanediylbiscarbamate, and bis(9-anthrylmethyl)1,6-hexanediylbiscarbamate. Examples of the α-aminoketone compound include 1-phenyl-2-(4-morpholinobenzoyl)-2-dimethylaminobutane, 2-(4-methylthiobenzoyl)-2-morpholinopropane, and the like.

[0152] Examples of quaternary ammonium compounds that can be used as photobase generators include 1-(4-phenylthiophenacyl)-1-azonia-4-azabicyclo[2,2,2]octanetetraphenylborate, 5-(4-phenylthiophenacyl)-1-aza-5-azoniabicyclo[4,3,0]-5-nonenetetraphenylborate, 8-(4-phenylthiophenacyl)-1-aza-8-azoniabicyclo[5,4,0]-7-undecenetetraphenylborate, etc. Examples of aminocyclopropenone compounds that can be used as photobase generators include 2-diethylamino-3-phenylcyclopropenone, 2-diethylamino-3-(1-naphthyl)cyclopropenone, 2-pyrrolidinyl-3-phenylcyclopropenone, 2-imidazolyl-3-phenylcyclopropenone, 2-isopropylamino-3-phenylcyclopropenone, etc.

[0153] The content of the base generator is preferably 0.001 to 50 parts by mass, and more preferably 0.01 to 20 parts by mass, relative to 100 parts by mass of the total solid content. When the content is within this range, a composition with excellent curability can be obtained, and a cured product with excellent heat resistance and solvent resistance can be obtained.

[0154] When the polymer (I) has an ethylenically unsaturated bond as a reactive group, the composition of the present invention may contain a radical polymerization initiator as a polymerization initiator. As the radical polymerization initiator, either a photoradical polymerization initiator or a thermal radical polymerization initiator can be used.

[0155] Examples of the photoradical polymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin propyl ether, and benzoin butyl ether; benzil ketals such as benzil dimethyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1-benzyl-1-dimethylamino-1-(4'-morpholinobenzoyl)propane, 2-morpholyl-2-(4'-methylmercapto)benzoylpropane, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-1-benzoylcyclohexane, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2-(4'-isopropyl)benzoylpropane, N,N-dimethylaminoacetophenone, 1,1-dichloroacetophenone, 4-butylbenzoyltrichloromethane, and 4-phenoxybenzoyl. Acetophenones such as dichloromethane; anthraquinones such as 2-methylanthraquinone, 1-chloroanthraquinone, and 2-amylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone benzophenones such as 4,4'-bisdiethylaminobenzophenone, Michler's ketone, and 4-benzoyl-4'-methyldiphenyl sulfide; oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; carbazoles such as 3-(2-methyl-2-morpholinopropionyl)-9-methylcarbazole; α-dicarbonyls such as benzyl and methyl benzoylformate;Oxygen compounds such as those described in JP-A-2000-80068, JP-A-2001-233842, JP-A-2005-97141, JP-T-2006-516246, Japanese Patent No. 3860170, Japanese Patent No. 3798008, WO2006 / 018973, JP-A-2011-132215, and WO2015 / 152153 esters; p-methoxyphenyl-2,4-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-butoxystyryl)-s-triazine triazines such as triazine; benzoyl peroxide, 2,2'-azobisisobutyronitrile, ethyl anthraquinone, 1,7-bis(9'-acridinyl)heptane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, benzophenone, phenyl biphenyl ketone, 4-benzoyl-4'-methyldiphenyl sulfide, 2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, thioxanthone / amine, and the like;

[0156] Examples of the thermal radical polymerization initiator include peroxides such as benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 4,4-di(t-butylperoxy)butylvalerate, and dicumyl peroxide; azo compounds such as 2,2′-azobisisobutyronitrile; and tetramethylthiuranium disulfide.

[0157] The content of the radical polymerization initiator is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, and even more preferably 1 part by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the total of the compound (I) having a carbon-carbon double bond and the polymer (I), since a composition excellent in curability and in the heat resistance and solvent resistance of the cured product can be obtained.

[0158] In addition to the above-mentioned components, the semiconductor film-forming material of the present invention may contain other components as needed, such as various additives including inorganic fillers, organic fillers, silane coupling agents, colorants, photosensitizers, antifoaming agents, thickeners, thixotropic agents, surfactants, leveling agents, flame retardants, plasticizers, stabilizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, antistatic agents, flow control agents, and adhesion promoters.

[0159] The semiconductor film-forming material of the present invention can be cured by heating using a hot plate or other hot plate, or an atmospheric oven, inert gas oven, vacuum oven, hot air circulation oven, or the like.

[0160] The heating temperature during thermal curing may be appropriately selected depending on the type of reactive group, but for example, when the reactive functional group is a carbon-carbon triple bond, it is preferably 200 to 400° C., more preferably 250 to 350° C. Furthermore, the curing time is not particularly limited, but from the viewpoint of improving productivity, it is preferably 1 to 60 minutes, more preferably 1 to 30 minutes.

[0161] The semiconductor film-forming material of the present invention can provide a film having excellent heat resistance and solvent resistance, and is therefore useful for forming semiconductor films that require high heat resistance and solvent resistance, and is particularly useful as a material for forming an underlayer film.

[0162] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these.

[0163] <Production Example 1> 29.3 g (250 mmol) of indole, 30.5 g (250 mmol) of 3-hydroxybenzaldehyde, and 166 g of acetonitrile were placed in a reaction flask equipped with a reflux condenser and completely dissolved with stirring. After cooling with water, 4.2 g (25 mmol) of 48% hydrobromic acid was slowly added dropwise. After confirming that the heat generation had subsided, the mixture was returned to room temperature and stirred for 2 hours. The reaction solution was cooled to 10°C, and the precipitate was filtered and washed with 70 g of acetonitrile. The residue was dried under reduced pressure at 40°C to obtain compound (M1) as a pale yellow powder. Yield: 28.5 g (54% yield) １ H-NMR (DMSO-d ６ ) δ / ppm: 5.57 (s, 2H), 6.59-7.25 (m, 16H), 9.16 (s, 2H), 10.66 (s, 2H).

[0164] 26.6 g (60 mmol) of compound (M1), 18.3 g (72 mmol) of iodine, and 80 g of acetonitrile were placed in a reaction flask equipped with a reflux condenser, and the mixture was heated and reacted at 80°C for 14 hours. The reaction solution was cooled to room temperature, and 25 g of a 10% aqueous sodium thiosulfate solution was added dropwise, followed by cooling to 10°C with stirring. The precipitate was filtered and washed with 50 g of acetonitrile, and the residue was dried under reduced pressure at 40°C to obtain compound (A1) as a pale yellow powder. Yield: 20.7 g (78%) １ H-NMR (DMSO-d ６ ) δ / ppm: 6.83-7.49 (m, 16H), 9.68 (s, 2H), 10.49 (s, 2H).

[0165]

[0166] <Production Example 2> 40.0 g (341 mmol) of indole, 47.2 g (341 mmol) of 2,5-dihydroxybenzaldehyde, and 243 g of acetonitrile were placed in a reaction flask equipped with a reflux condenser and completely dissolved with stirring. After cooling with water, 5.7 g (34 mmol) of 48% hydrobromic acid was slowly added dropwise. After confirming that the heat generation had subsided, the mixture was returned to room temperature and stirred for 2 hours. The reaction solution was cooled to 10°C, and the precipitate was filtered and washed with 100 g of acetonitrile. The residue was dried under reduced pressure at 40°C to obtain compound (M2) as a gray powder. Yield: 33.2 g (41%) １ H-NMR (DMSO-d ６ ) δ / ppm: 6.00 (s, 2H), 6.04-7.33 (m, 14H), 8.27 (s, 2H), 9.25 (s, 2H), 10.42 (s, 2H).

[0167] 30.0 g (63.2 mmol) of compound (M2), 19.3 g (75.9 mmol) of iodine, and 90 g of acetonitrile were placed in a reaction flask equipped with a reflux condenser, and the mixture was heated and reacted at 80°C for 14 hours. The reaction solution was cooled to room temperature, and 30 g of a 10% aqueous solution of sodium thiosulfate was added dropwise. The mixture was then cooled to 10°C with stirring. The precipitate was filtered and washed with 50 g of acetonitrile, and the residue was dried under reduced pressure at 40°C to obtain compound (A2) as a light brown powder. Yield: 29.7 g (99%) １ H-NMR (DMSO-d ６ ) δ / ppm: 6.80-7.43 (m, 14H), 8.60 (s, 2H), 8.89 (s, 2H), 10.27 (s, 2H).

[0168]

[0169] <Production Example 3> 6.61 g (15 mmol) of compound (A1) and 60 g of dimethyl sulfoxide (DMSO) were placed in a reaction flask equipped with a reflux condenser, and 5.29 g (66 mmol) of 48% aqueous sodium hydroxide solution was added dropwise at room temperature under a nitrogen stream while stirring. Subsequently, 7.55 g (63 mmol) of 3-bromo-1-propyne was added dropwise, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into 350 g of water, and after stirring for 30 minutes, the precipitate was filtered. The collected residue was dissolved in 50 g of ethyl acetate, and then 50 g of water was added and stirred for 30 minutes to separate the oil and water. The organic layer was desolvated, and the residue was dried under reduced pressure at 40°C to obtain compound (A3) as a light brown powder. Yield: 3.8 g (42%) １ H-NMR (DMSO-d ６ ) δ / ppm: 3.10 (t, 2H), 3.56 (t, 2H), 4.65 (d, 4H), 4.92 (d, 4H) 6.61-7.69 (m, 16H).

[0170]

[0171] <Production Example 4> 5.20 g (11 mmol) of compound (A2) and 50 g of tetrahydrofuran (THF) were placed in a reaction flask equipped with a reflux condenser, and 3.67 g (44 mmol) of 48% aqueous sodium hydroxide solution was added dropwise at room temperature under a nitrogen stream while stirring. Subsequently, 5.00 g (42 mmol) of 3-bromo-1-propyne was added dropwise, and the mixture was stirred at room temperature for 1 hour. The reaction solution was poured into 300 g of water, and after stirring for 30 minutes, the precipitate was filtered. 50 g of isopropanol was added to the collected residue, and after stirring for 30 minutes, the mixture was filtered. The residue was dried under reduced pressure at 40°C to obtain compound (A4) as a light brown powder. Yield: 1.3 g (20%) １ H-NMR (DMSO-d ６ ) δ / ppm: 3.39 (t, 2H), 3.53 (t, 2H), 4.61 (d, 4H), 6.82 (t, 2H), 7.09-7.43 (m, 12H), 10.41 (s, 2H).

[0172]

[0173] <Production Example 5> 5.20 g (11 mmol) of compound (A2) and 50 g of dimethyl sulfoxide (DMSO) were placed in a reaction flask equipped with a reflux condenser, and 5.50 g (66 mmol) of 48% aqueous sodium hydroxide solution was added dropwise at room temperature under a nitrogen stream while stirring. Subsequently, 7.50 g (63 mmol) of 3-bromo-1-propyne was added dropwise, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into 300 g of water, and after stirring for 30 minutes, the precipitate was filtered. The collected residue was dissolved in 50 g of ethyl acetate, and then 50 g of water was added and stirred for 30 minutes to separate the oil and water. The organic layer was desolvated, and the residue was dried under reduced pressure at 40°C to obtain compound (A5) as a light brown powder. Yield: 4.90 g (65%) １ H-NMR (DMSO-d ６ ) δ / ppm: 3.09 (t, 2H), 3.44 (t, 2H), 3.52 (t, 2H), 4.65-4.85 (m, 12H), 6.72-7.49 (m, 14H).

[0174]

[0175] <Production Example 6> A reaction flask equipped with a reflux condenser was charged with 30.0 g (256 mmol) of indole, 52.0 g (256 mmol) of 4-(trimethylsilyl)ethynylbenzaldehyde, and 230 g of acetonitrile, and while cooling with water and stirring, 9.0 g (52.0 mmol) of 48% hydrobromic acid was slowly added dropwise. The reaction solution was returned to room temperature and stirred for 2 hours. The reaction solution was cooled to 10°C, and the precipitate was filtered and washed with 100 g of acetonitrile. The residue was dried under reduced pressure at 40°C to obtain compound (M3) as a pale yellow powder. Yield: 25.0 g (33%)

[0176] 22.0 g (36 mmol) of compound (M3), 10.0 g (40 mmol) of chloranil, and 880 g of o-xylene were placed in a reaction flask equipped with a reflux condenser, and the mixture was heated and reacted at 100°C for 30 hours. The reaction solution was cooled to room temperature, and 200 g of methanol was added to the residue after removing the solvent, followed by stirring at room temperature for 30 minutes. The precipitate was filtered and washed twice with 200 g of methanol, and the residue was dried under reduced pressure at 40°C to obtain compound (M4) as a pale yellow powder. Yield: 10.9 g (50%)

[0177] 9.0 g (15 mmol) of compound (M4), 80 g of tetrahydrofuran, and 80 g of methanol were placed in a reaction flask equipped with a reflux condenser and stirred at room temperature for 30 minutes. 2.3 g (16 mmol) of potassium carbonate was added, and the mixture was allowed to react at room temperature for 3 hours. 20 g of ion-exchanged water was added to the reaction solution, and the precipitate was filtered. The residue was washed three times with 20 g of methanol and dried under reduced pressure at 40°C to obtain compound (A6) as a pale yellow powder. Yield: 6.1 g (88%) １ H-NMR (DMSO-d ６ ) δ / ppm: 4.37 (s, 2H), 6.88-7.83 (m, 16H), 10.64 (s, 2H).

[0178]

[0179] <Production Example 7> 11.7 g (100 mmol) of indole, 13.1 g (100 mmol) of 3-formylbenzonitrile, and 50 g of acetonitrile were placed in a reaction flask equipped with a reflux condenser and completely dissolved with stirring. The mixture was cooled with water, and 1.7 g (10 mmol) of 48% hydrobromic acid was slowly added dropwise. The reaction solution was returned to room temperature and stirred for 2 hours. The reaction solution was cooled to 10°C, and the precipitate was filtered and washed with 20 g of acetonitrile. The residue was dried under reduced pressure at 40°C to obtain compound (M5) as a gray powder. Yield: 3.8 g (yield 16.5%) １ H-NMR (DMSO-d ６ ) δ / ppm: 5.89 (s, 2H), 6.83-8.08 (m, 16H), 10.91 (s, 2H).

[0180] 2.12 g (4.6 mmol) of compound (M5) and 20 g of dimethyl sulfoxide (DMSO) were placed in a flask equipped with a reflux condenser, and 1.00 g (12.0 mmol) of 48% aqueous sodium hydroxide solution was added dropwise at room temperature under a nitrogen stream while stirring. Subsequently, 1.41 g (12.0 mmol) of 3-bromo-1-propyne was added dropwise, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into 120 g of water, and after stirring for 30 minutes, the precipitate was filtered. 40 g of methanol was added to the collected residue, and the mixture was stirred for 30 minutes. The suspension was filtered, and the residue was dried under reduced pressure at 40°C to obtain compound (A7) as a pale orange powder. Yield: 1.5 g (61%) １H-NMR (DMSO-d ６ ) δ / ppm: 2.89 (t, 2H), 4.81 (d, 2H), 5.03 (d, 2H), 6.19 (s, 2H), 7.00-7.94 (m, 16H).

[0181]

[0182] <Production Example 8> 11.7 g (100 mmol) of indole, 19.4 g (100 mmol) of 2-fluorenecarboxaldehyde, and 90 g of acetonitrile were placed in a reaction flask equipped with a reflux condenser and completely dissolved with stirring. The mixture was cooled with water, and 1.7 g (10 mmol) of 48% hydrobromic acid was slowly added dropwise. The reaction solution was returned to room temperature and stirred for 2 hours. The reaction solution was cooled to 10°C, and the precipitate was filtered and washed with 20 g of acetonitrile. The residue was dried under reduced pressure at 40°C to obtain compound (M6) as a brown powder. Yield: 27.0 g (yield 92.1%) １ H-NMR (DMSO-d ６ ) δ / ppm: 3.84 (s, 4H), 5.85 (s, 2H), 6.77-7.87 (m, 22H), 10.76 (s, 2H).

[0183] A reaction flask equipped with a reflux condenser was charged with 2.35 g (4.0 mmol) of compound (M6) and 30 g of dimethyl sulfoxide (DMSO), and while stirring, 3.0 g (36.0 mmol) of a 48% aqueous sodium hydroxide solution was added dropwise at room temperature under a nitrogen stream. Subsequently, 4.25 g (36.0 mmol) of 3-bromo-1-propyne was added dropwise, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into 120 g of water, and after stirring for 30 minutes, the precipitate was filtered. 20 g of methanol was added to the collected residue, and after stirring for 30 minutes, the mixture was filtered. The residue was dried under reduced pressure at 40°C to obtain compound (A8) as a pale orange powder. Yield: 1.6 g (49%) １ H-NMR (DMSO-d ６ ) δ / ppm: 2.47 (d, 8H), 2.94 (t, 4H), 3.05 (t, 2H), 4.72 (d, 2H), 4.92 (d, 2H), 6.10 (s, 2H), 6.90-8.34 (m, 22H).

[0184]

[0185] <Production Example 9> 3.10 g (7.0 mmol) of compound (M1) and 20 g of dimethyl sulfoxide (DMSO) were placed in a flask equipped with a reflux condenser, and 2.92 g (35.0 mmol) of a 48% aqueous sodium hydroxide solution was added dropwise at room temperature under a nitrogen stream while stirring. Subsequently, 4.23 g (35.0 mmol) of 3-bromo-1-propene was added dropwise, and the mixture was stirred at room temperature for 3 hours. The reaction solution was poured into 100 g of water, and after stirring for 30 minutes, the precipitate was filtered. 30 g of methanol was added to the collected residue, and the mixture was stirred for 30 minutes. The suspension was filtered, and the residue was dried under reduced pressure at 40°C to obtain compound (A9) as a pale yellow powder. Yield: 3.0 g (71%) １ H-NMR (DMSO-d ６ ) δ / ppm: 4.52 (m, 4H), 4.89 (m, 4H), 5.17-5.34 (m, 10H), 5.89 (s, 2H), 5.96 (m, 2H), 6.72-7.46 (m, 16H).

[0186]

[0187] <Production Example 10> 2.20 g of compound (M2), 0.54 g of benzaldehyde, and 24 g of PGMEA were placed in a reaction flask equipped with a reflux condenser, and while stirring, 0.14 g of methanesulfonic acid was added. The temperature was raised under a nitrogen stream, and stirring was carried out at 140°C for 20 hours. After cooling to room temperature and removing insoluble matter, the reaction solution was added dropwise to 120 g of a 2 / 1 mixed solvent of n-hexane and 2-propanol, and the mixture was stirred for 30 minutes. The precipitate was filtered and dried under reduced pressure at 60°C, yielding 2.2 g of polymer (A10) as a brown powder. The molecular weight (polystyrene equivalent) measured by GPC was a weight average molecular weight of 1,450 and a dispersity of 1.25.

[0188]

[0189] <Production Example 11> 2.20 g of compound (M2), 0.90 g of fluorenone, and 24 g of N-methylpyrrolidone were placed in a reaction flask equipped with a reflux condenser, and while stirring, 0.32 g of methanesulfonic acid was added. The temperature was raised under a nitrogen stream, and stirring was carried out at 140°C for 20 hours. After cooling to room temperature and removing insoluble matter, the reaction solution was added dropwise to 120 g of a 2 / 1 n-hexane / 2-propanol mixed solvent, and the mixture was stirred for 30 minutes. The precipitate was filtered and dried under reduced pressure at 60°C, yielding 2.3 g of polymer (A11) as a black powder. The molecular weight (polystyrene equivalent) measured by GPC was a weight average molecular weight of 1,990, and a dispersity of 1.07.

[0190]

[0191] <Production Example 12> 2.10 g of compound (A5), 0.32 g of benzaldehyde, and 24 g of PGMEA were placed in a reaction flask equipped with a reflux condenser, and while stirring, 0.20 g of methanesulfonic acid was added. The temperature was raised under a nitrogen stream, and stirring was carried out at 100°C for 20 hours. After cooling to room temperature and removing insoluble matter, the reaction solution was added dropwise to 100 g of a 2 / 1 n-hexane / 2-propanol mixed solvent, and the mixture was stirred for 30 minutes. The precipitate was filtered and dried under reduced pressure at 60°C, yielding 1.7 g of polymer (A12) as a black-brown powder. The molecular weight (polystyrene equivalent) measured by GPC was a weight average molecular weight of 2,640 and a dispersity of 1.17.

[0192]

[0193] <Production Example 13> 2.85 g of compound (M6), 0.37 g of benzaldehyde, and 30 g of propylene glycol monomethyl ether acetate (PGMEA) were placed in a reaction flask equipped with a reflux condenser, and while stirring, 0.22 g of methanesulfonic acid was added. The temperature was raised under a nitrogen stream, and stirring was carried out at 100°C for 20 hours. After cooling to room temperature and removing insoluble matter, the reaction solution was added dropwise to 150 g of a 2 / 1 n-hexane / 2-propanol mixed solvent and stirred for 30 minutes. The precipitate was filtered and dried under reduced pressure at 60°C, yielding 1.5 g of polymer (A13) as a brown powder. The molecular weight (polystyrene equivalent) measured by GPC was a weight average molecular weight of 2,350 and a dispersity of 1.17.

[0194]

[0195] [Examples 1 to 23 and Comparative Examples 1 to 6] Each component was weighed, mixed, and dissolved by stirring according to the formulation (parts by mass) shown in Tables 1 to 3. After confirming that the solid was completely dissolved, the mixture was filtered through a fluororesin filter (pore size: 0.2 μm) to obtain a composition for evaluation.

[0196] The components in the table are as follows: A1: Compound (A1) Compound (I) A2: Compound (A2) Compound (I) A3: Compound (A3) Compound (I) A4: Compound (A4) Compound (I) A5: Compound (A5) Compound (I) A6: Compound (A6) Compound (I) A7: Compound (A7) Compound (I) A8: Compound (A8) Compound (I) A9: Compound (A9) Compound (I) A10: Polymer (A10) Polymer (I) and Polymer (II) A11: Polymer (A11) Polymer (I) and Polymer (II) A12: Polymer (A12) Polymer (I) and Polymer (II) A13: Polymer (A13) Polymer (I) and Polymer (II) A14: Compound (A14) Compound other than Compound (I) A15: Compound (A15) Compound other than Compound (I) A16: Compound (A16) A compound other than Compound (I) A17: Compound (A17) A compound other than Compound (I) A18: Polymer (A18) A polymer containing a compound other than Compound (I) as a monomer B1: Compound (B1) below, crosslinking agent (glycoluril compound) B2: Compound (B2) below, crosslinking agent (phenol compound) C1: Bis(4-tert-butylphenyl)iodonium nonafluorobutanesulfonate (polymerization initiator: thermal acid generator) D1: Propylene glycol monomethyl ether acetate (PGMEA) solvent D2: Cyclohexanone solvent

[0197]

[0198]

[0199] (Preparation of Evaluation Substrate) The prepared evaluation composition was applied to a silicon wafer substrate using a spin coater so that the film thickness after heating would be 200 nm. The coated substrate was heated for 60 seconds on a hot plate set at 170°C, and then heated for an additional 60 seconds on a hot plate set at 300°C to prepare an evaluation substrate. Using this evaluation substrate, various evaluations were performed as follows. The evaluation results are summarized in Tables 1 to 3.

[0200] (Heat Resistance Evaluation) Using a Semilab SE-2000 spectroscopic ellipsometer, the film thickness was measured at five points on the evaluation substrate, and the average value was taken as the pre-test film thickness. The evaluation substrate was heated at 300°C for 60 seconds, and the film thickness after heating was measured in the same manner, and this was taken as the post-test film thickness. A film with a change in film thickness before and after the test of less than 5% was rated A, 5% or more but less than 10% was rated B, and 10% or more was rated C. The smaller the change in film thickness before and after the test, the more preferably the material can be used as a semiconductor film-forming material.

[0201] (Solvent Resistance Evaluation) Using a Semilab SE-2000 spectroscopic ellipsometer, film thicknesses at five points on the evaluation substrate were measured, and the average value was taken as the pre-test film thickness. The evaluation substrate was immersed in PGMEA at 25°C for 60 seconds, then heated at 170°C for 60 seconds, and the film thickness after evaporating the PGMEA was measured in the same manner, and this was taken as the post-test film thickness. A film with a change in film thickness before and after the test of less than 1% was rated A, 1% or more but less than 3% was rated B, and 3% or more was rated C. The smaller the change in film thickness before and after the test, the more preferably the film can be used as a semiconductor film-forming material.

[0202] (Dry Etching Test) Using a Semilab SE-2000 spectroscopic ellipsometer, film thickness was measured at five points on the evaluation substrate, and the average value was taken as the film thickness before the test. Using an etching device (ULVAC CE-300I), the film thickness after etching was measured in the same manner. Etching was performed under the following conditions, and film thickness was measured after etching for 15 seconds, 30 seconds, 60 seconds, and 120 seconds, and the film thickness etched per second (etching rate) was calculated. The etching conditions are as follows: Ar gas flow rate: 44 ml / min CF ４Gas flow rate: 11 ml / min Chamber pressure: 4.0 Pa RF power: 100 W When the etching rate of Comparative Example 2 (compound (A15)) was taken as 100, an etching rate of less than 90 was rated A, an etching rate of 90 or more but less than 100 was rated B, and an etching rate of 100 or more was rated C. The smaller the etching rate, the higher the etching resistance, and the more preferably the material can be used as a semiconductor film-forming material, and the more preferably the material can be used as an underlayer film-forming material.

[0203] (Filling property, flatness) SiO ２ The composition was applied to a stepped substrate (walls 500 nm wide and 100 nm high, trenches 500 nm wide). The composition was heated at 170°C for 60 seconds and at 300°C for 60 seconds to produce a film. The spin-coating conditions were adjusted so that the film thickness from the trench was 200 nm. Evaluation of embeddability: Substrate slices were prepared, and when observed with an SEM (Hitachi High-Technologies Corporation S-4800), those that were embedded in the steps without voids were rated A, and those with voids were rated B. Evaluation of flatness: Flatness was evaluated from the difference (film thickness difference) between the thickest point of the film formed on the wall of the substrate and the thinnest point of the film formed on the trench. A film thickness difference of less than 10 nm was rated A, 10 nm or more but less than 30 nm was rated B, and 30 nm or more was rated C. The smaller the film thickness difference, the higher the flatness, making the material suitable for use as a semiconductor film-forming material, and particularly suitable for use as an underlayer film-forming material.

[0204]

[0205]

[0206]

[0207] <Production Example 14> A flask equipped with a reflux condenser was charged with 15.0 g (26 mmol) of compound (M6) and 450 g of o-xylene, and 7.8 g (31 mmol) of iodine was added with stirring, followed by a reaction at 140°C for 5 hours. The reaction solution was cooled to room temperature, and 120 g of a 10% aqueous solution of sodium thiosulfate was added dropwise and stirred for 30 minutes. After filtering the precipitate, the filter cake was washed with 50 g of o-xylene and further washed twice with 100 g of a mixed solvent of water / methanol = 1 / 2 (weight ratio). The filter cake was dried under reduced pressure at 40°C to obtain compound (M7) as a gray powder. Yield: 13.3 g (yield 89%) １ H-NMR (THF-d ８ ) δ / ppm: 4.12 (s, 4H), 6.77-8.19 (m, 22H), 9.72 (s, 2H).

[0208] A reaction flask equipped with a reflux condenser was charged with 5.0 g (9.0 mmol) of compound (M7) and 250 g of dimethyl sulfoxide (DMSO), and while stirring, 9.0 g (77 mmol) of 48% aqueous potassium hydroxide solution was added dropwise at room temperature under a nitrogen stream. Subsequently, 9.2 g (77 mmol) of 3-bromo-1-propyne was added dropwise, and the mixture was stirred at room temperature for 1 hour. The reaction solution was poured into 250 g of water, stirred for 30 minutes, and then filtered. 250 g of water was added to the filtrate, stirred for 30 minutes, and then filtered. The residue was washed twice with 100 g of a water / methanol = 1 / 2 (weight ratio) mixed solvent. Compound (A19) was obtained as a yellow powder by drying under reduced pressure at 40 °C. Yield: 2.2 g (44%) １ H-NMR (THF-d ８ ) δ / ppm: 2.51 (d, 8H), 2.63 (t, 4H), 3.05 (t, 2H), 4.67 (d, 4H), 6.76-8.19 (m, 22H).

[0209]

[0210] <Production Example 15> 4.0 g (30 mmol) of 5-hydroxyindole, 5.8 g (30 mmol) of 2-fluorenecarboxaldehyde, and 30 g of acetonitrile were placed in a flask equipped with a reflux condenser. While stirring, 0.51 g (3 mmol) of 48% hydrobromic acid was added dropwise at room temperature, and the mixture was stirred for 2 hours. 10 g of water was added to the reaction solution, and the mixture was stirred at room temperature for 30 minutes and then filtered. The collected residue was washed three times with 10 g of methanol and dried under reduced pressure at 40°C, yielding compound (M8) as a greenish-gray powder. Yield: 5.2 g (56%) １ H-NMR (DMSO-d ６ ) δ / ppm: 4.12 (s, 4H), 5.66 (s, 2H), 6.13-8.29 (m, 20H), 10.09 (s, 2H), 10.33 (s, 2H).

[0211] In a flask equipped with a reflux condenser, 4.5 g (7 mmol) of compound (M8) and 90 g of acetonitrile were placed, and 2.2 g (9 mmol) of chloranil was added at room temperature while stirring. After stirring at room temperature for 30 minutes, the temperature was raised to 70°C and the mixture was heated and stirred for 7 hours. The reaction solution was cooled to room temperature and then filtered. The collected residue was washed six times with 30 g of o-xylene and dried under reduced pressure at 40°C to obtain compound (M9) as a gray powder. Yield: 4.5 g (100%) １ H-NMR (DMSO-d ６ ) δ / ppm: 4.12 (s, 4H), 6.43-8.24 (m, 20H), 10.09 (s, 2H), 10.33 (s, 2H)

[0212] 4.0 g (6 mmol) of compound (M9) and 60 g of dimethyl sulfoxide (DMSO) were placed in a flask equipped with a reflux condenser, and 4.3 g (52 mmol) of 48% aqueous potassium hydroxide solution was added at room temperature under a nitrogen stream while stirring. Subsequently, 6.2 g (52 mmol) of 3-bromo-1-propene was added, and the mixture was stirred at room temperature for 1 hour. 80 g of water was added dropwise to the reaction solution, and after stirring for 30 minutes, the precipitate was filtered. The collected residue was washed with 10 g of a 1 / 1 mixed solvent of methanol and water, and then dried under reduced pressure at 40°C to obtain compound (A20) as a reddish-brown powder. Yield: 3.7 g (61%) １ H-NMR (DMSO-d ６) δ / ppm: 2.55 (d, 8H), 2.73 (t, 4H), 3.05 (t, 2H), 3.38 (t, 2H), 4.65 (d, 4H), 4.74 (d, 4H), 6.74-8.26 (m, 20H.)

[0213]

[0214] <Production Example 16> 75.0 g (510 mmol) of 5-methoxyindole, 69.3 g (510 mmol) of 3-methoxybenzaldehyde, and 270 g of acetonitrile were placed in a flask equipped with a reflux condenser. While stirring, 8.59 g (51 mmol) of 48% hydrobromic acid was added dropwise at room temperature, and the mixture was stirred for 2 hours. The reaction solution was cooled, stirred for 30 minutes, and then filtered. The collected residue was washed three times with 20 g of acetonitrile and dried under reduced pressure at 40°C, yielding compound (M10) as a gray powder. Yield: 33.1 g (25%)

[0215] In a flask equipped with a reflux condenser, 45.0 g (85 mmol) of compound (M10) and 134 g of dimethylformamide were placed, and 21.9 g (89 mmol) of chloranil was added at room temperature while stirring. After stirring at room temperature for 30 minutes, the temperature was raised to 100 ° C. and the mixture was heated and stirred for 2 hours. The reaction solution was cooled to room temperature, and 202 g of methanol was added. After stirring for 30 minutes, the mixture was filtered. The collected residue was washed three times with 20 g of acetonitrile, washed with 120 g of a mixed solvent of tetrahydrofuran / methanol / water = 1 / 1 / 1, and then dried under reduced pressure at 40 ° C. to obtain compound (M11) as a greenish-brown powder. Yield: 32.1 g (72% yield)

[0216] A flask equipped with a reflux condenser was charged with 25.0 g (47 mmol) of compound (M11), 224 g of acetic acid, and 95.7 g (568 mmol) of 48% hydrobromic acid. After stirring at room temperature for 30 minutes, the mixture was heated to 120°C and stirred for 48 hours. The reaction solution was cooled to room temperature, and 202 g of water was added. After stirring for 30 minutes, the mixture was filtered. The collected residue was dissolved in 56 g of acetonitrile to remove insoluble materials, and the filtrate was dried under reduced pressure at 40°C to obtain a solid. This solid was washed with 116 g of ethyl acetate, washed with 17 g of a 1 / 1 mixed solvent of methanol and water, and then dried under reduced pressure at 40°C to obtain compound (M12) as a greenish-brown powder. Yield: 4.3 g (20% yield).

[0217] 2.0 g (4.2 mmol) of compound (M12) and 15 g of dimethylformamide were placed in a flask equipped with a reflux condenser, and 2.2 g (26 mmol) of 48% aqueous sodium hydroxide solution was added at room temperature under a nitrogen stream while stirring. Subsequently, 3.2 g (26 mmol) of 3-bromo-1-propene was added, and the mixture was stirred at room temperature for 1 hour. A mixed solvent of 15 g of methanol and 15 g of water was added dropwise to the reaction solution, and after stirring for 30 minutes, the precipitate was filtered. The collected residue was washed with 12 g of a mixed solvent of methanol / water = 1 / 1 and then dried under reduced pressure at 40 °C to obtain compound (A21) as a yellowish brown powder. Yield: 2.0 g (69%) １ H-NMR (DMSO-d ６ ) δ / ppm: 3.07 (t, 2H), 3.43 (t, 2H), 3.53 (t, 2H), 4.50 (d, 4H), 4.62 (d, 4H), 4.90 (d, 4H), 6.16 (d, 2H), 7.09-7.69 (m, 12H).

[0218]

[0219] Production Example 17: 2.28 g of compound (A19), 0.30 g of benzaldehyde, and 30 g of N-methylpyrrolidone were placed in a reaction flask equipped with a reflux condenser, and the mixture was heated to 50°C under a nitrogen stream. 0.18 g of methanesulfonic acid was slowly added dropwise, and the mixture was further heated and stirred at 80°C for 8 hours. After cooling to room temperature and removing insoluble matter, the reaction solution was added dropwise to 150 g of a 2 / 1 n-hexane / 2-propanol mixed solvent and stirred for 30 minutes. The precipitate was filtered and dried under reduced pressure at 60°C, yielding 1.3 g of polymer (A22) as a brown powder. The molecular weight (polystyrene equivalent) of the obtained powder measured by gel permeation chromatography (GPC) was a weight average molecular weight (Mw) of 2,490 and a dispersity of 1.17.

[0220]

[0221] [Examples 24 to 27] Each component was weighed, mixed, and dissolved by stirring according to the formulation (parts by mass) shown in Table 4. After confirming that the solid was completely dissolved, the mixture was filtered through a fluororesin filter (pore size: 0.2 μm) to obtain a composition for evaluation.

[0222] The components in the table are as follows: A19: Compound (A19) Compound (I) A20: Compound (A20) Compound (I) A21: Compound (A21) Compound (I) A22: Polymer (A22) Polymer (I) and Polymer (II) D1: Propylene glycol monomethyl ether acetate (PGMEA) Solvent D2: Cyclohexanone Solvent

[0223] Using the prepared evaluation composition, various evaluations were carried out in the same manner as in Example 1. The results are summarized in Table 4.

[0224]

[0225] As shown in Tables 1 to 4, the semiconductor film-forming material of the present invention using compound (I) or polymer (I) gave a film having excellent heat resistance and solvent resistance, compared to the comparative example material not using compound (I) or polymer (I). Furthermore, the semiconductor film-forming material of the present invention gave a film having excellent dry etching properties, and also had good embedding properties and flatness during film formation.

Claims

1. A semiconductor film-forming material containing a compound represented by the following general formula (I) and having one or more reactive groups in the molecule, or a polymer whose monomer is a compound represented by the following general formula (I) and having one or more reactive groups in the molecule, and a solvent. In the formula, A represents a hydrocarbon ring having 6 carbon atoms; １ and X ２ each independently represents an aryl group having 6 to 30 carbon atoms which may be substituted with a reactive group or a group having a reactive group, a heterocyclic group having 2 to 30 carbon atoms which may be substituted with a reactive group or a group having a reactive group, or a heterocyclic-containing group having 3 to 30 carbon atoms which may be substituted with a reactive group or a group having a reactive group, １ , R ２ , R ３ , R ４ , R ６ , R ７ , R ８ and R ９ each independently represents a hydrogen atom, a halogen atom, a reactive group, a nitro group, a hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a reactive group, a heterocyclic group of 2 to 10 carbon atoms which may be substituted with a reactive group, or a heterocyclic group containing 3 to 30 carbon atoms which may be substituted with a reactive group, or a group in which one or more methylene groups in the hydrocarbon group of 1 to 20 carbon atoms have been substituted with a divalent group selected from the following <Group A>, or a group in which one or more methylene groups in the heterocyclic group containing 3 to 30 carbon atoms have been substituted with a divalent group selected from the following <Group A>, R ５ and R １０ each independently represents a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms which may be substituted with a reactive group, a heterocyclic group of 2 to 10 carbon atoms which may be substituted with a reactive group, or a heterocyclic ring-containing group of 3 to 30 carbon atoms which may be substituted with a reactive group, or a group in which one or more methylene groups in the hydrocarbon group of 1 to 20 carbon atoms have been substituted with a divalent group selected from <Group A> below, or a group in which one or more methylene groups in the heterocyclic ring-containing group of 3 to 30 carbon atoms have been substituted with a divalent group selected from <Group A> below. <Group A>: -O-, -CO-, -COO-, -OCO-, -NR １１ -, -NR １２ CO-, -S-R １１ and R １２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

2. X in general formula (I) １ and X ２ is a phenyl group which may be substituted with a reactive group or a group having a reactive group, a hydrocarbon-type aromatic fused ring group having 7 to 30 carbon atoms which may be substituted with a reactive group or a group having a reactive group, or a heterocycle-containing fused ring group having 3 to 30 carbon atoms which may be substituted with a reactive group or a group having a reactive group.

3. R ​​in general formula (I) ５ and R １０ 2. The semiconductor film-forming material according to claim 1, wherein is a hydrocarbon group having 1 to 20 carbon atoms substituted with a reactive group.

4. The semiconductor film-forming material according to claim 1, wherein the reactive group is a carbon-carbon triple bond or a phenolic hydroxyl group.

5. A film-forming material for semiconductors according to claim 1, wherein the compound represented by general formula (I) has two or more reactive groups in the molecule.

6. The semiconductor film-forming material according to claim 1, wherein the compound represented by general formula (I) is a compound represented by the following general formula (Ia), (Ib) or (Ic): Each symbol in the formula is the same as in the general formula (I).

7. The semiconductor film-forming material according to claim 1, which contains a crosslinking agent.

8. The semiconductor film-forming material according to claim 1, which contains a polymerization initiator.

9. A semiconductor member-forming material containing the semiconductor film-forming material according to any one of claims 1 to 8.

10. A semiconductor process member forming material containing the semiconductor film forming material according to any one of claims 1 to 8.

11. A material for forming an underlayer film, comprising the semiconductor film-forming material according to any one of claims 1 to 8.

12. An underlayer film formed using the underlayer film forming material according to claim 11.

13. A semiconductor device manufactured using the semiconductor film-forming material according to any one of claims 1 to 8.

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