Composition for forming silicon-containing underlayer film for directed self-assembly

Abstract

A composition for forming a silicon-containing underlayer film, which is used for forming a self-assembled pattern, and which contains [A] a polysiloxane, [B] 0 parts by mass or more but less than 2 parts by mass of a strongly acidic additive per 100 parts by mass of the polysiloxane, and [C] a solvent, the polysiloxane contains a structural unit derived from a hydrolyzable silane (A) represented by formula (A-1). (In formula (A-1), a represents an integer of 1-3. And b represents an integer of 0-2. And a + b represents an integer of 1-3. R1 represents an organic group having a ring structure other than an aromatic hydrocarbon ring. And R2 represents a specific group. ).

Description

TECHNICAL FIELD

[0001] The present application relates to a silicon-containing underlayer film forming composition for forming an underlayer film of a self-assembled film, and a self-assembly pattern forming method using the same. BACKGROUND

[0002] A thermosetting self-assembled film having a nanoscale repeating structure is known to have different properties from a general homogenous film, and a self-assembled film having a nanoscale repeating structure using a block copolymer has been proposed.

[0003] For example, a pattern forming method in which a plurality of segments constituting a block polymer are regularly arranged to form a pattern in a block polymer layer has been disclosed (Patent Literature 1).

[0004] In addition, a composition for forming a thermosetting self-assembled film, which includes a block copolymer, a crosslinking agent, and an organic solvent, has been disclosed (Patent Literature 2).

[0005] In recent years, with further miniaturization of large scale integrated circuits (LSIs), a technology for processing finer structures has been required. In response to such a requirement, attempts have been made to form a finer pattern using a phase separation structure formed by self-assembly of a block copolymer formed by bonding polymers that are not compatible with each other to each other. For example, a pattern forming method in which an underlayer film for easily arranging a self-assembled film into a desired vertical pattern is formed, a self-assembled film including a block copolymer formed by bonding two or more polymers is formed on the underlayer film, the block copolymer in the self-assembled film is phase separated, and a phase of at least one of the polymers constituting the block copolymer is selectively removed has been proposed.

[0006] As a material for forming the above underlayer film, for example, an underlayer film forming composition including a polymer having a unit structure including a polycyclic aromatic vinyl compound in a main chain has been disclosed (Patent Literature 3), an underlayer film forming composition for a self-assembled film including a polymer having a unit structure including an aliphatic polycyclic structure of an aliphatic polycyclic compound in a main chain has been disclosed (Patent Literature 4), and the like.

[0007] In addition, aspects in which, in order to arrange a self-assembled pattern at a target position, ultraviolet rays or radiation are irradiated to the above underlayer film in a manner of overlapping with the arrangement position to cause changes in the concave-convex of the surface of the underlayer film, the surface energy (hydrophilicity / hydrophobicity) have been disclosed (see Patent Literature 2 and the like).

[0008] On the other hand, in the field of manufacturing semiconductor devices, a technique of forming a fine pattern on a substrate by a photolithography technique, etching the substrate in accordance with the pattern, and processing the substrate is widely used. With the progress of the photolithography technique, fine patterning has been developed, and the active light used has been shortened in wavelength. In order to suppress the influence of reflection of the active light from the semiconductor substrate, a method of providing a lower film containing silicon or the like, which is called an antireflection film, is widely used (Patent Literature 5 and the like).

[0009] The present applicant has proposed a composition for forming a silicon-containing lower film of a self-assembled film, which is a composition for forming a silicon-containing lower film of a self-assembled film, contains [A] a polysiloxane and [B] a solvent, but does not contain a strongly acidic additive (Patent Literature 6).

[0010] Prior Art Documents Patent Literatures Patent Literature 1: Japanese Patent Application Laid-Open (JP A) No. 2009-234114 Patent Literature 2: Japanese Patent Application Laid-Open (JP A) No. 2011-122081 Patent Literature 3: International Publication No. 2014 / 097993 Patent Literature 4: International Publication No. 2015 / 041208 Patent Literature 5: Japanese Patent Application Laid-Open (JP A) No. 2007-163846 Patent Literature 6: International Publication No. 2022 / 210960 SUMMARY PROBLEMS TO BE SOLVED BY THE INVENTION A technology for realizing a desired self-assembled pattern (also referred to as a pattern structure of a self-assembled film, a microphase separation structure), that is, a microphase separation structure of a layer containing a block copolymer induced vertically with respect to a substrate, is expected.

[0011] The present application relates to a silicon-containing lower film provided between a substrate and a self-assembled film containing a block copolymer, and aims to provide a composition for forming a lower film that contributes to the induction of a microphase separation structure of a layer containing a block copolymer vertically with respect to a substrate. In addition, the present application relates to a self-assembled pattern forming method using the composition for forming a lower film.

[0012] TECHNICAL SOLUTION FOR SOLVING THE PROBLEMS The present inventors and the like have conducted intensive studies in order to solve the above-described problems, and as a result, have found that the above-described problems can be solved, and have completed the present application having the following gist.

[0013] That is, the present application includes the following.

[0014] [1] A silicon-containing underlayer film forming composition for forming a self-assembly pattern, the silicon-containing underlayer film forming composition containing: [A] a polysiloxane, [B] a strong acidic additive in an amount of 0 mass part or more and less than 2 mass parts with respect to 100 mass parts of the polysiloxane, and [C] a solvent, the polysiloxane contains structural units derived from a hydrolyzable silane (A) represented by the following formula (A-1).

[0015] [Chemical Formula 1] (In formula (A-1), a represents an integer of 1 to 3.

[0016] b represents an integer of 0 to 2.

[0017] a + b represents an integer of 1 to 3.

[0018] R 1 represents an organic group having a ring structure other than an aromatic hydrocarbon ring.

[0019] R 2 represents an alkyl group which can be substituted, an aryl group which can be substituted, an aralkyl group which can be substituted, a halogenated alkyl group which can be substituted, a halogenated aryl group which can be substituted, a halogenated aralkyl group which can be substituted, an alkoxyalkyl group which can be substituted, an alkoxyaryl group which can be substituted, an alkoxyaralkyl group which can be substituted, or an alkenyl group which can be substituted, or, R 2 represents an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more of them.

[0020] X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0021] In the case where R 1 , R 2 , and X are plural, the plural R 1 , R 2 , and X can be the same or different. [2] The silicon-containing underlayer film forming composition according to [1], wherein the strong acidic additive is a strong acidic additive having a first acid dissociation constant of 1 or less in water.

[0022] [3] The silicon-containing underlayer film forming composition according to [1] or [2], wherein the strong acidic additive is a photo-acid generator.

[0023] [4] The silicon-containing underlayer film-forming composition according to any one of [1] to [3], wherein the ring structure in the R 1 contains a heteroatom.

[0024] [5] The silicon-containing underlayer film-forming composition according to any one of [1] to [4], wherein the proportion of Q units in all the structural units of the [A] component is 65 mol% or less.

[0025] [6] A method for manufacturing a substrate having a self-assembly pattern, comprising: a step of forming an underlayer film on a substrate using the silicon-containing underlayer film-forming composition according to any one of [1] to [5], and a step of forming a self-assembly film on the upper side of the underlayer film to form a self-assembly pattern.

[0026] [7] A method for manufacturing a substrate having a self-assembly pattern, comprising: a step of forming an underlayer film on a substrate using the silicon-containing underlayer film-forming composition according to any one of [1] to [5], a step of forming a neutral film on the underlayer film, and a step of forming a self-assembly film on the neutral film to form a self-assembly pattern.

[0027] [8] A method for manufacturing a substrate having a self-assembly pattern, comprising: a step of forming an underlayer film on a substrate using the silicon-containing underlayer film-forming composition according to any one of [1] to [5], a step of forming a neutral film on a part of the underlayer film, a step of forming a brush film on the underlayer film on which the neutral film is not formed to form a template film for a self-assembly pattern formed of the neutral film and the brush film, and a step of forming a self-assembly film on the template film for a self-assembly pattern to obtain a self-assembly pattern.

[0028] [9] A method for manufacturing a substrate having a self-assembly pattern, comprising: a step of forming an organic underlayer film on a substrate, a step of forming an underlayer film on the organic underlayer film using the silicon-containing underlayer film-forming composition according to any one of [1] to [5], a step of forming a neutral film on a part of the underlayer film, a step of forming a brush film on the underlayer film on which the neutral film is not formed to form a template film for a self-assembly pattern formed of the neutral film and the brush film, and a step of forming a self-assembled film on the self-assembled pattern template film.

[0029]

[10] A method for manufacturing a substrate having a self-assembled pattern, comprising: a step of forming an organic underlayer film on a substrate, a step of forming an underlayer film on the organic underlayer film using the silicon-containing underlayer film-forming composition according to any one of [1] to [5], a step of forming a neutral film on the underlayer film, a step of forming a resist film on the neutral film, a step of exposing and developing the resist film to obtain a resist pattern, a step of etching the neutral film using the resist pattern as a mask, a step of etching or stripping the resist pattern to obtain a patterned neutral film on the underlayer film, a step of forming a brush film on the underlayer film and the patterned neutral film on the underlayer film, a step of etching or stripping the brush film on the patterned neutral film to expose the neutral film, thereby forming a self-assembled pattern template film composed of the neutral film and the brush film, and a step of forming a self-assembled film on the self-assembled pattern template film to obtain a self-assembled pattern.

[0030]

[11] The method for manufacturing a substrate having a self-assembled pattern according to [6], which is used for forming a self-assembled pattern by directed self-assembly (DSA).

[0031]

[12] A method for manufacturing a semiconductor device, comprising: (1) a step of forming an underlayer film on a substrate using the silicon-containing underlayer film-forming composition according to any one of [1] to [5], (2) a step of forming a layer containing a block copolymer on the underlayer film, (3) a step of phase-separating the block copolymer, (4) a step of removing a part of the phase-separated block copolymer, and (5) a step of etching the substrate.

[0032] Effects of the Invention According to the present invention, it is possible to provide a silicon-containing underlayer film-forming composition which can form a self-assembled film that induces a desired vertical pattern. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1Ais a schematic diagram showing one mode of self-assembly pattern formation (1).

[0034] Figure 1B is a schematic diagram showing one mode of self-assembly pattern formation (2).

[0035] Figure 1C is a schematic diagram showing one mode of self-assembly pattern formation (3).

[0036] Figure 1D is a schematic diagram showing one mode of self-assembly pattern formation (4).

[0037] Figure 1E is a schematic diagram showing one mode of self-assembly pattern formation (5).

[0038] Figure 1F is a schematic diagram showing one mode of self-assembly pattern formation (6).

[0039] Figure 1G is a schematic diagram showing one mode of self-assembly pattern formation (7).

[0040] Figure 1H is a schematic diagram showing one mode of self-assembly pattern formation (8).

[0041] Figure 1I is a schematic diagram showing one mode of self-assembly pattern formation (9).

[0042] Figure 1J is a schematic diagram showing one mode of self-assembly pattern formation (10).

[0043] Figure 2 is a photograph showing a microphase separation structure of a self-assembly film produced in Example 17.

[0044] Figure 3 is a photograph showing a microphase separation structure of a self-assembly film produced in Comparative Example 2. DETAILED DESCRIPTION

[0045] In order to arrange the self-assembly pattern at the above-mentioned target position, as one of the means for setting the contrast of the concavo-convex of the film surface that becomes the lower layer, the lower layer film can be patterned using the photolithography technique known in the field of semiconductor device production.

[0046] If the above-mentioned lower layer film is patterned, a step is generated between the patterned lower layer film portion and the portion exposed by the lower layer (substrate or the like) that is further below and is not covered with the lower layer film, but this step can become a cause of causing the arrangement of the self-assembly film to be poor.

[0047] In addition, in the case where the layer under the above-mentioned patterned lower layer film is a silicon-containing film, the exposed portion (portion where the lower layer film for pattern arrangement is not present) of the silicon-containing film becomes a state where the hydrophilicity is high due to the silanol group contained in the silicon-containing film. However, if the hydrophilicity of the exposed portion is too high, when a self-assembled film using a block copolymer described later is formed, the block copolymer cannot be arranged in a desired vertical pattern, and it can cause arrangement failure.

[0048] In order to eliminate these unevenness and eliminate the adverse situation of hydrophilicity and hydrophobicity, there is a method of burying the exposed portion of the above-mentioned silicon-containing film in a brush material composed of a high molecular polymer. The brush material is provided to have an effect of not showing a self-assembled pattern in a portion outside the target, but if the brush material exists in the upper portion of the above-mentioned patterned lower layer film which is the starting point of vertical arrangement of the block copolymer which becomes a self-assembled film, it becomes a cause of causing arrangement failure of the self-assembled film.

[0049] The present inventors and others have researched the above-mentioned technical problem, and as a result, it has been found that if an acidic additive contained in the above-mentioned lower layer film and the silicon-containing film disposed thereunder is excessively leached, the hydrophilicity and hydrophobicity of the surface of the above-mentioned lower layer film are disturbed, as a result, the brush material also adheres to the lower layer film, thereby causing arrangement failure of the block copolymer which constitutes the self-assembled film.

[0050] Based on the above-mentioned insight, the present inventors and others have researched the composition of the silicon-containing film, and completed a composition for forming a silicon-containing lower layer film which can form a self-assembled film which induces a desired vertical pattern, and a pattern forming method using the same.

[0051] Note that the present inventors and others have proposed a composition for forming a silicon-containing lower layer film of a self-assembled film which does not contain a strong acidic additive in International Publication No. 2022 / 210960, but the present inventors and others have further researched repeatedly, and as a result, it has been found that if the acidic additive is a small amount, a self-assembled film which induces a desired vertical pattern can be formed.

[0052] Hereinafter, the present application will be described.

[0053] [Composition for forming a silicon-containing lower layer film] The composition for forming a silicon-containing lower layer film of the present application contains: [A] a polysiloxane, [B] a strong acidic additive in an amount of 0 mass part or more and less than 2 mass parts with respect to 100 mass parts of the polysiloxane, and [C] a solvent.

[0054] The [A] polysiloxane contains a structural unit derived from a hydrolyzable silane (A) represented by the following formula (A-1).

[0055] [Chemical 2] (In formula (A-1), a represents an integer of 1 to 3.

[0056] b represents an integer of 0 to 2.

[0057] a + b represents an integer of 1 to 3.

[0058] R 1 represents an organic group having a ring structure other than an aromatic hydrocarbon ring.

[0059] R 2 represents an alkyl group which can be substituted, an aryl group which can be substituted, an aralkyl group which can be substituted, a haloalkyl group which can be substituted, a haloaryl group which can be substituted, a haloaralkyl group which can be substituted, an alkoxyalkyl group which can be substituted, an alkoxyaryl group which can be substituted, an alkoxyaralkyl group which can be substituted, or an alkenyl group which can be substituted, or, R 2 represents an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more of them.

[0060] X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0061] In the case where R 1 , R 2 , and X are plural, the plural R 1 , R 2 , and X can be the same or different. Note that R 2 is not an organic group having an unsaturated bond and having a ring structure.

[0062] Note that, in the present application, as the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned.

[0063] R 1 in formula (A-1) is R 1 represents an organic group having a ring structure other than an aromatic hydrocarbon ring.

[0064] The ring structure can have a hetero atom or can not have a hetero atom. As the hetero atom, for example, a nitrogen atom, an oxygen atom, and the like can be mentioned.

[0065] As the ring structure in R 1 , an aliphatic hydrocarbon ring or a heterocycle can be mentioned. As the atom other than a carbon atom constituting the heterocycle, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like can be mentioned.

[0066] As the ring structure, it can be an aromatic heterocycle, or it can be a non-aromatic ring.

[0067] As the ring structure, for example, a 3-membered ring to a 10-membered ring, and the like can be given. Specifically, a 3-membered ring, a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, an 8-membered ring, and the like can be given. Among them, a 5-membered ring to a 7-membered ring is preferred.

[0068] The ring structure can be a monocyclic structure, or it can be a polycyclic structure. As the polycyclic structure, for example, it can be a bicyclic structure, or it can be a tricyclic structure.

[0069] In the polycyclic structure, the bonding mode of each ring to each other, for example, includes the following 3.

[0070] • Sharing 1 atom: for example, a spiro compound • Sharing 2 atoms: a case where 2 rings share 2 atoms like decalin • Bridged structure: a case where 2 rings are considered to share 3 or more atoms like norbornane Note that, in the case of a polycyclic structure, the number of atoms constituting the ring is taken as the number of its member rings. For example, norbornane is a 7-membered ring.

[0071] R 1 The ring structure can be one, or it can be a plurality. R 1 The ring structure, for example, can be 1 to 3, or it can be 1 to 2.

[0072] R 1 For example, it does not have a Si-O group.

[0073] As R 1 , the number of carbon atoms is not particularly limited, and the number of carbon atoms of R 1 is preferably 4 to 30, and more preferably 4 to 20.

[0074] R 1 Generally has a hydrogen atom. In addition to carbon atoms and hydrogen atoms, R 1 may have an oxygen atom, can have a nitrogen atom, can have a sulfur atom, and can have a halogen atom.

[0075] R 1 may have an ionic bond, or it can not have an ionic bond. In the case where R 1 has an ionic bond, R 1 may have an ionic bond in the atom row linking the ring structure and the silicon atom, or it can have an ionic bond in the atom row branching from the atom row linking the ring structure and the silicon atom.

[0076] R 1is preferably represented by the following formula (A-2a).

[0077] [Chemical Formula 3] (In formula (A-2a), R 11 represents a single bond, or a divalent organic group which can have an ionic bond.

[0078] R 12 represents a group having a ring structure other than an aromatic hydrocarbon ring.

[0079] represents a binding bond. In the case where R 11 is a divalent organic group which can have an ionic bond, the number of carbon atoms of R 11 is not particularly limited, and the number of carbon atoms of R 11 is preferably 1 to 25, and more preferably 1 to 15.

[0080] From the viewpoint of appropriately obtaining the effects of the present application, R 12 is preferably any one of the following formulas (A-2c-1) to (A-2c-7). In other words, from the viewpoint of appropriately obtaining the effects of the present application, R 12 in formula (A-2a) is preferably any one of the following formulas (A-2c-1) to (A-2c-7).

[0081] [Chemical Formula 4] (In formula (A-2c-1), R 1b to R b10 each independently represent a hydrogen atom, a halogen atom, or a monovalent group. R b1 and R b8 may together form a methylene group, or a 1,2-ethylene group. Among them, one of R 1b to R b10 represents a binding bond to R 11 in formula (A-2a).

[0082] In formula (A-2c-2), X 1 to X 5 represent N or CR (wherein R each independently represents a hydrogen atom, a halogen atom, or a monovalent group). Among them, at least one of X 1 to X 5 is N. represents a binding bond.

[0083] In formula (A-2c-3), X 11represents N or CR (wherein R represents a hydrogen atom, a halogen atom, or a monovalent group.). c1 ~R c5 each independently represents a hydrogen atom, a halogen atom, or a monovalent group. Among them, R c1 ~R c5 one of them represents a binding bond to R 11 in formula (A-2a).

[0084] In formula (A-2c-4), X 21 represents O or S. R d1 ~R d4 each independently represents a hydrogen atom, a halogen atom, or a monovalent group. Among them, R d1 ~R d4 one of them represents a binding bond to R 11 in formula (A-2a).

[0085] In formula (A-2c-5), R e1 ~R e4 each independently represents a hydrogen atom, a halogen atom, or a monovalent group. Among them, R e1 ~R e4 one of them represents a binding bond to R 11 in formula (A-2a).

[0086] In formula (A-2c-6), X 31 represents -C(=O)-N(R f3 )-, -C(=O)-C(R f4 )(R f5 )-, or -C(R f6 )(R f7 )-. R f1 ~R f7 each independently represents a hydrogen atom, a halogen atom, or a monovalent group. Among them, R f1 and R f2 one of them represents a binding bond to R 11 in formula (A-2a).

[0087] In formula (A-2c-7), represents a binding bond. As R 1b ~R b10 , R c1 ~R c5 , R d1 ~R d4 , R e1 ~R e4 , R f1 ~R f7As the monovalent group having 1 to 10 carbon atoms, for example, a monovalent organic group having 1 to 10 carbon atoms can be given. As the monovalent organic group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms can be given.

[0088] As the alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclobutyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, n-pentyl group, 1-methyln-butyl group, 2-methyln-butyl group, 3-methyln-butyl group, 1,1-dimethyln-propyl group, 1,2-dimethyln-propyl group, 2,2-dimethyln-propyl group, 1-ethyln-propyl group, cyclopentyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 3-methylcyclobutyl group, 1,2-dimethylcyclopropyl group, 2,3-dimethylcyclopropyl group, 1-ethy lcyclopropyl group, 2-ethy lcyclopropyl group, n-hexyl group, 1-methyln-pentyl group, 2-methyln-pentyl group, 3-methyln-pentyl group, 4-methyln-pentyl group, 1,1-dimethyln-butyl group, 1,2-dimethyln-butyl group, 1,3-dimethyln-butyl group, 2,2-dimethyln-butyl group, 2,3-dimethyln-butyl group, 3,3-dimethyln-butyl group, 1-ethyln-butyl group, 2-ethyln-butyl group, 1,1,2-trimethyln-propyl group, 1,2,2-trimethyln-propyl group, 1-ethy l-1-methy ln-propyl group, 1-ethy l-2-methy ln-propyl group, cyclohexyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 1-ethy lcyclobutyl group, 2-ethy lcyclobutyl group, 3-ethy lcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-isopropylcyclopropyl group, 2-isopropylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1-ethy l-2-methy lcyclopropyl group, 2-ethy l-1-methy lcyclopropyl group, 2-ethy l-2-methy lcyclopropyl group, 2-ethy l-3-methy lcyclopropyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, and the like can be given.

[0089] As the alkoxy group having 1 to 10 carbon atoms, for example, a methoxy group, an ethoxy group, a n-propoxy group, an i-propoxy group, a n-butoxy group, an i-butoxy group, a sec-butoxy group, a t-butoxy group, a n-pentoxy group, a 1-methyln-butoxy group, a 2-methyln-butoxy group, a 3-methyln-butoxy group, a 1,1-dimethyln-propoxy group, a 1,2-dimethyln-propoxy group, a 2,2-dimethyln-propoxy group, a 1-ethyln-propoxy group, a n-hexyloxy group, a 1-methyln-pentoxy group, a 2-methyln-pentoxy group, a 3-methyln-pentoxy group, a 4-methyln-pentoxy group, a 1,1-dimethyln-butoxy group, a 1,2-dimethyln-butoxy group, a 1,3-dimethyln-butoxy group, a 2,2-dimethyln-butoxy group, a 2,3-dimethyln-butoxy group, a 3,3-dimethyln-butoxy group, a 1-ethyln-butoxy group, a 2-ethyln-butoxy group, a 1,1,2-trimethyln-propoxy group, a 1,2,2-trimethyln-propoxy group, a 1-ethy l-1-methyln-propoxy group, a 1-ethy l-2-methyln-propoxy group, a cyclopentoxy group, a cyclohexyloxy group, a norbornyloxy group, an adamantyloxy group, an adamantylmethyloxy group, an adamantylethyloxy group, a tetracyclodeca- oxy group, a tricyclodeca-oxy group, and the like can be given.

[0090] As the alkenyl group having 2 to 10 carbon atoms, for example, there are mentioned ethenyl, 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylethenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylethenyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylethenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylethenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-l-ethyl-2-propenyl, 1-ethyl-2-methyl-l-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-l-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-l-cyclopentenyl, 2-methyl-2-cyclopentenyl, 2-methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylenecyclopentyl, 3-methyl-l-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylenecyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl, and the like.

[0091] Note that in the present specification, "iso" means "isopropyl", "sec" means "sec-butyl", and "tert" means "tert-butyl".

[0092] As the formula (A-2c-2), for example, the following formula (A-2c-2-1) can be given.

[0093] As the formula (A-2c-6), for example, the following formulae (A-2c-6-1) to (A-2c-6-3) can be given.

[0094] [Chemical Formula 5] (In the formula (A-2c-2-1), each of R independently represents a hydrogen atom, a halogen atom, or a monovalent group. represents a binding bond.

[0095] In the formulae (A-2c-6-1) to (A-2c-6-3), each of R f1 to R f7 independently represents a hydrogen atom, a halogen atom, or a monovalent group. Among them, one of R f1 and R f2 represents a binding bond to R 11 in the formula (A-2a). < < R 11 > > > As R 11 , a single bond, or any one of the following divalent organic groups represented by the formulae (A-2-1) to (A-2-4) is preferable.

[0096] [Chemical Formula 6] (In the formula (A-2-1), R 21 represents an alkylene group having 1 to 6 carbon atoms.

[0097] In formula (A-2-2), R 31 represents an alkylene group having 1 to 6 carbon atoms. R 32 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 33 represents a single bond or an alkylene group having 1 to 6 carbon atoms.

[0098] In formula (A-2-3), R 41 represents an alkylene group having 1 to 6 carbon atoms. R 42 represents a single bond or an alkylene group having 1 to 6 carbon atoms.

[0099] In formula (A-2-4), R 51 represents an alkylene group having 1 to 6 carbon atoms. R 52 and R 53 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 54 represents a single bond or an alkylene group having 1 to 6 carbon atoms.

[0100] In formulae (A-2-1) to (A-2-4), 1 represents a binding bond to Si. 2 represents a binding bond to R 12 ). Note that the amino group (-N(R 32 )-) in formula (A-2-2) can be cationized in the silicon-containing underlayer film-forming composition and the underlayer film. For example, in the case where nitric acid is added to the silicon-containing underlayer film-forming composition, the amino group (-N(R 32 )-) in formula (A-2-2) can be cationized to form a nitrate salt.

[0101] As the alkylene group having 1 to 6 carbon atoms in R 21 , R 31 , R 33 , R 41 , R 42 , and R 51 , any one of a linear shape and a branched shape can be used. As the alkylene group having 1 to 6 carbon atoms, for example, a linear alkylene group such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and the like can be used. Among them, methylene, ethylene, trimethylene, and tetramethylene are preferable.

[0102] As the alkyl group having 1 to 4 carbon atoms in R 32 , R 52 , and R 53 , any one of a linear shape and a branched shape can be used. As the alkyl group having 1 to 4 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, and the like can be used.

[0103] As R 32 R 52 and R 53 The preferred atoms are hydrogen atoms, methyl groups, and ethyl groups.

[0104] << R in equation (A-1) 2 >> The alkyl group can be any of the straight-chain, branched, or cyclic forms, and its number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.

[0105] Specific examples of alkyl groups, specifically straight-chain or branched alkyl groups, include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-propyl. It includes 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl, etc.

[0106] Specific examples of cyclic alkyl groups include: cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl Cycloalkyl groups, including 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl and 2-ethyl-3-methylcyclopropyl; and cross-linked cycloalkyl groups, including bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl and bicyclodecyl.

[0107] The aryl group can be any one of a monovalent group derived from a benzene group, a condensed ring aromatic hydrocarbon compound by removing one hydrogen atom therefrom, and a ring- linked aromatic hydrocarbon compound by removing one hydrogen atom therefrom, and the number of carbon atoms thereof is not particularly limited, and is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.

[0108] For example, as the aryl group, there can be mentioned an aryl group having 6 to 20 carbon atoms, and as one example, there can be mentioned a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, a 1-chrysenyl group, a 2-chrysenyl group, a 5-chrysenyl group, a 2-brylenyl group, a 1-pyrenyl group, a 2-pyrenyl group, a pentaphenyl group, a benzopyrenyl group, a triphenylene group; a biphenyl-2-yl group (o-biphenyl group), a biphenyl-3-yl group (m-biphenyl group), a biphenyl-4-yl group (p-biphenyl group), a p-terphenyl-4-yl group, an m-terphenyl-4-yl group, an o-terphenyl-4-yl group, a 1, 1'-binaphthyl-2-yl group, a 2, 2'-binaphthyl-1-yl group, and the like, but is not limited thereto.

[0109] The aralkyl group is an alkyl group substituted with an aryl group, and as specific examples of such aryl group and alkyl group, the same specific examples as described above can be mentioned. The number of carbon atoms of the aralkyl group is not particularly limited, and is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.

[0110] As specific examples of the aralkyl group, there can be mentioned a phenylmethyl group (benzyl group), a 2-phenyl ethylene group, a 3-phenyl n-propyl group, a 4-phenyl n-butyl group, a 5-phenyl n-pentyl group, a 6-phenyl n-hexyl group, a 7-phenyl n-heptyl group, a 8-phenyl n-octyl group, a 9-phenyl n-nonyl group, a 10-phenyl n-decyl group, and the like, but is not limited thereto.

[0111] The haloalkyl group, haloaryl group and haloaralkyl group are respectively an alkyl group, an aryl group and an aralkyl group substituted with one or more halogen atoms, and as specific examples of such alkyl group, aryl group and aralkyl group, the same specific examples as described above can be mentioned.

[0112] As the halogen atom, there can be mentioned a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

[0113] The number of carbon atoms of the haloalkyl group is not particularly limited, and is preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and further more preferably 10 or less.

[0114] Specific examples of the halogenated alkyl group include monofluoromethyl, difluoromethyl, trifluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoropropan-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl, and the like, but are not limited thereto.

[0115] The number of carbon atoms of the halogenated aryl group is not particularly limited, and is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.

[0116] Specific examples of the halogenated aryl group include 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl, pentafluorophenyl, 2-fluoro-1-naphthyl, 3-fluoro-1-naphthyl, 4-fluoro-1-naphthyl, 6-fluoro-1-naphthyl, 7-fluoro-1-naphthyl, 8-fluoro-1-naphthyl, 4,5-difluoro-1-naphthyl, 5,7-difluoro-1-naphthyl, 5,8-difluoro-1-naphthyl, 5,6,7,8-tetrafluoro-1-naphthyl, heptafluoro-1-naphthyl, 1-fluoro-2-naphthyl, 5-fluoro-2-naphthyl, 6-fluoro-2-naphthyl, 7-fluoro-2-naphthyl, 5,7-difluoro-2-naphthyl, heptafluoro-2-naphthyl, and the like, and in addition to these, a group in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group), but is not limited thereto.

[0117] The number of carbon atoms of the halogenated aralkyl group is not particularly limited, and is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less.

[0118] Specific examples of the halogenated aralkyl group include 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl, 2,5-difluorobenzyl, 2,6-difluorobenzyl, 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2,3,4-trifluorobenzyl, 2,3,5-trifluorobenzyl, 2,3,6-trifluorobenzyl, 2,4,5-trifluorobenzyl, 2,4,6-trifluorobenzyl, 2,3,4,5-tetrafluorobenzyl, 2,3,4,6-tetrafluorobenzyl, 2,3,5,6-tetrafluorobenzyl, 2,3,4,5,6-pentafluorobenzyl, and the like, and in addition, groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group) can also be mentioned, but the list is not limited thereto.

[0119] The alkyl group, the aryl group, and the aralkyl group in the alkoxyl group, the aryloxy group, and the aralkyloxy group are each a group in which 1 or more hydrogen atoms are replaced with an alkyl group, an aryl group, or an aralkyl group. Specific examples of the alkyl group, the aryl group, and the aralkyl group include the same examples as those described above.

[0120] As the alkyl group in the alkoxyl group, for example, a straight-chain, branched, and cyclic alkyl group having 1 to 20 carbon atoms can be mentioned.

[0121] As the straight-chain or branched alkyl group, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, a 1-methyln-butyl group, a 2-methyln-butyl group, a 3-methyln-butyl group, a 1,1-dimethyln-propyl group, a 1,2-dimethyln-propyl group, a 2,2-dimethyln-propyl group, a 1-ethyln-propyl group, a n-hexyl group, a 1-methyln-pentyl group, a 2-methyln-pentyl group, a 3-methyln-pentyl group, a 4-methyln-pentyl group, a 1,1-dimethyln-butyl group, a 1,2-dimethyln-butyl group, a 1,3-dimethyln-butyl group, a 2,2-dimethyln-butyl group, a 2,3-dimethyln-butyl group, a 3,3-dimethyln-butyl group, a 1-ethyln-butyl group, a 2-ethyln-butyl group, a 1,1,2-trimethyln-propyl group, a 1,2,2-trimethyln-propyl group, a 1-ethyl-1-methyln-propyl group, a 1-ethyl-2-methyln-propyl group, and the like can be mentioned.

[0122] Further, as the cyclic alkoxy group, for example, there are mentioned cyclopropyloxy group, cyclobutyloxy group, 1-methylcyclopropyloxy group, 2-methylcyclopropyloxy group, cyclopentyloxy group, 1-methylcyclobutyloxy group, 2-methylcyclobutyloxy group, 3-methylcyclobutyloxy group, 1,2-dimethylcyclopropyloxy group, 2,3-dimethylcyclopropyloxy group, 1-ethylcyclopropyloxy group, 2-ethylcyclopropyloxy group, cyclohexyloxy group, 1-methylcyclopentyloxy group, 2-methylcyclopentyloxy group, 3-methylcyclopentyloxy group, 1-ethylcyclobutyloxy group, 2-ethylcyclobutyloxy group, 3-ethylcyclobutyloxy group, 1,2-dimethylcyclobutyloxy group, 1,3-dimethylcyclobutyloxy group, 2,2-dimethylcyclobutyloxy group, 2,3-dimethylcyclobutyloxy group, 2,4-dimethylcyclobutyloxy group, 3,3-dimethylcyclobutyloxy group, 1-n-propylcyclopropyloxy group, 2-n-propylcyclopropyloxy group, 1-isopropylcyclopropyloxy group, 2-isopropylcyclopropyloxy group, 1,2,2-trimethylcyclopropyloxy group, 1,2,3-trimethylcyclopropyloxy group, 2,2,3-trimethylcyclopropyloxy group, 1-ethyl-2-methylcyclopropyloxy group, 2-ethyl-1-methylcyclopropyloxy group, 2-ethyl-2-methylcyclopropyloxy group and 2-ethyl-3-methylcyclopropyloxy group, and the like.

[0123] As the specific examples of the alkoxyalkyl group, there are mentioned methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, ethoxymethyl group and the like lower (about 5 or less in the number of carbon atoms) alkoxy lower (about 5 or less in the number of carbon atoms) alkyl group, but not limited thereto.

[0124] As the specific examples of the alkoxyaryl group, there are mentioned 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-(1-ethoxy)phenyl group, 3-(1-ethoxy)phenyl group, 4-(1-ethoxy)phenyl group, 2-(2-ethoxy)phenyl group, 3-(2-ethoxy)phenyl group, 4-(2-ethoxy)phenyl group, 2-methoxynaphth-1-yl group, 3-methoxynaphth-1-yl group, 4-methoxynaphth-1-yl group, 5-methoxynaphth-1-yl group, 6-methoxynaphth-1-yl group, 7-methoxynaphth-1-yl group, and the like, but not limited thereto.

[0125] As the specific examples of the alkoxyarylalkyl group, there are mentioned 3-(methoxyphenyl)benzyl group, 4-(methoxyphenyl)benzyl group, and the like, but not limited thereto.

[0126] The alkenyl group can be either of linear or branched, and the number of carbon atoms thereof is not particularly limited, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, further preferably 10 or less.

[0127] As specific examples of the alkenyl group, the following can be given: ethenyl (vinyl), 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylethenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylethenyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylethenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylethenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-t-butylethenyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, and the like.

[0128] Further, as the substituent in the alkyl group, aryl group, aralkyl group, haloalkyl group, haloaryl group, haloaralkyl group, alkoxyalkyl group, aryloxy group, alkoxyaryl group, alkoxyaralkyl group, alkoxy group, and aralkyloxy group, for example, an alkyl group, aryl group, aralkyl group, haloalkyl group, haloaryl group, haloaralkyl group, alkoxyalkyl group, aryloxy group, alkoxyaryl group, alkoxyaralkyl group, alkoxy group, and aralkyloxy group can be mentioned, and as specific examples thereof and preferred numbers of carbon atoms thereof, the same specific examples and numbers of carbon atoms as mentioned above or hereinafter can be mentioned.

[0129] Further, the aryloxy group mentioned above as the substituent is a group in which an aryl group is bonded via an oxygen atom (-O-), and as specific examples of such an aryl group, the same specific examples as mentioned above can be mentioned. The number of carbon atoms of the aryloxy group is not particularly limited, and is preferably 40 or less, more preferably 30 or less, and still more preferably 20 or less, and as specific examples thereof, a phenoxy group, a naphthalen-2-yloxy group, and the like can be mentioned, but is not limited thereto.

[0130] Further, in the case where two or more substituents are present, the substituents can be bonded to each other to form a ring.

[0131] As the organic group having an acryloyl group, an acryloyloxy methyl group, an acryloyloxy ethyl group, an acryloyloxy propyl group, and the like can be mentioned.

[0132] As the organic group having a methacryloyl group, a methacryloyloxy methyl group, a methacryloyloxy ethyl group, a methacryloyloxy propyl group, and the like can be mentioned.

[0133] As the organic group having a mercapto group, a mercaptoethyl group, a mercaptobutyl group, a mercaptohexyl group, a mercaptooctyl group, and the like can be mentioned.

[0134] As the organic group having an amino group, an amino group, an aminomethyl group, an aminoethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, and the like can be mentioned, but is not limited thereto. The organic group having an amino group will be described in further detail hereinafter.

[0135] As the organic group having an alkoxy group, for example, a methoxymethyl group, a methoxyethyl group can be mentioned, but is not limited thereto. Among them, an alkoxy group directly bonded to a silicon atom is excluded.

[0136] As the organic group having a sulfonyl group, for example, a sulfonylalkyl group can be mentioned, but is not limited thereto.

[0137] As the organic group having a cyano group, a cyanoethyl group, a cyanopropyl group, a thiocyanate group, and the like can be mentioned.

[0138] As the organic group having an amino group, an organic group having at least any one of a primary amino group, a secondary amino group, and a tertiary amino group can be mentioned. A hydrolyzed condensate in which a hydrolyzable silane having a tertiary amino group is hydrolyzed with a strong acid to form a counter cation having a tertiary ammonium group can be preferably used. Further, the organic group can contain a hetero atom such as an oxygen atom, a sulfur atom, in addition to the nitrogen atom constituting the amino group.

[0139] As the organic group having an amino group, an organic group represented by the following formula (A1) can be mentioned as a preferable example.

[0140] [Chemical Formula 7] In formula (A1), R 101 and R 102 independently represent a hydrogen atom or a hydrocarbon group, and L independently represents an alkylene group which can be substituted. represents a bond.

[0141] As the hydrocarbon group, an alkyl group, an alkenyl group, and the like can be mentioned, but are not limited thereto. As specific examples of these alkyl group and alkenyl group, the same specific examples as mentioned above in R 2 can be mentioned.

[0142] Further, as the alkylene group, either of a linear form and a branched form can be mentioned, and the number of carbon atoms is usually from 1 to 10, and preferably from 1 to 5. For example, a linear alkylene group such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene can be mentioned.

[0143] As the organic group having an amino group, an amino group, an aminomethyl group, an aminoethyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, and the like can be mentioned, but are not limited thereto.

[0144] X in formula (A-1) As the alkoxy group in X, for example, the same alkoxy group as exemplified in the explanation of R 2 can be mentioned.

[0145] As the halogen atom in X, for example, the same halogen atom as exemplified in the explanation of R 2 can be mentioned.

[0146] The aralkyloxy group is a monovalent group derived from the hydroxy group of an aralkyl alcohol by removing a hydrogen atom therefrom, and as specific examples of the aralkyl group in the aralkyloxy group, the same specific examples as mentioned above can be mentioned.

[0147] The number of carbon atoms in the aralkyloxy group is not particularly limited, and for example, can be 40 or less, preferably 30 or less, and more preferably 20 or less.

[0148] As specific examples of the aralkyl group, the same specific examples as those of the aryl group described above can be given, but are not limited thereto. As specific examples of the aralkyl group, for example, phenylmethyl (benzyl), 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, 8-phenyl-n-octyl, 9-phenyl-n-nonyl, 10-phenyl-n-decyl, and the like can be given, but are not limited thereto.

[0149] The acyloxy group is a monovalent group derived from removal of a hydrogen atom from a carboxyl group (-COOH) of a carboxylic acid compound, and typically, an alkylcarbonyloxy group, an arylcarbonyloxy group, or an aralkylcarbonyloxy group derived from removal of a hydrogen atom from a carboxyl group of an alkyl carboxylic acid, an aryl carboxylic acid, or an aralkyl carboxylic acid can be given, but is not limited thereto. As specific examples of the alkyl group, the aryl group, and the aralkyl group in such an alkyl carboxylic acid, an aryl carboxylic acid, and an aralkyl carboxylic acid, the same specific examples as those described above can be given.

[0150] As specific examples of the acyloxy group, an acyloxy group having 2 to 20 carbon atoms can be given, for example, methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, t-butylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl-n-butylcarbonyloxy, 3-methyl-n-butylcarbonyloxy, 1,1-dimethyl-n-propylcarbonyloxy, 1,2-dimethyl-n-propylcarbonyloxy, 2,2-dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentylcarbonyloxy, 2-methyl-n-pentylcarbonyloxy, 3-methyl-n-pentylcarbonyloxy, 4-methyl-n-pentylcarbonyloxy, 1,1-dimethyl-n-butylcarbonyloxy, 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, phenylcarbonyloxy, and tosylcarbonyloxy can be given, but are not limited thereto.

[0151] As specific examples of the hydrolyzable silane (A) represented by Formula (A-1), for example, the following compounds can be given, but the hydrolyzable silane (A) represented by Formula (A-1) is not limited to these compounds.

[0152] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] In the formula, T represents X in formula (A-1). T represents, for example, methoxy group or ethoxy group. Me represents methyl group, Et represents ethyl group, Pr represents propyl group, Bu represents butyl group, and Ac represents acetyl group.

[0153] As the amount of the hydrolyzable silane (A) in the synthesis of the polysiloxane [A] containing the structural unit derived from the hydrolyzable silane (A) represented by formula (A-1), from the viewpoint of more fully obtaining the effects of the present application, it is preferably 0.01 to 100 parts by mass, more preferably 0.05 to 50 parts by mass, still more preferably 0.1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the hydrolyzable silane used in the synthesis of the polysiloxane.

[0154] <[A] Component: Polysiloxane> The polysiloxane as the [A] component is not particularly limited as long as it is a polymer containing the structural unit derived from the hydrolyzable silane (A) represented by formula (A-1) and having a siloxane bond.

[0155] The polysiloxane can be a modified polysiloxane in which a part of silanol groups is modified, for example, a polysiloxane modified product in which a part of silanol groups is modified with an alcohol or protected with an acetal.

[0156] In addition, as one example, the polysiloxane can be a hydrolytic condensate of the hydrolyzable silane, and can also be a modified product in which at least a part of the silanol groups of the hydrolytic condensate is modified with an alcohol or protected with an acetal (hereinafter, sometimes referred to as "modified product of the hydrolytic condensate". The hydrolyzable silane involved in the hydrolytic condensate can include one or two or more kinds of hydrolyzable silanes.

[0157] In addition, the polysiloxane as the [A] component can have a structure having any one of a cage type, a ladder type, a straight chain type, and a branched chain type main chain. Furthermore, the polysiloxane as the [A'] component can use a commercially available polysiloxane.

[0158] Note that, in the present application, the "hydrolytic condensate" of the hydrolyzable silane, that is, the product of the hydrolysis and condensation, includes not only a condensate in which the condensation is completely completed, that is, a polysiloxane polymer, but also a partial hydrolytic condensate in which the condensation is not completely completed, that is, a polysiloxane polymer. Such a partial hydrolytic condensate, like the condensate in which the condensation is completely completed, is a polymer obtained by the hydrolysis and condensation of the hydrolyzable silane, but since the partial hydrolysis is terminated without condensation, the Si-OH group remains. In addition, the silicon-containing underlayer film-forming composition can further contain, in addition to the hydrolytic condensate, uncondensed hydrolyzate (complete hydrolyzate, partial hydrolyzate), monomer (hydrolyzable silane).

[0159] Note that, in the present specification, a "hydrolyzable silane" is also sometimes referred to simply as a "silane compound".

[0160] As the polysiloxane of the [A] component, for example, a hydrolysis condensate of a hydrolyzable silane containing a hydrolyzable silane (A) represented by formula (A-1) or a modified product thereof can be given.

[0161] As the polysiloxane of the [A] component, for example, a hydrolysis condensate of a hydrolyzable silane containing a hydrolyzable silane (A) represented by formula (A-1) and at least one kind of hydrolyzable silane represented by the following formula (1) or a modified product thereof can be given.

[0162] < Formula (1) > [Chemical Formula 13] In formula (1), R 1 is a group bonded to a silicon atom, and independently represents an alkyl group which can be substituted, a halogenated alkyl group which can be substituted, an alkoxyalkyl group which can be substituted, or an alkenyl group which can be substituted, or, R 1 represents an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more of them.

[0163] In addition, R 2 is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0164] a represents an integer of 0 to 3.

[0165] As the specific examples of each group and atom in R 1 in formula (1), and the preferred number of carbon atoms thereof, the groups and the number of carbon atoms described with respect to R 2 in formula (A-1) can be given.

[0166] As the specific examples of each group and atom in R 2 in formula (1), and the preferred number of carbon atoms thereof, the groups and the number of carbon atoms described with respect to X in formula (A-1) can be given.

[0167] < Specific examples of hydrolyzable silanes represented by formula (1) > As specific examples of the hydrolyzable silane represented by formula (1), there are tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltripentoxy-silane, methyltriphenoxysilane, methyltribenzoxysilane, methyltriphenethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyl-dimethoxysilane, methylvinyl-diethoxysilane, methylvinyl-dichlorosilane, methylvinyl-diacetoxysilane, dimethylvinyl-methoxysilane, dimethylvinyl-ethoxysilane, dimethylvinyl-chlorosilane, dimethylvinyl-acetoxysilane, di-vinyl-dimethoxysilane, di-vinyl-diethoxysilane, di-vinyl-dichlorosilane, di-vinyl-diacetoxysilane, aryltrimethoxysilane, aryltriethoxysilane, aryltrichlorosilane, aryltriacetoxysilane, arylmethyl-dimethoxysilane, arylmethyl-diethoxysilane, arylmethyl-dichlorosilane, arylmethyl-diacetoxysilane, aryl-dimethyl-methoxysilane, aryl-dimethyl-ethoxysilane, aryl-dimethyl-chlorosilane, aryl-dimethyl-acetoxysilane, diaryl-dimethoxysilane, diaryl-diethoxysilane, diaryl-dichlorosilane, diaryl-diacetoxysilane, 3-arylaminopropyl-trimethoxysilane, 3-arylaminopropyl-triethoxysilane, p-styryl-trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyl-dimethoxysilane, phenylmethyl-diethoxysilane, phenylmethyl-dichlorosilane, phenylmethyl-diacetoxysilane, phenyl-dimethyl-methoxysilane, phenyl-dimethyl-ethoxysilane, phenyl-dimethyl-chlorosilane, phenyl-dimethyl-acetoxysilane, diphenyl-methyl-methoxysilane, diphenyl-methyl-ethoxysilane, diphenyl-methyl-chlorosilane, diphenyl-methyl-acetoxysilane, diphenyl-dimethoxysilane, diphenyl-diethoxysilane, diphenyl-dichlorosilane, diphenyl-diacetoxysilane, triphenyl-methoxysilane, triphenyl-ethoxysilane, triphenyl-acetoxysilane, triphenyl-chlorosilane, 3-phenylaminopropyl-trimethoxysilane, 3-phenylaminopropyl-triethoxysilane, dimethoxy-methyl-3-(3-phenoxypropylthiopropyl)silane, triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyl-dimethoxysilane, benzylmethyl-diethoxysilane, benzyl-dimethyl-methoxysilane, benzyl-dimethyl-ethoxysilane, benzyl-dimethyl-chlorosilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltrichlorosilane, phenethyltriacetoxysilane,phenethylmethyldimethoxysilane, phenethylmethyldiethoxysilane, phenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane, tert-butoxyphenyltrimethoxysilane, tert-butoxyphenyltriethoxysilane, tert-butoxyphenyltriacetoxysilane, tert-butoxyphenyltrichlorosilane, tert-butoxybenzyltrimethoxysilane, tert-butoxybenzyltriethoxysilane, tert-butoxybenzyltriacetoxysilane, tert-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, gamma chloropropyltrimethoxysilane, gamma chloropropyltriethoxysilane, gamma chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, gamma methacryloyloxypropyltrimethoxysilane, gamma mercaptopropyltrimethoxysilane, gamma mercaptopropyltriethoxysilane, β cyanoethyltriethoxysilane, thiocyanatopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiarylisocyanurate, bicyclo[2,2,1]heptenyltriethoxysilane, phenylsulfonylpropyltriethoxysilane, phenylsulfonamidopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, gamma chloropropylmethyldimethoxysilane, gamma chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane,gamma - methacryloyloxypropylmethyldimethoxysilane, gamma - methacryloyloxypropylmethyldiethoxysilane, gamma - mercaptopropylmethyldimethoxysilane, gamma - mercaptomethyldiethoxysilane, methylvinyl dimethoxysilane, methylvinyl diethoxysilane, silane represented by the following formula, and the like, but are not limited thereto.

[0168] [Chem. 14] [Chem. 15] [Chem. 16] [Chem. 17] [Chem. 18] [Chem. 19] [Chem. 20] [Chem. 21] [Chem. 22] [Chem. 23] [Chem. 24] [Chem. 25] [Chem. 26]

[0169] [Chem. 27] [Chem. 28]

[0170] [Chem. 29]

[0171] [Chem. 30]

[0172] [Chem. 31]

[0173] [Chemical Formula 32]

[0174] [Chemical Formula 33]

[0175] [Chemical Formula 34]

[0176] [Chemical Formula 35]

[0177] In the formula, T independently represents an alkoxy group, an acyloxy group, or a halogen group, and preferably represents a methoxy group or an ethoxy group.

[0178] Further, as the [A] polysiloxane, a hydrolytic condensate of a hydrolytic silane represented by the following formula (2) and a hydrolytic silane represented by the following formula (A-1) or a modified product thereof can be mentioned.

[0179] Further, as the [A] polysiloxane, a hydrolytic condensate of a hydrolytic silane represented by the following formula (2), a hydrolytic silane represented by the following formula (1), and a hydrolytic silane represented by the following formula (A-1) or a modified product thereof can be mentioned.

[0180] <Formula (2)> [Chemical Formula 36]

[0181] In the formula (2), R 3 is a group bonded to a silicon atom, and independently represents an alkyl group which can be substituted, a halogenated alkyl group which can be substituted, an alkoxyalkyl group which can be substituted, or an alkenyl group which can be substituted, or, R 3 represents an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more of them.

[0182] Further, R 4 is a group or atom bonded to a silicon atom, and independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0183] R 5 is a group bonded to a silicon atom, and independently represents an alkylene group or an arylene group.

[0184] b represents 0 or 1, and c represents 0 or 1.

[0185] Specific examples of each group and atom in R 3 and the preferred number of carbon atoms thereof can be exemplified by the groups and atoms and the number of carbon atoms described with respect to R 2 in formula (A-1).

[0186] Specific examples of each group and atom in R 4 and the preferred number of carbon atoms thereof can be exemplified by the groups and atoms and the number of carbon atoms described with respect to X in formula (A-1).

[0187] Specific examples of the alkylene group in R5may be exemplified by: methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, and the like straight-chain alkylene groups, 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-ethyltrimethylene, and the like branched-chain alkylene groups, methanetriyl, ethane-1,1,2-triyl, ethane-1,2,2-triyl, ethane-2,2,2-triyl, propane-1,1,1-triyl, propane-1,1,2-triyl, propane-1,2,3-triyl, propane-1,2,2-triyl, propane-1,1,3-triyl, butane-1,1,1-triyl, butane-1,1,2-triyl, butane-1,1,3-triyl, butane-1,2,3-triyl, butane-1,2,4-triyl, butane-1,2,2-triyl, butane-2,2,3-triyl, 2-methylpropane-1,1,1-triyl, 2-methylpropane-1,1,2-triyl, 2-methylpropane-1,1,3-triyl alkane triyl groups, and the like, but are not limited thereto.

[0188] Specific examples of the arylene group in R 5 may be exemplified by: 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; 1,5-naphthalene diyl, 1,8-naphthalene diyl, 2,6-naphthalene diyl, 2,7-naphthalene diyl, 1,2-anthracene diyl, 1,3-anthracene diyl, 1,4-anthracene diyl, 1,5-anthracene diyl, 1,6-anthracene diyl, 1,7-anthracene diyl, 1,8-anthracene diyl, 2,3-anthracene diyl, 2,6-anthracene diyl, 2,7-anthracene diyl, 2,9-anthracene diyl, 2,10-anthracene diyl, 9,10-anthracene diyl, and the like groups derived by removing two hydrogen atoms on the aromatic rings of a fused ring aromatic hydrocarbon compound; 4,4'-biphenyl diyl, 4,4"-p-terphenyl diyl, and the like groups derived by removing two hydrogen atoms on the aromatic rings of a ring-linked aromatic hydrocarbon compound, and the like, but are not limited thereto.

[0189] b is preferably 0.

[0190] c is preferably 1.

[0191] Specific examples of hydrolyzable silanes shown in formula (2) include: methylene bis(trimethoxysilane), methylene bis(trichlorosilane), methylene bis(triacetoxysilane), ethyl bis(triethoxysilane), ethyl bis(trichlorosilane), ethyl bis(triacetoxysilane), propylene bis(triethoxysilane), butyl bis(trimethoxysilane), phenyl bis(trimethoxysilane), phenyl bis(triethoxysilane), phenyl bis(methyl)ethoxysilane, phenyl bis(methyl)methoxysilane, naphthyl bis(trimethoxysilane), bis(trimethoxy)silane, bis(triethoxy)silane, bis(ethyl)ethoxysilane, bis(methyl)methoxysilane, etc., but are not limited to these.

[0192] As [A] polysiloxane, examples include hydrolytic silanes (A) containing formula (A-1), hydrolytic silanes containing formula (1) and / or hydrolytic silanes containing formula (2), as well as hydrolytic condensates of other hydrolytic silanes listed below or their modifications.

[0193] <<Silane compounds with intramolecular ononium groups (hydrolyzable organosilanes)>> It is expected that silane compounds with intramolecular ononium groups can effectively and efficiently promote the cross-linking reaction of hydrolyzable silanes.

[0194] A preferred example of a silane compound having an intramolecular ononium group is represented by formula (3).

[0195] [Chemistry 37]

[0196] R 11 The group that bonds to silicon atoms represents an onnnage group or an organic group having that onnnage group.

[0197] R 12 The group bonded to the silicon atom, independently representing a substituted alkyl group, a substituted haloalkyl group, a substituted alkoxyalkyl group, or a substituted alkenyl group, or R 12 It refers to an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, or an organic group having a cyano group, or a combination of two or more of them.

[0198] R 13 The group or atom bonded to the silicon atom is represented independently of each other as an alkoxy, arylalkoxy, acyloxy, or halogen atom.

[0199] f represents 1 or 2, g represents 0 or 1, and satisfies 1 ≤ f + g ≤ 2.

[0200] Specific examples of the alkyl group, the haloalkyl group, the alkoxyalkyl group, the alkenyl group, and the organic group having an epoxy group, the organic group having an acryloyl group, the organic group having a methacryloyl group, the organic group having a mercapto group, the organic group having an amino group, and the organic group having a cyano group, specific examples of the alkoxy group, the aralkyloxy group, the acyloxy group, the halogen atom, and specific examples of the substituent of the alkyl group, the haloalkyl group, the alkoxyalkyl group, and the alkenyl group, and the preferred number of carbon atoms thereof, with respect to R 12 Specific examples of R 2 Specific examples and the number of carbon atoms described with respect to R 13 Specific examples and the number of carbon atoms described with respect to X in formula (A-1) can be cited.

[0201] More specifically, as specific examples of the onium group, a cyclic ammonium group or a chain ammonium group, preferably a tertiary ammonium group or a quaternary ammonium group can be cited.

[0202] That is, as preferred specific examples of the onium group or the organic group having the onium group, an organic group having at least one of a cyclic ammonium group or a chain ammonium group, preferably an organic group having at least one of a tertiary ammonium group or a quaternary ammonium group can be cited.

[0203] Note that, in the case where the onium group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as an atom constituting the ring. At this time, there are a case where the nitrogen atom constituting the ring is bonded to the silicon atom directly or via a 2-valent linking group and a case where the carbon atom constituting the ring is bonded to the silicon atom directly or via a 2-valent linking group.

[0204] In one example of the preferred mode, the group R 11 may be a heteroaliphatic cyclic ammonium group represented by the following formula (S2).

[0205] [Chem. 38]

[0206] In formula (S2), A 5 , A 6 , A 7 , and A 8 independently of one another represent a group represented by any one of the following formulae (J4) to (J6), A 5 to A 8 at least one of A 5 to A 8 is bonded to the silicon atom in formula (3), the ring formed shows non-aromaticity, and A 5 to A 8whether the bond to the atom adjacent to each of them and constituting a ring is a single bond or a double bond. represents a bond.

[0207] [Chemical Formula 39]

[0208] In Formulae (J4) to (J6), R 10 independently of one another represent a single bond, a hydrogen atom, an alkyl group, or a haloalkyl group, and as specific examples of the alkyl group and haloalkyl group and the preferred number of carbon atoms thereof, the same specific examples and numbers of carbon atoms as described above can be given. represents a bond.

[0209] In Formula (S2), R 15 independently of one another represent an alkyl group, a haloalkyl group, or a hydroxyl group, and as specific examples of the alkyl group and haloalkyl group and the preferred number of carbon atoms thereof, the same specific examples and numbers of carbon atoms as described above can be given. 15 in the case where two or more are present, the two R 15 may be bonded to each other to form a ring, and the two R 15 The ring formed can be a crosslinked ring structure, and in this case, the cyclic ammonium group has an adamantane ring, a spiro ring, or the like.

[0210] as specific examples of the alkyl group and haloalkyl group and the preferred number of carbon atoms thereof, the same specific examples and numbers of carbon atoms as described above can be given.

[0211] In Formula (S2), n 2 is an integer of 1 to 8, m 3 is 0 or 1, and m 4 is a positive integer from 0 or 1 to the maximum number capable of being substituted as a monocyclic or polycyclic ring.

[0212] in the case where m 3 is 0, a (4+n 5 )membered ring including A 8 to A 2 is formed. That is, when n 2 is 1, a 5-membered ring is formed, when n 2 is 2, a 6-membered ring is formed, when n 2 is 3, a 7-membered ring is formed, when n 2 is 4, an 8-membered ring is formed, when n 2 is 5, a 9-membered ring is formed, when n 2 is 6, a 10-membered ring is formed, when n 2 is 7, an 11-membered ring is formed, and when n 2 is 8, a 12-membered ring is formed.

[0213] in the case where m 3 is 1, a (4+n 5 )membered ring including A 7 to A 2 is formed, and a (4+m 8a fused ring formed by condensation of a 6-membered ring.

[0214] A 5 ~A 8 According to any one of Formula (J4) to Formula (J6), there are a case where a hydrogen atom is present on an atom constituting a ring and a case where a hydrogen atom is not present. 5 ~A 8 In the case where a hydrogen atom is present on an atom constituting a ring, the hydrogen atom can be replaced with R 15 . In addition, R 5 ~A 8 may also be substituted on a ring-constituting atom other than the ring-constituting atom in A 15 .

[0215] According to such a case, as described above, m 4 is selected from 0 or 1 to an integer up to the maximum number of rings that can be substituted as a monocyclic ring or a polycyclic ring.

[0216] The bonding of the heteroaliphatic cyclic ammonium group represented by Formula (S2) is present at any carbon atom or nitrogen atom present on such a monocyclic ring or fused ring, is bonded directly to a silicon atom, or is bonded to a linking group to constitute an organic group having a cyclic ammonium, which is bonded to a silicon atom.

[0217] As such a linking group, an alkylene group can be given, and as specific examples and the preferred number of carbon atoms of the alkylene group, the same specific examples and the number of carbon atoms as described above can be given.

[0218] As specific examples of the silane compound (hydrolyzable organosilane) represented by Formula (3) having a heteroaliphatic cyclic ammonium group represented by Formula (S2), silanes represented by the following formulae, and the like can be given, but are not limited thereto.

[0219] [Chemical Formula 40]

[0220] [Chemical Formula 41]

[0221] Further, in another example, the group bonded to a silicon atom in Formula (3), that is, R 11 can be provided as a chain ammonium group represented by the following Formula (S3).

[0222] [Chemical Formula 42]

[0223] In Formula (S3), R 10 independently represent a hydrogen atom, an alkyl group, a halogenated alkyl group, or an alkenyl group, and as specific examples and the preferred number of carbon atoms of the alkyl group, the halogenated alkyl group, and the alkenyl group, the same specific examples and the number of carbon atoms as described above can be given. represents a bond.

[0224] The chain-like ammonium group represented by formula (S3) is directly bonded to a silicon atom, or is bonded to a linking group to constitute an organic group having a chain-like ammonium group, which is bonded to a silicon atom.

[0225] As such a linking group, an alkylene group or an alkenylene group can be given, and as specific examples of the alkylene group and the alkenylene group, the same specific examples as described above can be given.

[0226] As specific examples of the silane compound (hydrolyzable organosilane) represented by formula (3) having a chain-like ammonium group represented by formula (S3), silanes represented by the following formulae can be given, but are not limited thereto.

[0227] [Chemical Formula 43]

[0228] [Chemical Formula 44]

[0229] The proportion of the Q unit in the total structural units of the [A] polysiloxane ([A] component) is not particularly limited, and is preferably 65 mol% or less.

[0230] In the case where the proportion of the Q unit in the total structural units of the [A] polysiloxane ([A] component) is 65 mol% or less, the [A] polysiloxane preferably has at least any one of a hydroxyl group, a carboxyl group, and an isocyanuric acid structure. Thereby, even in the case where the proportion of the Q unit in the [A] polysiloxane is relatively small, the coatability of the composition for forming a silicon-containing underlayer film is improved.

[0231] Note that the total structural units refer to the total of the M unit, the D unit, the T unit, and the Q unit that constitute the polysiloxane. Note that the polysiloxane need not have all of the M unit, the D unit, the T unit, and the Q unit.

[0232] The M unit refers to a siloxy unit represented by formula (R)3SiO 1 / 2 Here, R each independently represents a hydrogen atom or an organic group. The number (3 in this case) written after (R) means that 3 hydrogen atoms or organic groups are bonded to a silicon atom. That is, the M unit has 1 silicon atom, 3 hydrogen atoms or organic groups, and 1 oxygen atom O More specifically, the M unit has 3 hydrogen atoms or organic groups bonded to 1 silicon atom, and an oxygen atom O bonded to 1 silicon atom.

[0233] The D unit refers to a siloxy unit represented by formula (R)2SiO 2 / 2(Reach independently represents a hydrogen atom or an organic group.) The siloxy unit represented by (Reach independently represents a hydrogen atom or an organic group.) The siloxy unit represented by

[0234] The T unit refers to a siloxy unit represented by RSiO 3 / 2 (Reach independently represents a hydrogen atom or an organic group.) The siloxy unit represented by (Reach independently represents a hydrogen atom or an organic group.) The siloxy unit represented by

[0235] The Q unit refers to a siloxy unit represented by SiO2. That is, the Q unit is a unit having 1 silicon atom, 4 oxygen atoms O (Reach independently represents a hydrogen atom or an organic group.) The siloxy unit represented by

[0236] On the other hand, for example, in the case where the strong acid additive is 0 parts by mass relative to 100 parts by mass of the [A] polysiloxane, the proportion of the Q unit in the entire structural units of the [A] polysiloxane ([A] component) can be 60 mol% or more, or can be 65 mol% or more.

[0237] In a range not impairing the effects of the present application, the [A] polysiloxane can be a hydrolytic condensate of a hydrolyzable silane including other silane compounds than the above-described examples or a modified product thereof.

[0238] As described above, as the [A] polysiloxane, a modified product obtained by modifying at least a part of the silanol groups of the hydrolytic condensate can be used. For example, a modified product obtained by alcohol-modifying a part of the silanol groups or a modified product obtained by acetal protection can be used.

[0239] As the modified product of the polysiloxane, a reaction product obtained by the reaction of at least a part of the silanol groups possessed by the hydrolytic condensate of the hydrolyzable silane with the hydroxyl group of an alcohol, a dehydration reaction product of the condensate and an alcohol, and a modified product obtained by protecting at least a part of the silanol groups possessed by the condensate with an acetal group, and the like can be mentioned.

[0240] As the alcohol, monohydric alcohols can be used, and examples thereof include methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, t-amyl alcohol, neopentyl alcohol, 2-methyl-l-propanol, 2-methyl-l-butanol, 3-methyl-l-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-l-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-l-butanol, 2-methyl-l-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-l-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-l-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, and cyclohexanol.

[0241] Further, for example, 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monobutyl ether (1-butoxy-2-propanol), and the like can be used as the alcohol containing an alkoxy group.

[0242] The reaction of the silanol group of the hydrolytic condensate with the hydroxyl group of the alcohol is carried out by contacting the hydrolytic condensate with the alcohol at a temperature of 40 to 160°C, for example, 60°C, for a period of 0.1 to 48 hours, for example, 24 hours, to thereby obtain a modified product in which the silanol group is capped. At this time, the alcohol of the capping agent can be used as the solvent in the polysiloxane-containing composition.

[0243] Further, the dehydration product of the hydrolytic condensate of the hydrolyzable silane and the alcohol can be produced by reacting the hydrolytic condensate with the alcohol in the presence of an acid as a catalyst, capping the silanol group with the alcohol, and removing the generated water by dehydration to the outside of the reaction system.

[0244] The acid can use an organic acid having an acid dissociation constant (pKa) of -1 to 5, preferably 4 to 5. For example, the acid can be exemplified by trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, acetic acid, and the like, and in particular, benzoic acid, isobutyric acid, acetic acid, and the like.

[0245] Further, the acid can use an acid having a boiling point of 70 to 160°C, and for example, trifluoroacetic acid, isobutyric acid, acetic acid, nitric acid, and the like can be exemplified.

[0246] Thus, as the acid, it is preferable to use any one of the acids having an acid dissociation constant (pKa) of 4 to 5 or a boiling point of 70 to 160°C. That is, an acid having a weak acidity or an acid having a strong acidity but a low boiling point can be used.

[0247] Then, as the acid, any one of the acids can be used according to the properties of the acid dissociation constant and the boiling point.

[0248] The hydrolytic condensate having an acetal-protected silanol group can use a vinyl ether, for example, a vinyl ether represented by the following formula (5) can be used, and a partial structure represented by the following formula (6) can be introduced into the polysiloxane by a reaction thereof.

[0249] [Chem. 45]

[0250] In formula (5), R 1a , R 2a , and R 3a each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, R 4a represents an alkyl group having 1 to 10 carbon atoms, R 2a , and R 4a may be bonded to each other to form a ring. The alkyl group can be exemplified as described above.

[0251] [Chem. 46]

[0252] In formula (6), R 1 ', R 2 ', and R 3 ' each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, R 4 ' represents an alkyl group having 1 to 10 carbon atoms, R 2 ', and R 4 ' can be bonded to each other to form a ring. In formula (6), represents a bond to an adjacent atom. The adjacent atom can be exemplified as, for example, an oxygen atom of a siloxane bond, an oxygen atom of a silanol group, a carbon atom of R 1 from formula (1). The alkyl group can be exemplified as described above.

[0253] As the vinyl ether represented by formula (5), for example, aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, t-butyl vinyl ether, and cyclohexyl vinyl ether, cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran can be used. In particular, it is preferable that ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, or 2,3-dihydrofuran can be used.

[0254] The acetal protection of the silanol group can be performed using a hydrolysis condensate, a vinyl ether, aprotic solvents such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, 1,4-dioxane, and the like as a solvent, and a catalyst such as pyridine p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, sulfuric acid, and the like.

[0255] It should be noted that the endcapping of the silanol group using an alcohol and the acetal protection can be performed at the same time as the hydrolysis and condensation of the hydrolyzable silane described later.

[0256] The weight average molecular weight of the hydrolysis condensate of the hydrolyzable silane or a modified product thereof can be set to, for example, 500 to 1,000,000. From the viewpoint of inhibiting the precipitation of the hydrolysis condensate of the composition or a modified product thereof, and the like, the weight average molecular weight is preferably set to 500,000 or less, more preferably 250,000 or less, and still more preferably 100,000 or less, and from the viewpoint of balancing the storage stability and the coating properties, the weight average molecular weight is preferably set to 700 or more, and more preferably 1,000 or more.

[0257] It should be noted that the weight average molecular weight is a molecular weight obtained by GPC analysis in terms of polystyrene. The GPC analysis can be performed, for example, as follows: GPC device (trade name HLC-8220GPC, manufactured by Tosoh Corporation), GPC column (trade names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), column temperature set to 40°C, tetrahydrofuran used as an eluent (elution solvent), flow rate set to 1.0 mL / minute, and polystyrene (manufactured by Showa Denko K.K. Shodex (registered trademark)) used as a standard sample.

[0258] The hydrolysis condensate of the hydrolyzable silane is obtained by hydrolyzing and condensing the silane compound (hydrolyzable silane) described above.

[0259] The silane compound (hydrolyzable silane) described above contains an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom directly bonded to a silicon atom, that is, contains an alkoxysilyl group, an aralkyloxysilyl group, an acyloxysilyl group, or a halosilyl group (hereinafter, referred to as a hydrolyzable group).

[0260] In the hydrolysis of the hydrolyzable group, generally, 0.1 to 100 moles, for example, 0.5 to 100 moles, and preferably 1 to 10 moles of water are used per 1 mole of the hydrolyzable group.

[0261] The hydrolysis and condensation can be carried out with or without using a hydrolysis catalyst for the purpose of promoting the reaction, and the like. In the case of using a hydrolysis catalyst, generally 0.0001 to 10 moles, preferably 0.001 to 1 mole of the hydrolysis catalyst can be used per 1 mole of the hydrolyzable group.

[0262] The reaction temperature at the time of hydrolysis and condensation is generally in the range of room temperature or higher and the reflux temperature of the organic solvent that can be used for hydrolysis at normal pressure or lower, and can be set to, for example, 20 to 110°C, and can be set to, for example, 20 to 80°C.

[0263] The hydrolysis can be complete hydrolysis in which all of the hydrolyzable groups are changed to silanol groups, or partial hydrolysis in which unreacted hydrolyzable groups remain.

[0264] As the hydrolysis catalyst that can be used at the time of hydrolysis and condensation, metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases can be given.

[0265] As the metal chelate compound as a hydrolysis catalyst, for example, there can be mentioned: titanium triethoxide monobis(acetylacetone), titanium tri-n-propoxide monobis(acetylacetone), titanium triisopropoxide monobis(acetylacetone), titanium tri-n-butoxide monobis(acetylacetone), titanium tri-sec-butoxide monobis(acetylacetone), titanium tri-t-butoxide monobis(acetylacetone), titanium diethoxide bis(acetylacetone), titanium di-n-propoxide bis(acetylacetone), titanium diisopropoxide bis(acetylacetone), titanium di-n-butoxide bis(acetylacetone), titanium di-sec-butoxide bis(acetylacetone), titanium di-t-butoxide bis(acetylacetone), titanium monoethoxide tris(acetylacetone), titanium monon-propoxide tris(acetylacetone), titanium monoisopropoxide tris(acetylacetone), titanium monon-butoxide tris(acetylacetone), titanium mono-sec-butoxide tris(acetylacetone), titanium mono-t-butoxide tris(acetylacetone), titanium tetrakis(acetylacetone), titanium triethoxide monobis(ethylacetoacetate), titanium tri-n-propoxide monobis(ethylacetoacetate), titanium triisopropoxide monobis(ethylacetoacetate), titanium tri-n-butoxide monobis(ethylacetoacetate), titanium tri-sec-butoxide monobis(ethylacetoacetate), titanium tri-t-butoxide monobis(ethylacetoacetate), titanium diethoxide bis(ethylacetoacetate), titanium di-n-propoxide bis(ethylacetoacetate), titanium diisopropoxide bis(ethylacetoacetate), titanium di-n-butoxide bis(ethylacetoacetate), titanium di-sec-butoxide bis(ethylacetoacetate), titanium di-t-butoxide bis(ethylacetoacetate), titanium monoethoxide tris(ethylacetoacetate), titanium monon-propoxide tris(ethylacetoacetate), titanium monoisopropoxide tris(ethylacetoacetate), titanium monon-butoxide tris(ethylacetoacetate), titanium mono-sec-butoxide tris(ethylacetoacetate), titanium mono-t-butoxide tris(ethylacetoacetate), titanium tetrakis(ethylacetoacetate), titanium mono(acetylacetone) tris(ethylacetoacetate), titanium bis(acetylacetone) bis(ethylacetoacetate), titanium tris(acetylacetone) mon(ethylacetoacetate), and the like.tris(ethylacetoacetato)aluminum, and the like, but are not limited thereto.

[0266] As the organic acid as the hydrolysis catalyst, for example, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzene sulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, and the like, but are not limited thereto.

[0267] As the inorganic acid as the hydrolysis catalyst, for example, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, and the like, but are not limited thereto.

[0268] As the organic base as the hydrolysis catalyst, for example, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, and the like can be given, but are not limited thereto.

[0269] As the inorganic base as the hydrolysis catalyst, for example, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like can be given, but are not limited thereto.

[0270] Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and one kind thereof can be used alone, or two or more kinds thereof can be used in combination.

[0271] Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and one kind thereof can be used alone, or two or more kinds thereof can be used in combination.

[0272] Further, as described above, nitric acid can be used also at the time of obtaining the modified product of the hydrolysis condensate, for example, at the time of capping of the silanol group with an alcohol, and thus is also preferred from the viewpoint that it can be a substance that can contribute to both the hydrolysis and condensation of the hydrolyzable silane and the alcohol capping of the hydrolysis condensate.

[0273] As the solvent used in the hydrolysis and condensation, an organic solvent can be used, and as specific examples thereof, aliphatic hydrocarbon-based solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isohexane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, methylcyclohexane, and the like; aromatic hydrocarbon-based solvents such as benzene, toluene, xylene, ethylbenzene, mesitylene, methyl ethyl benzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, n-amyl naphthalene, and the like; monohydric alcohol-based solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decyl alcohol, sec-undecyl alcohol, trimethyl nonanol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, cresol, and the like; polyhydric alcohol-based solvents such as ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, and the like; ketone-based solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetylacetone, diacetone alcohol, phenyl ethyl ketone, fenchone, and the like; ether-based solvents such as diethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, oxirane, 1,2-epoxypropane, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mononormal butyl ether, ethylene glycol mononormal hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mononormal butyl ether, diethylene glycol dinormal butyl ether, diethylene glycol mononormal hexyl ether, ethoxy triethylene glycol, tetraethylene glycol dinormal butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and the like; ester-based solvents such as diethyl carbonate, methyl acetate, ethyl acetate, gamma - butyrolactone, gamma- pentyl lactate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriglycol acetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, isopentyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like; N-methyl formamide, N,N-dimethyl formamide, N,N-diethyl formamide, acetamide, N-methyl acetamide, N,N-dimethyl acetamide, N-methyl propionamide, N-methyl-2-pyrrolidone, and the like; dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, 1,3-propane sultone, and the like; and the like, but are not limited thereto. One or two or more of these solvents can be used in combination.

[0274] After the hydrolysis and condensation reaction is completed, the reaction solution is directly or diluted or concentrated, neutralized, and treated using an ion exchange resin, whereby the hydrolysis catalyst such as acid, base, and the like used in the hydrolysis and condensation can be removed. In addition, before or after such treatment, by-products such as alcohol, water, and the like used in the hydrolysis and condensation can be removed from the reaction solution by, for example, reduced pressure distillation.

[0275] The hydrolysis-condensation product thus obtained or a modified product thereof (hereinafter, also referred to as a polysiloxane) is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, and can be directly used for the preparation of the silicon-containing underlayer film-forming composition. That is, the reaction solution can be directly (or diluted) used for the preparation of the silicon-containing underlayer film-forming composition, and in this case, the hydrolysis catalyst used in the hydrolysis and condensation, by-products, and the like can remain in the reaction solution, as long as the effects of the present application are not impaired. For example, nitric acid used in the alcohol capping of the silanol group can remain in the polymer varnish solution at about 100 ppm to 5000 ppm.

[0276] The obtained polysiloxane varnish can be subjected to solvent replacement, and can also be diluted with a suitable solvent. Note that the obtained polysiloxane varnish, if its storage stability is not deteriorated, can also be distilled to remove the organic solvent, so that the film-forming component concentration becomes 100%. Note that the film-forming component refers to a component obtained by removing the solvent component from all components of the composition.

[0277] The organic solvent used in the solvent replacement, dilution, and the like of the polysiloxane varnish and the organic solvent used in the hydrolysis and condensation reaction of the hydrolyzable silane can be the same or different. The dilution solvent is not particularly limited, and one or two or more kinds can be arbitrarily selected and used.

[0278] <[C] Component: Solvent> As the [C] component, a solvent that can dissolve and mix the [A] component and other components contained in the silicon-containing underlayer film-forming composition as needed is used without particular limitation.

[0279] As the [C] solvent, an alcohol-based solvent is preferred, an alkylene glycol monoalkyl ether as the alcohol-based solvent is more preferred, and a propylene glycol monoalkyl ether is further preferred. These solvents also function as a capping agent for the silanol groups of the hydrolyzate, and thus the silicon-containing underlayer film-forming composition can be prepared from the solution obtained by preparing the [A] polysiloxane without the need for solvent replacement and the like.

[0280] As the alkylene glycol monoalkyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, propylene glycol monobutyl ether, and the like can be given.

[0281] As specific examples of the other [C] solvent, mention can be made of: methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, gamma - butyrolactone, and the like, and the solvent can be used singly or in combination of two or more.

[0282] In addition, the silicon-containing underlayer film-forming composition of the present application can contain water as a solvent. In the case where water is contained as a solvent, the content thereof can be set to, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less, relative to the total mass of the solvent contained in the composition.

[0283] [Strongly acidic additive] The silicon-containing underlayer film-forming composition contains 0 or more and less than 2 parts by mass of the strong acid additive with respect to 100 parts by mass of the [A] polysiloxane. That is, the embodiment of the silicon-containing underlayer film-forming composition includes a case where the content of the strong acid additive is 0 mass %.

[0284] As the strong acid additive, a compound having a first acid dissociation constant of 1 or less in water can be given.

[0285] In addition, as the strong acid additive, an acid generator such as a photo-acid generator can be given.

[0286] In the present application, the strong acid additive can be an additive that becomes an acidic substance by decomposition by a stimulus from the outside (for example, light, heat, or the like). Such an additive can be referred to as a latent strong acid additive. Typical examples of the latent strong acid additive are a thermal acid generator and a photo-acid generator.

[0287] As the photo-acid generator, an onium salt compound, a sulfimide compound, a disulfonyl diazomethane compound, or the like can be given.

[0288] As specific examples of the onium salt compound, iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, triphenylsulfonium chloride, and the like can be given.

[0289] As specific examples of the sulfimide compound, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(trifluoromethanesulfonyloxy)naphthalene dicarboxylic acid imide, and the like can be given.

[0290] As specific examples of the disulfonyl diazomethane compound, bis(trifluoromethylsulfonyl) diazomethane, bis(cyclohexylsulfonyl) diazomethane, bis(phenylsulfonyl) diazomethane, bis(p-toluenesulfonyl) diazomethane, bis(2,4-dimethylphenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyl diazomethane, and the like can be given.

[0291] In addition, as the acid generator, a thermal acid generator such as tetramethylammonium nitrate can be given.

[0292] [Preparation of the silicon-containing underlayer film-forming composition] The silicon-containing underlayer film-forming composition can be produced by mixing the above-mentioned [A] polysiloxane, [C] solvent, and, in the case of including other components, the other components. At this time, a solution containing the [A] polysiloxane can also be prepared in advance, and the solution can be mixed with the [C] solvent and the other components. Alternatively, the reaction solution at the time of producing the [A] polysiloxane can be directly used for the production of the silicon-containing underlayer film-forming composition.

[0293] The order of mixing is not particularly limited. For example, the [C] solvent can be added to a solution containing the [A] polysiloxane and mixed, and the other components can be added to the mixture, or the solution containing the [A] polysiloxane, the [C] solvent, and the other components can be mixed at the same time.

[0294] If necessary, the [C] solvent can be further added at the end, or a part of the components that are relatively easily dissolved in the [C] solvent can not be included in the mixture in advance, but can be added at the end. From the viewpoint of inhibiting aggregation or separation of the components and producing a composition having excellent uniformity with good reproducibility, it is preferable to prepare a solution in which the [A] polysiloxane is well dissolved in advance, and to produce the composition using the solution. It should be noted that attention should be paid to the fact that the [A] polysiloxane has a possibility of aggregation or precipitation when they are mixed, depending on the kind and amount of the [C] solvent to be mixed together, or the amount and properties of the other components. In addition, it should be noted that, in the case where the composition is produced using a solution in which the [A] polysiloxane is dissolved, it is necessary to determine the concentration of the solution of the [A] polysiloxane and the amount thereof to be used in order to make the [A] polysiloxane in the finally obtained composition be a desired amount.

[0295] In the production of the composition, heating can be appropriately performed within a range in which the components do not decompose or deteriorate.

[0296] In the present application, at a stage during the production of the silicon-containing underlayer film-forming composition, or after all the components are mixed, filtration can be performed using a submicron filter or the like. It should be noted that the kind of the material of the filter to be used at this time is not limited, and for example, a nylon filter, a fluororesin filter, or the like can be used.

[0297] It should be noted that the concentration of the solid components in the silicon-containing underlayer film-forming composition can be, for example, 0.1 to 50% by mass, 0.1 to 30% by mass, 0.1 to 25% by mass, or 0.5 to 20.0% by mass, with respect to the total mass of the composition. It should be noted that the above-mentioned solid components refer to the components after the removal of the [C] solvent component from all the components of the composition.

[0298] The content of the above-mentioned [A] polysiloxane in the solid content is usually 20 to 100 mass%, and from the viewpoint of obtaining the effects of the present application with good reproducibility, the lower limit is preferably 50 mass%, more preferably 60 mass%, still more preferably 70 mass%, further preferably 80 mass%, and the upper limit is preferably 99 mass%, and the remainder can be the additive described later.

[0299] Further, the silicon-containing underlayer film-forming composition preferably has a pH of 2 to 5, more preferably a pH of 3 to 4.

[0300] The silicon-containing underlayer film-forming composition of the present application, as described later, can be suitably used as a composition for forming an underlayer film for a self-assembly pattern using directed self-assembly, and in particular, as a composition for forming an underlayer film for an underlayer of a neutral film for improving the alignment of a self-assembly film.

[0301] [Other additives] In the silicon-containing underlayer film-forming composition of the present application, various additives can be incorporated within a range that does not impair the effects of the present application.

[0302] As the above-mentioned additives, for example, the following can be mentioned: well-known additives incorporated in various materials (compositions) that can be used in the production of semiconductor devices such as resist underlayer films, antireflection films, pattern reversal films, and the like: curing catalysts (ammonium salts, phosphine-based compounds, phosphonium salts, sulfonium salts, nitrogen-containing silane compounds, and the like), crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, and the like), organic polymer compounds, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicone-based surfactants, fluorine-based surfactants, UV-curable surfactants, and the like), pH adjustors, metal oxides, rheology modifiers, adhesion aids, and the like.

[0303] Note that the following examples illustrate various additives, but are not limited thereto. In addition, as described above, the silicon-containing underlayer film-forming composition of the present application is a composition that does not contain strongly acidic additives, such as compounds having a first acid dissociation constant of 1 or less in water, acid generators, and in particular, compounds having the function of a photoacid generator, and the like are excluded from the various additives that can be incorporated in the composition of the present application.

[0304] < Curing Catalyst > The silicon-containing underlayer film-forming composition of the present application can contain a curing catalyst, and can also be made into a composition that does not contain a curing catalyst.

[0305] As the above curing catalyst, an ammonium salt, a phosphine, a phosphonium salt, a sulfonium salt, or the like can be used. Note that the following salts described as one example of the curing catalyst can be added as a salt or can be any of a substance that forms a salt in the above composition (a substance that is added as another compound and forms a salt in the system).

[0306] As the above ammonium salt, a quaternary ammonium salt having a structure represented by Formula (D-1), [Chem. 47]

[0307] (In the formula, m a represents an integer of 2 to 11, n a represents an integer of 2 to 3, R 21 represents an alkyl group or an aryl group, Y - represents an anion.) ; a quaternary ammonium salt having a structure represented by Formula (D-2), [Chem. 48]

[0308] (In the formula, R 22 , R 23 , R 24 , and R 25 represent an alkyl group or an aryl group, N represents a nitrogen atom, Y - represents an anion, and R 22 , R 23 , R 24 , and R 25 are each bonded to the nitrogen atom) ; a quaternary ammonium salt having a structure represented by Formula (D-3), [Chem. 49]

[0309] (In the formula, R 26 and R 27 represent an alkyl group or an aryl group, N represents a nitrogen atom, Y - represents an anion) ; a quaternary ammonium salt having a structure represented by Formula (D-4), [Chem. 50]

[0310] (In the formula, R 28 represents an alkyl group or an aryl group, N represents a nitrogen atom, Y - represents an anion) ; a quaternary ammonium salt having a structure represented by Formula (D-5), [Chem. 51]

[0311] (in the formula, R 29 and R 30 represent an alkyl group or an aryl group, N represents a nitrogen atom, Y - represents an anion) ; a tertiary ammonium salt having a structure represented by formula (D-6), [Chemical Formula 52]

[0312] (in the formula, m a represents an integer of 2 to 11, n a represents an integer of 2 to 3, H represents a hydrogen atom, N represents a nitrogen atom, Y - represents an anion).

[0313] In addition, as the above-mentioned phosphonium salt, a quaternary phosphonium salt represented by formula (D-7) can be given, [Chemical Formula 53]

[0314] (in the formula, R 31 , R 32 , R 33 and R 34 represent an alkyl group or an aryl group, P represents a phosphorus atom, Y - represents an anion, and R 31 , R 32 , R 33 and R 34 are respectively bonded to the phosphorus atom).

[0315] In addition, as the above-mentioned sulfonium salt, a tertiary sulfonium salt represented by formula (D-8) can be given, [Chemical Formula 54]

[0316] (in the formula, R 35 , R 36 and R 37 represent an alkyl group or an aryl group, S represents a sulfur atom, Y - represents an anion, and R 35 , R 36 and R 37 are respectively bonded to the sulfur atom).

[0317] The above-mentioned compound of formula (D-1) is a quaternary ammonium salt derived from an amine, m a represents an integer of 2 to 11, n a represents an integer of 2 to 3. R 21alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, for example, straight-chain alkyl groups such as ethyl, propyl, butyl, and the like, benzyl, cyclohexyl, cyclohexylmethyl, dicyclopentadienyl, and the like. Further, anions (Y - ) include halide ions such as chloride (CI - ), bromide (Br - ), iodide (I - ), and the like, acid groups such as carboxylate (-COO - ), sulfonate (-SO3 - ), alcoholate (-O - ), and the like.

[0318] The above-mentioned compound of formula (D-2) is a quaternary ammonium salt represented by the formula: R 22 R 23 R 24 R 25 N + Y - . R 22 , R 23 , R 24 , and R 25 in the quaternary ammonium salt are an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Anions (Y - ) include halide ions such as chloride (CI - ), bromide (Br - ), iodide (I - ), and the like, acid groups such as carboxylate (-COO - ), sulfonate (-SO3 - ), alcoholate (-O - ), and the like. The quaternary ammonium salt can be obtained as a commercially available product, for example, tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, and the like.

[0319] The above-mentioned compound of formula (D-3) is a quaternary ammonium salt derived from a 1-substituted imidazole, and preferably, R 26 and R 27 have a carbon atom number of 1 to 18, and the sum of the carbon atom numbers of R 26 and R 27 is 7 or more. For example, R 26 may be exemplified by methyl, ethyl, propyl, phenyl, benzyl, and R 27 may be exemplified by benzyl, octyl, octadecyl. Anions (Y - ) include halide ions such as chloride (CI - ), bromide (Br - ), iodide (I - ), and the like, acid groups such as carboxylate (-COO- ), sulfonate (-SO3 - ), alcoholate (-O - ), and the like. The compound can also be obtained as a commercially available product, for example, by reacting an imidazole compound such as 1-methylimidazole, 1-benzylimidazole, or the like, with a halogenated alkyl group such as benzyl bromide, methyl bromide, or the like, or a halogenated aryl group.

[0320] The above-mentioned compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, R 28 is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and examples thereof include a butyl group, an octyl group, a benzyl group, and a lauryl group. The anion (Y - ) can be a halide ion such as a chloride ion (CI - ), a bromide ion (Br - ), an iodide ion (I - ), and the like, a carboxylate (-COO - ), a sulfonate (-SO3 - ), an alcoholate (-O - ), and the like. The compound can also be obtained as a commercially available product, for example, by reacting a pyridine with a halogenated alkyl group such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, octyl bromide, or the like, or a halogenated aryl group. Examples of the compound include N-laurylpyridinium chloride, N-benzylpyridinium bromide, and the like.

[0321] The above-mentioned compound of formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine such as a methylpyridine, and the like, R 29 is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and examples thereof include a methyl group, an octyl group, a lauryl group, a benzyl group, and the like. R 30 is an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and, for example, in the case of a quaternary ammonium salt derived from a methylpyridine, R 30 is a methyl group. The anion (Y - ) can be a halide ion such as a chloride ion (CI - ), a bromide ion (Br - ), an iodide ion (I - ), and the like, a carboxylate (-COO - ), a sulfonate (-SO3 - ), an alcoholate (-O - ), and the like. The compound can also be obtained as a commercially available product, for example, by reacting a substituted pyridine such as a methylpyridine with a halogenated alkyl group such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, benzyl bromide, or the like, or a halogenated aryl group. Examples of the compound include N-benzylmethylpyridinium chloride, N-benzylmethylpyridinium bromide, N-laurylmethylpyridinium chloride, and the like.

[0322] The compound of the above formula (D-6) is a tertiary ammonium salt derived from an amine, m a represents an integer of 2 to 11, n a represents an integer of 2 to 3. In addition, the anion (Y - ) can be exemplified by halide ions such as chloride ions (Cl - ), bromide ions (Br - ), iodide ions (I - ), acid radicals such as carboxylate radicals (-COO - ), sulfonate radicals (-SO3 - ), and alcohol radicals (-O - ). This compound can be produced by the reaction of an amine with a weak acid such as a carboxylic acid or a phenol. As the carboxylic acid, formic acid or acetic acid can be exemplified, in the case of using formic acid, the anion (Y - ) is (HCOO - ), and in the case of using acetic acid, the anion (Y - ) is (CH3COO - ). In addition, in the case of using a phenol, the anion (Y - ) is (C6H5O - ).

[0323] The compound of the above formula (D-7) is a quaternary phosphonium salt having a structure of R 31 R 32 R 33 R 34 P + Y - . R 31 , R 32 , R 33 , and R 34 are alkyl groups having 1 to 18 carbon atoms, or aryl groups having 6 to 18 carbon atoms, and preferably 3 of the 4 substituents of R 31 to R 34 are phenyl groups or substituted phenyl groups, and the remaining 1 is an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. In addition, the anion (Y - ) can be exemplified by halide ions such as chloride ions (Cl - ), bromide ions (Br - ), iodide ions (I - ), acid radicals such as carboxylate radicals (-COO - ), sulfonate radicals (-SO3 - ), and alcohol radicals (-O -acid groups. Such compounds are commercially available, and examples thereof include halogenated tetra-n-butylphosphonium, halogenated tetra-n-propylphosphonium, and the like halogenated tetraalkylphosphonium, halogenated triethylbenzylphosphonium, and the like halogenated trialkylbenzylphosphonium; halogenated triphenylmethylphosphonium, halogenated triphenylethylphosphonium, and the like halogenated triphenylmonoalkylphosphonium; halogenated triphenylbenzylphosphonium, halogenated tetraphenylphosphonium, halogenated tri-mesitylmonoarylphosphonium, or halogenated tri-mesitylmonoalkylphosphonium (in the above, the halogen atom is a chlorine atom or a bromine atom). Particularly preferred are halogenated triphenylmethylphosphonium, halogenated triphenylethylphosphonium, and the like halogenated triphenylmonoalkylphosphonium; halogenated triphenylbenzylphosphonium, and the like halogenated triphenylmonoarylphosphonium; halogenated tri-mesitylmonoarylphosphonium, and the like halogenated tri-mesitylmonoarylphosphonium; halogenated tri-mesitylmonomethylphosphonium, and the like halogenated tri-mesitylmonoalkylphosphonium (the halogen atom is a chlorine atom or a bromine atom).

[0324] Further, as the phosphine, there are exemplified primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisopentylphosphine, diphenylphosphine; tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine.

[0325] The above-mentioned compound of formula (D-8) is a tertiary sulfonium salt having a structure of R 35 R 36 R 37 S + Y - R 35 , R 36 , and R 37 are an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and are preferably R 35 to R 37 of the three substituents are a phenyl group or a substituted phenyl group, and examples thereof include a phenyl group, a tolyl group, and the remaining one is an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Further, the anion (Y - ) is exemplified by halide ions such as chloride (Cl - ), bromide (Br - ), iodide (I - ), and the like; carboxylate (-COO - ), sulfonate (-SO3 - ), alkoxide (-O -acid anion, nitric acid anion, and the like. Such a compound can be obtained as a commercial product, and examples thereof include halogenated tri-n-butylsulfonium, halogenated tri-n-propylsulfonium, and the like; halogenated diethylbenzylsulfonium, and the like; halogenated diphenylmethylsulfonium, halogenated diphenylethylsulfonium, and the like; halogenated triphenylsulfonium (in the above, halogen atom is chlorine atom or bromine atom), tri-n-butylsulfonium carboxylate, tri-n-propylsulfonium carboxylate, and the like; diethylbenzylsulfonium carboxylate, and the like; diphenylmethylsulfonium carboxylate, diphenylethylsulfonium carboxylate, and the like; triphenylsulfonium carboxylate. In addition, halogenated triphenylsulfonium and triphenylsulfonium carboxylate are preferably used.

[0326] In addition, a nitrogen-containing silane compound can be added as a curing catalyst in the present application. As the nitrogen-containing silane compound, an imidazole ring-containing silane compound such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole can be mentioned.

[0327] In the case where a curing catalyst is used, 0.01 parts by mass to 10 parts by mass, or 0.01 parts by mass to 5 parts by mass, or 0.01 parts by mass to 3 parts by mass, relative to 100 parts by mass of [A] the polysiloxane.

[0328] <Stabilizer> The above-mentioned stabilizer can be added for the purpose of stabilization of the hydrolysis condensate of the above-mentioned hydrolyzable silane mixture, and the like, and as specific examples thereof, an organic acid, water, an alcohol, or a combination thereof can be added.

[0329] As the above-mentioned organic acid, for example, oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, salicylic acid, and the like can be mentioned. Among them, oxalic acid and maleic acid are preferred. In the case where an organic acid is added, the amount of addition thereof is 0.1 to 5.0% by mass relative to the mass of the hydrolysis condensate of the above-mentioned hydrolyzable silane mixture. These organic acids can also function as a pH adjuster.

[0330] As the above-mentioned water, pure water, ultrapure water, ion-exchanged water, and the like can be used, and in the case where water is used, the amount of addition thereof can be set to 1 part by mass to 20 parts by mass relative to 100 parts by mass of the silicon-containing underlayer film-forming composition.

[0331] As the above-mentioned alcohol, an alcohol that is easily scattered (volatilized) by heating after coating is preferred, and for example, methanol, ethanol, propanol, isopropanol, butanol, and the like can be mentioned. In the case where an alcohol is added, the amount of addition thereof can be set to 1 part by mass to 20 parts by mass relative to 100 parts by mass of the silicon-containing underlayer film-forming composition.

[0332] <Organic Polymer> The above organic polymer compound, by being added to the silicon-containing underlayer film-forming composition, can adjust the dry etching rate (amount of decrease in film thickness per unit time) and the attenuation coefficient, refractive index, and the like of the film (underlayer film) formed from the composition. As the organic polymer compound, there is no particular limitation, and it can be appropriately selected from various organic polymers (polycondensation polymers and addition polymerization polymers) according to the purpose of addition thereof.

[0333] As specific examples thereof, addition polymerization polymers and polycondensation polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolak, naphthol novolak, polyether, polyamide, polycarbonate, and the like can be given.

[0334] In the present application, an organic polymer containing an aromatic ring, a heteroaromatic ring, such as a benzene ring, a naphthalene ring, an anthracene ring, a triazine ring, a quinoline ring, a quinoxaline ring, which functions as a light-absorbing site, can also be preferably used in cases where such a function is required. As specific examples of such an organic polymer compound, addition polymerization polymers containing, as structural units thereof, addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthracene methacrylate, anthracene methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenyl maleimide, polycondensation polymers such as phenol novolak and naphthol novolak, and the like can be given, but are not limited thereto.

[0335] In the case where an addition polymerization polymer is used as the organic polymer compound, the polymer compound can be any one of a homopolymer or a copolymer.

[0336] As specific examples of such an addition polymerizable monomer, acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, acrylonitrile, and the like can be given, but are not limited thereto.

[0337] As specific examples of the acrylate compound, there are mentioned methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthrylmethyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxy- norbornene-2-carboxy-6-lactone, 3-acryloyloxypropyltriethoxysilane, glycidyl acrylate, etc., but are not limited thereto.

[0338] As specific examples of the methacrylate compound, there are mentioned methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthrylmethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxy- norbornene-2-carboxy-6-lactone, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, etc., but are not limited thereto.

[0339] As specific examples of the acrylamide compound, there are mentioned acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-benzyl acrylamide, N-phenyl acrylamide, N,N-dimethyl acrylamide, N-anthryl acrylamide, etc., but are not limited thereto.

[0340] As specific examples of the methacrylamide compound, there are mentioned methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-benzyl methacrylamide, N-phenyl methacrylamide, N,N-dimethyl methacrylamide, N-anthryl methacrylamide, etc., but are not limited thereto.

[0341] As specific examples of the vinyl compound, there are mentioned vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc., but are not limited thereto.

[0342] As specific examples of the styrene compound, there can be mentioned styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetylstyrene, and the like, but the present application is not limited thereto.

[0343] As the maleimide compound, there can be mentioned maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-hydroxyethylmaleimide, and the like, but the present application is not limited thereto.

[0344] In the case where a polycondensation polymer is used as the polymer, as such a polymer, for example, there can be mentioned a polycondensation polymer of a diol compound and a dicarboxylic acid compound. As the diol compound, there can be mentioned diethylene glycol, hexamethylene glycol, butanediol, and the like. As the dicarboxylic acid compound, there can be mentioned succinic acid, adipic acid, terephthalic acid, maleic anhydride, and the like. Further, for example, there can be mentioned polyphthalazinone, poly(paraphenylene terephthalamide), polybutylene terephthalate, polyethylene terephthalate and the like polyesters, polyamides, polyimides, but the present application is not limited thereto.

[0345] In the case where the organic polymer compound contains a hydroxyl group, the hydroxyl group can be crosslinked with a hydrolytic condensate or the like.

[0346] The weight average molecular weight of the above-mentioned organic polymer compound can generally be set to 1000 to 1000000. In the case where the organic polymer compound is compounded, from the viewpoint of sufficiently obtaining the effect as the polymer while suppressing precipitation in the composition, the weight average molecular weight thereof can be set to, for example, 3000 to 300000, or 5000 to 300000, or 10000 to 200000, and the like.

[0347] Such an organic polymer compound can be used alone in one kind, or two or more kinds in combination.

[0348] In the case where the silicon-containing underlayer film-forming composition of the present application contains an organic polymer compound, the content thereof is appropriately determined in consideration of the function or the like of the organic polymer compound, and thus cannot be generalized, and generally, it can be set to a range of 1 to 200 mass% with respect to the mass of the above-mentioned [A] silicone, and from the viewpoint of suppressing precipitation in the composition or the like, it can be set to, for example, 100 mass% or less, preferably 50 mass% or less, more preferably 30 mass% or less, and from the viewpoint of sufficiently obtaining the effect thereof or the like, it can be set to, for example, 5 mass% or more, preferably 10 mass% or more, more preferably 30 mass% or more.

[0349] <SURFACTANT> The surfactant is effective in suppressing the generation of pinholes, streaks (Japanese: sutorēshon), and the like when the above-mentioned composition for forming a silicon-containing underlayer film is applied to a substrate. As the above-mentioned surfactant, nonionic surfactants, anionic surfactants, cationic surfactants, silicone-based surfactants, fluorine-based surfactants, UV-curable surfactants, and the like can be given, but are not limited thereto. More specifically, for example, polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and the like; polyoxyethylene alkyl aryl ether such as polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, and the like; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, and the like; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, and the like; nonionic surfactants such as EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Materials Co., Ltd. (formerly Tochem Products Co., Ltd.)), Megafac (registered trademark) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corp.), Fluorad FC430, FC431 (manufactured by 3M Japan Co., Ltd.), AsahiGuard (registered trademark) AG710 (manufactured by AGC Inc.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and the like; and silicone oxane polymers such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like can be given.

[0350] The surfactant can be used alone or in combination with two or more kinds.

[0351] In the case where the composition for forming a silicon-containing underlayer film of the present application contains a surfactant, the content thereof is usually 0.0001 to 5% by mass, preferably 0.001 to 4% by mass, and more preferably 0.01 to 3% by mass, relative to the mass of [A] the polysiloxane.

[0352] <Flow modifier> The above-mentioned rheology modifier is added mainly for the purpose of improving the flowability of the silicon-containing underlayer film-forming composition, particularly in the baking process, and improving the film thickness uniformity of the formed film. As specific examples, phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate, and the like; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, octyl decyl adipate, and the like; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, dinonyl maleate, and the like; oleic acid derivatives such as methyl oleate, butyl oleate, tetrahydrofurfuryl oleate, and the like; or stearic acid derivatives such as n-butyl stearate, glycerol stearate, and the like, can be given.

[0353] In the case where these rheology modifiers are used, the amount of addition is usually less than 30 mass% relative to the total solid content of the silicon-containing underlayer film-forming composition.

[0354] <Adhesion aid> The above-mentioned adhesion aid is added mainly for the purpose of improving the adhesion between the film (neutral film, brush film, etc.) provided on the substrate or the upper layer and the film (underlayer film) formed from the silicon-containing underlayer film-forming composition. As specific examples, chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, and the like; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylylvinylethoxysilane, and the like; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, and the like, gamma - chloropropyltrimethoxysilane, gamma - aminopropyltriethoxysilane, gamma - glycidoxypropyltrimethoxysilane, and the like; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopurine, and the like; ureas such as 1,1-dimethylurea, 1,3-dimethylurea, and the like; or thiourea compounds.

[0355] In the case where these adhesion aids are used, the amount of addition is usually less than 5 mass%, preferably less than 2 mass%, relative to the total solid content of the silicon-containing underlayer film-forming composition.

[0356] <pH adjuster> In addition, as the pH adjuster, in addition to the acid having one or more than two carboxylic acid groups such as the organic acid mentioned as the above-mentioned <stabilizer>, bisphenol S or a bisphenol S derivative can be added. In the case of using the pH adjuster, the amount of addition can be set to 0.01 to 20 parts by mass, or 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, with respect to 100 parts by mass of the [A] polysiloxane.

[0357] Hereinafter, as specific examples of the bisphenol S or the bisphenol S derivative, the compounds represented by the following Formulas (C-1) to (C-23) can be mentioned, but are not limited thereto.

[0358] [Formula 55]

[0359] <metal oxide> Further, as the metal oxide which can be added in the silicon-containing underlayer film-forming composition of the present application, for example, the oxide of one or more than two kinds of combination of metals such as tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten), and semi-metals such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te) can be mentioned, but are not limited thereto.

[0360] [Method for manufacturing substrate having self-assembly pattern] Further, the present application is directed to a method for forming a self-assembly pattern using the above-mentioned silicon-containing underlayer film-forming composition, and in particular, is directed to a method for manufacturing a substrate having a self-assembly pattern formed by directed self-assembly (DSA).

[0361] Note that, in the present specification, the underlayer film (also referred to as a silicon-containing underlayer film) refers to a film formed from the silicon-containing underlayer film-forming composition of the present application.

[0362] One example of the method for manufacturing a substrate having a self-assembly pattern includes: a step of forming an underlayer film on a substrate using the silicon-containing underlayer film-forming composition of the present application, and a step of forming a self-assembly film on the upper side of the underlayer film, thereby forming a self-assembly pattern.

[0363] Another example of the method for manufacturing a substrate having a self-assembly pattern includes: a step of forming an underlayer film on a substrate using the silicon-containing underlayer film-forming composition of the present application, a step of forming a neutral film on the underlayer film, and a step of forming a self-assembly film on the neutral film, thereby forming a self-assembly pattern.

[0364] Another example of the method for manufacturing a substrate having a self-assembled pattern includes: a step of forming a lower layer film on the substrate using the silicon-containing lower layer film-forming composition of the present application, a step of forming a neutral film on a part of the lower layer film, a step of forming a brush film on the lower layer film on which the neutral film is not formed, forming a template film for a self-assembled pattern composed of the neutral film and the brush film, and a step of forming a self-assembled film on the template film for a self-assembled pattern, obtaining a self-assembled pattern.

[0365] Another example of the method for manufacturing a substrate having a self-assembled pattern includes: a step of forming an organic lower layer film on the substrate, a step of forming a lower layer film on the organic lower layer film using the silicon-containing lower layer film-forming composition of the present application, a step of forming a neutral film on a part of the lower layer film, a step of forming a brush film on the lower layer film on which the neutral film is not formed, forming a template film for a self-assembled pattern composed of the neutral film and the brush film, and a step of forming a self-assembled film on the template film for a self-assembled pattern, obtaining a self-assembled pattern.

[0366] Another example of the method for manufacturing a substrate having a self-assembled pattern includes: a step of forming an organic lower layer film on the substrate, a step of forming a lower layer film on the organic lower layer film using the silicon-containing lower layer film-forming composition of the present application, a step of forming a neutral film on the lower layer film, a step of forming a resist film on the neutral film, a step of exposing and developing the resist film, obtaining a resist pattern, a step of etching the neutral film using the resist pattern as a mask, a step of etching or peeling the resist pattern, obtaining a patterned neutral film on the lower layer film, a step of forming a brush film on the lower layer film and the patterned neutral film on the lower layer film, a step of etching or peeling the brush film on the patterned neutral film, exposing the neutral film, forming a template film for a self-assembled pattern composed of the neutral film and the brush film, and a step of forming a self-assembled film on the template film for a self-assembled pattern, obtaining a self-assembled pattern.

[0367] The method for manufacturing a substrate having a self-assembly pattern includes a step of forming a lower layer film on a substrate using the composition for forming a silicon-containing lower layer film of the present application; and a step of forming a self-assembly film as a layer on the upper side of the lower layer film, and forming a self-assembly pattern (a pattern structure of the self-assembly film, also referred to as a microphase separation structure).

[0368] In a preferred mode, a neutralization treatment is performed in a layer in which the self-assembly film is provided (e.g., on the lower layer film), and then the self-assembly film is formed, thereby forming a self-assembly pattern.

[0369] In the technical field, the neutralization treatment refers to a treatment for changing the surface of a substrate or the like on which the self-assembly film is formed to have affinity with any of the polymers constituting the block copolymer of the self-assembly film. By performing the neutralization treatment, it is possible to inhibit only the phase composed of a specific polymer from contacting the surface of a substrate or the like by phase separation. This neutralization treatment is an important treatment for forming a cylindrical structure, a dot structure, a gyroid structure, or the like that is free to orient with respect to the surface of a substrate by phase separation.

[0370] Specifically, the neutralization treatment can be performed by forming a thin film (neutral film) containing a base agent having affinity with any of the polymers constituting the block copolymer on the surface of a substrate or the like on which the self-assembly film is formed.

[0371] In the case of using the neutral film in order to pattern the block copolymer into a cylindrical shape by changing the surface energy (hydrophilicity and hydrophobicity) when forming a self-assembly pattern, the value of the water contact angle of the polymer in the neutral film is preferably a value between the values of the water contact angles of the respective polymer chains of the block copolymer constituting the self-assembly film.

[0372] In the present application, it is possible to form a neutral film before forming the self-assembly film, and the neutral film can store pattern information by electron beam drawing or laser irradiation.

[0373] In addition, photolithography using a resist can be performed before forming the self-assembly film, and photolithography can also be performed without using a resist. In the case where the block copolymer itself has a pattern formation ability based on self-assembly, a resist is not necessarily required in order to utilize the performance thereof.

[0374] In the present application, for example, a silicon-containing lower layer film can be formed on a substrate from the composition for forming a silicon-containing lower layer film of the present application, a neutral film can be formed thereon, and a self-assembly film can be formed thereon, and a pattern can be formed by the self-assembly film. The self-assembly film can be applied along a pattern guide that is set in advance, and the pattern guide can be formed using a photolithography technique.

[0375] The self-assembled film self-assembled along the pattern guide is selectively removed by using a developing solution, etching gas, or the like, and the removed portion can be selectively removed, and the pattern width can be shrunk and a sidewall can be formed.

[0376] In addition, in the case of patterning the neutral film, a brush material can be used to eliminate the difference in level between the patterned neutral film and the lower layer (silicon-containing lower layer film) exposed by the removal of the pattern and to control the hydrophilic and hydrophobic properties. The brush material is disposed so that the self-assembled pattern does not appear on the portion outside the target. That is, the portion of the lower layer (silicon-containing lower layer film) exposed by the removal of the pattern can be embedded in the brush material, and a self-assembled pattern template film composed of the patterned neutral film and the brush film can be formed.

[0377] As a method for manufacturing a substrate having a self-assembled pattern using the silicon-containing lower layer film, the neutral film, and the brush film, the following method can be used.

[0378] That is, the following method can be used: a step of forming a lower layer film on a substrate using a silicon-containing lower layer film-forming composition, a step of forming a neutral film on a portion of the lower layer film, a step of forming a brush film on the lower layer film on which the neutral film is not formed, and forming a self-assembled pattern template film composed of the neutral film and the brush film, and a step of forming a self-assembled film on the self-assembled pattern template film, and obtaining a self-assembled pattern.

[0379] Further, an organic lower layer film can be formed on the lower layer of the lower layer film (silicon-containing lower layer film). In addition, in the step of forming a neutral film on a portion of the lower layer film, that is, in order to form a patterned neutral film, a resist pattern can be used. As such a method, that is, the following method can be used: a step of forming an organic lower layer film on a substrate, a step of forming a lower layer film on the organic lower layer film using a silicon-containing lower layer film-forming composition, a step of forming a neutral film on the lower layer film, a step of forming a resist film on the neutral film, a step of exposing and developing the resist film to obtain a resist pattern, a step of etching the neutral film using the resist pattern as a mask, a step of etching or peeling the resist pattern to obtain a patterned neutral film on the lower layer film, a step of forming a brush film on the lower layer film and the patterned neutral film on the lower layer film, a step of etching or peeling the brush film on the patterned neutral film to expose the neutral film, and forming a self-assembly pattern template film composed of the neutral film and the brush film, and a step of forming a self-assembly film on the self-assembly pattern template film to obtain a self-assembly pattern.

[0380] Hereinafter, one example of a method for manufacturing a substrate having a self-assembly pattern (self-assembly pattern forming method) of the present application will be described using the drawings.

[0381] Figures 1A-1J is a view showing one example of a method for manufacturing a substrate having a self-assembly pattern (self-assembly pattern forming method) of the present application.

[0382] A lower layer film 2 is formed on a substrate 1 using a composition for forming a silicon-containing lower layer film of the present application. Figure 1A ).

[0383] Next, a neutral film 3 is formed on the lower layer film 2 Figure 1B ).

[0384] Next, a resist film 4 is formed on the neutral film 3 Figure 1C ).

[0385] Next, the resist film 4 is subjected to light irradiation or electron beam irradiation, and then the resist film 4 is developed to obtain a resist pattern (patterned resist film 4) Figure 1D ).

[0386] Next, the neutral film 3 is etched using the resist pattern (patterned resist film 4) as a mask to form a patterned neutral film 3 Figure 1E ).

[0387] Next, the resist pattern (patterned resist film 4) is removed Figure 1F ).

[0388] Next, a brush film 5 is formed on the lower layer film 2 and the patterned neutral film 3 Figure 1G ).

[0389] Next, a part of the brush film 5 is removed to form the brush film 5 in the gaps of the pattern of the patterned neutral film 3 Figure 1H ). Thus, a self-assembly pattern template film 11 composed of the neutral film 3 and the brush film 5 is formed.

[0390] Next, a self-assembly film 6 is formed on the self-assembly pattern template film 11. The self-assembly film 6 is, for example, a film of a block copolymer having an A block and a B block. By phase separating the self-assembly film 6, a microphase separation structure having a region 6a of the A block and a region 6b of the B block is obtained Figure 1I ).

[0391] By selectively removing a portion of the self-assembled film 6 after microphase separation (e.g., the region 6b of the B block), a pattern corresponding to the morphology of the microphase-separated region is obtained. Figure 1J

[0392] <Formation of lower layer film (formation of silicon-containing lower layer film)> First, on a substrate used in the production of a precision integrated circuit element (for example, a semiconductor substrate such as a silicon wafer coated with a silicon oxide film, a silicon nitride film, or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, a glass substrate (including an alkali-free glass, a low-alkali glass, a crystallized glass), a glass substrate on which an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film is formed, a plastic (polyimide, PET, etc.) substrate, a low-dielectric constant material (low-k material) coated substrate, a flexible substrate, etc.), the silicon-containing lower layer film-forming composition of the present application is applied by an appropriate coating method such as a spin coater or a coater, and then the composition is cured by heating using a hot plate or the like to form a lower layer film.

[0393] As the conditions for the curing, the curing temperature is appropriately selected from 40°C to 400°C, or 80°C to 250°C, and the curing time is appropriately selected from 0.3 minutes to 60 minutes. The curing temperature is preferably 150°C to 250°C, and the curing time is preferably 0.5 minutes to 2 minutes.

[0394] The film thickness of the lower layer film formed here is, for example, 10 nm to 1000 nm, or 20 nm to 500 nm, or 50 nm to 300 nm, or 100 nm to 200 nm, or 10 nm to 150 nm.

[0395] <Formation of organic lower layer film> In the present application, it is also possible to form an organic lower layer film on the above-mentioned substrate, and then form the above-mentioned lower layer film thereon.

[0396] The organic lower layer film used here is not particularly limited, and can be arbitrarily selected from the organic lower layer films conventionally used in photolithography processes.

[0397] The organic lower layer film is formed by applying the organic lower layer film-forming composition described below to the substrate using the above-mentioned appropriate coating method, and then curing it by heating.

[0398] The film thickness of the organic lower layer film formed on the substrate can be appropriately adjusted, and can be, for example, 0.01 to 30 mu m, etc.

[0399] <Organic lower layer film-forming composition (SOC composition)> ​The organic lower layer film-forming composition can contain an organic lower layer film-forming compound (SOC compound) and a solvent, and can also contain, as needed, a crosslinking agent, an acid or an acid generator (thermal acid generator, photo acid generator), a rheology modifier, an adhesion aid, a surfactant, and the like.

[0400] As the organic lower layer film-forming compound (SOC compound), the following compounds, polymers, and the like can be given, but are not limited thereto. Also, as the solvent, there is no particular limitation as long as the following organic lower layer film-forming compound (SOC compound), other components can be dissolved and dispersed, and for example, the solvents listed as the above [C] solvent and the like can be appropriately used.

[0401] In the organic lower layer film-forming composition, the solid content can be, for example, 0.1 to 70% by mass, or 0.1 to 60% by mass, or the like. Here, the solid content refers to the content after the solvent content is removed from the total content of the organic lower layer film-forming composition.

[0402] Also, the proportion of the above organic lower layer film-forming compound in the solid content can be, for example, 1 to 100% by mass, or 1 to 99.9% by mass, or 50 to 99.9% by mass, or the like.

[0403] << Organic Lower Layer Film-Forming Compound (SOC Compound) >> As the compound forming the organic lower layer film, for example, the following organic lower layer film-forming compounds 1 (SOC1 compound) to 28 (SOC28 compound) shown below can be given, but are not limited thereto.

[0404] << Organic Lower Layer Film-Forming Compound 1 >> As the organic lower layer film-forming compound 1 (SOC1 compound), for example, the compounds listed in International Publication No. 2010 / 147155 (Japanese Patent No. 5641253) and International Publication No. 2012 / 077640 (Japanese Patent No. 5867732) can be used. The entire disclosures of International Publication No. 2010 / 147155 (Japanese Patent No. 5641253) and International Publication No. 2012 / 077640 are incorporated herein by reference.

[0405] Specifically, for example, a polymer containing a unit structure represented by the following formula (SOC1-1) can be given.

[0406] Note that the symbols of the groups in the formula (SOC1-1) defined below and the definitions of the symbols are limited only to the description in the formula (SOC1-1), that is, the description of << Organic Lower Layer Film-Forming Compound 1 >> unless specifically noted.

[0407] [Chemical Formula 56]

[0408] [In formula (SOC1-1), R1and R2each represent a group selected from a hydrogen atom, a halogen atom, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group, or the aryl group can include a group having an ether bond, a ketone bond, or an ester bond, R3represents a group selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group, or the aryl group can include a group having an ether bond, a ketone bond, or an ester bond, R4represents a hydrogen atom, or an aryl group or a heterocyclic group having 6 to 40 carbon atoms which can be substituted with a halogen atom, a nitro group, an amino group, or a hydroxyl group, R5represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group or a heterocyclic group having 6 to 40 carbon atoms which can be substituted with a halogen atom, a nitro group, an amino group, or a hydroxyl group, and R4and R5may form a ring together with the carbon atom to which they are bonded, n1and n2are each an integer of 1 to 3. <Organic Underlayer Film Forming Compound 2> As the organic underlayer film forming compound 2 (SOC2 compound), for example, the compounds set forth in International Publication No. 2022 / 030468, International Publication No. 2022 / 030469, and International Publication No. 2013 / 047516 (Japanese Patent No. 6066092) can be used. The entire disclosures of International Publication No. 2022 / 030468, International Publication No. 2022 / 030469, and International Publication No. 2013 / 047516 (Japanese Patent No. 6066092) are incorporated herein by reference.

[0409] Specifically, for example, a polymer including a unit structure represented by the following formula (SOC2-1) and / or a unit structure represented by formula (SOC2-2) can be mentioned.

[0410] Note that the symbols of the groups in formula (SOC2-1) and formula (SOC2-2) defined below and the definitions of the symbols are limited only to the description of <Organic Underlayer Film Forming Compound 2> in formula (SOC2-1) and formula (SOC2-2), unless otherwise specified.

[0411] [Formula 57]

[0412] [In the formula, Ar 1 and Ar 2 respectively represent a benzene ring or a naphthalene ring, Ar 1 and Ar 2 may be bonded via a single bond, Ar 3 represents an aromatic compound having 6 to 60 carbon atoms which can contain a nitrogen atom, R 1 and R 2 are respectively a group substituting a hydrogen atom on the ring of Ar 1 and Ar 2 , selected from a halogen atom, a nitro group, an amino group, a cyano group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group, the alkenyl group and the aryl group can contain an ether bond, a ketone bond or an ester bond, R 3 and R 8 are respectively selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group, the alkynyl group and the aryl group can contain an ether bond, a ketone bond or an ester bond, the aryl group can be substituted with an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group, R 4 and R 6 are respectively selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a trifluoromethyl group, an aryl group having 6 to 40 carbon atoms and a heterocyclic group, and the aryl group and the heterocyclic group can be substituted with a halogen atom, a nitro group, an amino group, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, a formyl group, a carboxyl group or a hydroxyl group, and the alkyl group, the alkenyl group, the alkynyl group and the aryl group can contain an ether bond, a ketone bond or an ester bond, R 5 and R 7 are respectively selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a trifluoromethyl group, an aryl group having 6 to 40 carbon atoms and a heterocyclic group, and the aryl group and the heterocyclic group can be substituted with a halogen atom, a nitro group, an amino group, a cyano group, a hydroxyl group, a trifluoromethyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and the alkyl group, the alkenyl group, the alkynyl group and the aryl group can contain an ether bond, a ketone bond or an ester bond, and R 4 and R 5 and R 6 and R 7may also form a ring together with the carbon atom to which they are bonded, respectively.

[0413] n1 and n2 are each an integer of 0 to 3, n3 is 1 or more, and is Ar 3 the number of substituents capable of being substituted in the above is an integer of 0 to 3, n4 is 0 or 1, but when n4 is 0, R 8 is bonded to the nitrogen atom contained in Ar 3 is bonded to the nitrogen atom contained in Ar <Organic Underlayer Film Forming Compound 3> As the organic underlayer film forming compound 3 (SOC3 compound), the compounds set forth in International Publication No. 2017 / 154921 can be used. The entire disclosure of International Publication No. 2017 / 154921 is incorporated herein by reference.

[0414] Specifically, for example, a compound containing partial structure (I) and partial structure (II) shown below can be cited.

[0415] Partial structure (I) is at least one partial structure selected from the group consisting of partial structures shown in formulae (SOC3-1-1) to (SOC3-1-5) below, or is a partial structure containing a combination of a partial structure shown in formula (SOC3-1-6) and a partial structure shown in formula (SOC3-1-7) or formula (SOC3-1-8), and the partial structure (II) can be a partial structure shown in formula (SOC3-2-1) or formula (SOC3-2-2) below.

[0416] Note that the symbols of the groups and the definitions of the symbols in the formulae (SOC3-1-1) to (SOC3-1-8) and formulae (SOC3-2-1) to (SOC3-2-2) defined below are limited only to the descriptions in these formulae, i.e., the description of the <Organic Underlayer Film Forming Compound 3> unless specifically noted.

[0417] [Formula 58]

[0418] [In the formula, R 1 , R 1a , R 3 , R 5 , R 5a , and R 6a each represent a group containing a saturated hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 40 carbon atoms, an oxygen atom, a carbonyl group, a sulfur atom, a nitrogen atom, an amide group, an amino group, or a combination thereof, R 2 , R 2a , R 4 , and R 6R represents a group containing a hydrogen atom, a saturated hydrocarbon group with 1 to 10 carbon atoms, an unsaturated hydrocarbon group with 2 to 10 carbon atoms, an oxygen atom, a carbonyl group, an amide group, an amino group, or a combination thereof. 2 R 2a R 4 R 6 R represents a monovalent group. 1 R 1a R 3 R 5a and R 6a R represents a divalent group. 5 R represents a trivalent group. 7 R 8 R 9 R 10 and R 11 [These represent hydrogen atoms or saturated hydrocarbon groups with 1 to 10 carbon atoms, respectively; n represents the number of repeating units from 1 to 10; and the dashed line represents the chemical bond with adjacent atoms.] <<Organic Lower Membrane Formation Compound 4>> As an organic lower membrane forming compound 4 (SOC4 compound), compounds such as those illustrated in International Publication No. 2018 / 186310 can be used. The entire disclosure of International Publication No. 2018 / 186310 is incorporated herein by reference.

[0419] Specifically, examples include polymers having the unit structure shown in the following formula (SOC4-1).

[0420] It should be noted that, unless otherwise specified, the symbols and definitions of the groups in formulas (SOC4-1) and (SOC4-2) defined below are limited to those in formulas (SOC4-1) and (SOC4-2), namely, <<Organic Lower Membrane Forming Compound 4>>.

[0421] [Chemistry 59]

[0422] In formula (SOC4-1), A 1 A 2 and A 3 Each can independently represent an aromatic ring with 6 to 100 carbon atoms that may contain heteroatoms, or represent a hydrocarbon group containing an aromatic ring with 6 to 100 carbon atoms that may contain heteroatoms. 1 B 2 and B 3 Each can be represented independently as an inclusion expression (SOC4-2): [Transformation 60]

[0423] (In formula (SOC4-2), R 1 represents an alkylene group having 1 to 10 carbon atoms, an alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, an arylene group having 6 to 40 carbon atoms (the alkylene group, the alkenylene group, the alkynylene group and the arylene group can be optionally substituted by 1 or 2 or more cyano groups and / or 1 or 2 or more hydroxyl groups), an oxygen atom, a carbonyl group, a sulfur atom, -C(O)-O-, -C(O)-NR a -, -NR b - or a group containing a combination thereof, R a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R b represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkylcarbonyl group having 2 to 10 carbon atoms, R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the dotted line represents a bond to A 1 , A 2 or A 3 . ), X represents a carbonyl group, a sulfonyl group, -CR 2 2- group (R 2 each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ), or a -C(CF3)2- group, n1 is an integer of 1 ≤ n1 ≤ 4, n2 is an integer of 0 ≤ n2 ≤ 4, n3 is an integer of 0 ≤ n3 ≤ 4, and n1 + n2 + n3 = an integer of 1 to 12. As the organic underlayer film-forming compound 4, in addition to the unit structure represented by the above formula (SOC4-1), a polymer containing a unit structure represented by the following formula (SOC4-3) can be given.

[0424] It should be noted that the symbols of the groups in formula (SOC4-3) defined below and the definitions of the symbols are limited only to the description of formula (SOC4-3), i.e. the description of the < < organic underlayer film-forming compound 4 > > unless otherwise specified.

[0425] [Formula (SOC4-3)]

[0426] (In formula (SOC4-3), A 4 and A 5 each represent an aromatic ring having 6 to 48 carbon atoms which can contain a hetero atom, or represent a hydrocarbon group containing an aromatic ring having 6 to 48 carbon atoms which can contain a hetero atom, B 4 and B 5 represent B 1 , B 2 and B 3For the same group, n4 is an integer where 1 ≤ n4 ≤ 4, n5 is an integer where 0 ≤ n5 ≤ 4, and n4 + n5 = an integer from 1 to 8. <<Organic Lower Membrane Formation Compound 5>> As the organic lower film forming compound 5 (SOC5 compound), polymers comprising unit structures consisting of reactants of condensed heterocyclic compounds and bicyclic compounds, such as those described in International Publication No. 2013 / 005797 (Japanese Patent No. 6041104), can be used. The entire disclosure of International Publication No. 2013 / 005797 (Japanese Patent No. 6041104) is incorporated herein by reference.

[0427] Specifically, examples include polymers comprising the unit structures shown in formula (SOC5-1), formula (SOC5-2), formula (SOC5-3), or combinations thereof.

[0428] It should be noted that, unless otherwise specified, the symbols and definitions of the groups in formulas (SOC5-1) to (SOC5-3) defined below are limited to those in formulas (SOC1-1) to (SOC5-3), namely, <<Organic Lower Membrane Forming Compound 5>>.

[0429] [Chemistry 62]

[0430] [In the formula, R] 1 ~R 14 Substituents for hydrogen atoms are, independently, halogen atoms, nitro groups, amino groups, or hydroxyl groups, or alkyl groups with 1 to 10 carbon atoms or aryl groups with 6 to 40 carbon atoms that can be substituted by these groups; Ar is an aromatic cyclic group with 6 to 40 carbon atoms; n1, n2, n5, n6, n9, n 10 n 13 n 14 and n 15 The integers n3, n4, n7, n8, and n are from 0 to 3. 11 and n 12 These are integers from 0 to 4. <<Organic Lower Membrane Formation Compound 6>> As an organic lower membrane forming compound 6 (SOC6 compound), for example, the compounds exemplified in International Publication No. 2021 / 172295 can be used. The entire disclosure of International Publication No. 2021 / 172295 is incorporated herein by reference.

[0431] Specifically, for example, a polymer (SOC6 polymer) containing the same or different plural structural units having a methoxymethyl group and an ROCH2- group (here, R is a monovalent organic group, a hydrogen atom, or a mixture thereof, and the definition of R is limited only to the SOC6 compound unless otherwise specified) other than the methoxymethyl group, and a linking group linking the plural structural units can be mentioned.

[0432] In the above SOC6 polymer, R as the monovalent organic group is preferably a C2-C20 straight chain or branched chain saturated or unsaturated aliphatic hydrocarbon group which can be substituted with a phenyl group or a naphthyl group, an anthracenyl group, and which can be interrupted with an oxygen atom or a carbonyl group. 20 aliphatic hydrocarbon group, a C3-C20 cycloaliphatic hydrocarbon group, or a mixture thereof. The "mixture" means that the plural ROCH2- groups present in a single structural unit can be different, and also means that the ROCH2- groups in two or more structural units can be different. 20 aliphatic hydrocarbon group, a C3-C20 cycloaliphatic hydrocarbon group, or a mixture thereof. The "mixture" means that the plural ROCH2- groups present in a single structural unit can be different, and also means that the ROCH2- groups in two or more structural units can be different.

[0433] As typical examples of the above saturated aliphatic hydrocarbon group, a straight chain or branched chain alkyl group having 2 to 20 carbon atoms, and a cyclic alkyl group having, for example, 3 to 20 carbon atoms can be mentioned.

[0434] As typical examples of the above unsaturated aliphatic hydrocarbon group, an alkenyl group having 2 to 20 carbon atoms can be mentioned.

[0435] The above saturated aliphatic hydrocarbon group, unsaturated aliphatic hydrocarbon group, and cyclic alkyl group can be interrupted once or two or more times with an oxygen atom and / or a carbonyl group. R is particularly preferably a -CH2CH2CH2CH3 group and a -CH(CH3)CH2OCH3 group.

[0436] <<Organic Underlayer Film-Forming Compound 7>> As the organic underlayer film-forming compound 7 (SOC7 compound), for example, the compound mentioned in International Publication No. 2020 / 184380 can be used. The entire disclosure of International Publication No. 2020 / 184380 is incorporated herein by reference.

[0437] Specifically, for example, a copolymer having a repeating structural unit represented by the following formula (SOC7-1) and / or a repeating unit represented by the following formula (SOC7-2) can be mentioned.

[0438] Note that the symbols and definitions of the symbols of the groups in the above formula (SOC7-1) and formula (SOC7-2), and formula (SOC7-3) are limited only to the description of the <Organic Underlayer Film-Forming Compound 7> unless otherwise specified.

[0439] [Chemical Formula 63]

[0440] [Formula (SOC7-1) and Formula (SOC7-2) in which, R 1 represents a functional group represented by Formula (SOC7-3), In Formula (SOC7-3), Q1and Q2each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, represents a binding end to an oxygen atom, In Formula (SOC7-2), X 1 represents an organic group having 1 to 50 carbon atoms, and i and j each independently represent 0 or 1. The group X in the above Formula (SOC7-2) 1 For example, it represents a 2-valent hydrocarbon group having 2 to 20 carbon atoms in a linear, branched, or cyclic shape, a 2-valent organic group having 2 to 20 carbon atoms in a linear, branched, or cyclic shape having at least one sulfur atom or oxygen atom, or a 2-valent organic group including at least one aromatic ring having 6 to 20 carbon atoms or a heterocyclic ring having 3 to 12 carbon atoms, the heterocyclic ring having at least one sulfur atom or oxygen atom.

[0441] <<Organic Underlayer Film Forming Compound 8>> As the organic underlayer film forming compound 8 (SOC8 compound), the compounds exemplified in International Publication No. 2014 / 024836 (Japanese Patent No. 6191831) can be used. The entire disclosure of International Publication No. 2014 / 024836 (Japanese Patent No. 6191831) is incorporated herein by reference.

[0442] Specifically, for example, a polymer having any one or two or more of the repeating structural units represented by Formula (SOC8-1a), Formula (SOC8-1b), and Formula (SOC8-1c) described below can be exemplified.

[0443] Note that the symbols of the groups in Formula (SOC8-1a), Formula (SOC8-1b), Formula (SOC8-1c), and Formula (SOC8-2) defined below are limited only to the description of < < Organic Underlayer Film Forming Compound 8 > > unless otherwise specified.

[0444] [Formula 64]

[0445] [In the formula, 2 R 1each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aromatic hydrocarbon group, a halogen atom, a nitro group, or an amino group, 2R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an acetal group, an acyl group, or a glycidyl group, R 3 each independently represents an aromatic hydrocarbon group which can have a substituent, R 4 each independently represents a hydrogen atom, a phenyl group, or a naphthyl group, R 3 and R 4 each represent a phenyl group, they can be bonded to each other to form a fluorene ring, In formula (SOC8-1b), 2R 3 the groups represented by R 4 and the atoms or groups represented by R 1 each independently represent an integer of 0 or 1, m represents an integer of 3 to 500, n, n1, and n2 represent integers of 2 to 500, p represents an integer of 3 to 500, X represents a single bond or a hetero atom, and 2Q each independently represents a structural unit represented by the following formula (SOC8-2): [Chemical Formula 65]

[0446] (in the formula, 2R 1 , 2R 2 , 2R 3 , 2R 4 , 2k, n1, n2, and X each have the same meaning as in formula (SOC8-1b), and 2Q 1 each independently represents a structural unit represented by the formula (SOC8-2). <<Organic Underlayer Film-Forming Compound 9>> As the organic underlayer film-forming compound 9 (SOC9 compound), for example, a compound set forth in International Publication No. 2012 / 050064 (Japanese Patent No. 5920588) can be used. The entire disclosure of International Publication No. 2012 / 050064 (Japanese Patent No. 5920588) is incorporated herein by reference.

[0447] Specifically, for example, a polymer containing a unit structure represented by the following formula (SOC9-1), a unit structure represented by formula (SOC9-2), or a combination of the unit structure represented by formula (SOC9-1) and the unit structure represented by formula (SOC9-2) can be mentioned.

[0448] It should be noted that the symbols of the groups in the formula (SOC9-1), the formula (SOC9-2) and the definition of the symbols described below are limited only to the description of the formula (SOC9-1) and the formula (SOC9-2), that is, the description of the “< < Organic underlayer film forming compound 9 > >”, unless otherwise specified.

[0449] [Chemical Formula 66]

[0450] [In the formula (SOC9-1), Ar1 represents an organic group including an arylene group or a heterocyclic group having 6 to 50 carbon atoms.] [Chemical Formula 67]

[0451] [In the formula (SOC9-2), Ar2, Ar3, and Ar4 each represent an organic group including an arylene group or a heterocyclic group having 6 to 50 carbon atoms, and T represents a carbonyl group or a sulfonyl group.] The unit structure represented by the formula (SOC9-1) represents a unit structure having a polyether structure, and the unit structure represented by the formula (SOC9-2) represents a unit structure having a polyether ether ketone structure or a polyether ether sulfone structure.

[0452] The arylene group or the heterocyclic group in the organic group represented by the above Ar1 to Ar4 can be used in one or two or more combinations, respectively. The arylene group and the heterocyclic group, for example, represent 2 to 4 valences.

[0453] “< < Organic underlayer film forming compound 10 > >” As the organic underlayer film forming compound 10 (SOC10 compound), the compounds described in International Publication No. 2022 / 107759 can be used. The matters described in International Publication No. 2022 / 107759 are all incorporated by reference in the present application.

[0454] Specifically, for example, a polymer (SOC10 polymer) including a repeating structural unit in which an aromatic compound A having an ROCH2- group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof, and the definition of R is limited only to the SOC10 compound unless otherwise specified) and an aromatic compound B different from A having 120 or less carbon atoms are alternately bonded via a linking group -O-, and 1 to 6 B are bonded with respect to 1 A can be mentioned.

[0455] The above SOC10 polymer, for example, is a polymer including a repeating structural unit represented by the following formula (SOC10-1).

[0456] It should be noted that the symbols and definitions of the groups in the following formula (SOC10-1) are limited to those in formula (SOC10-1), i.e., <<Organic Lower Membrane Forming Compound 10>>, unless otherwise specified.

[0457] [Chemistry 68]

[0458] [In formula (SOC10-1), A1 represents an organic group from aromatic compound A having a ROCH2- group (R being a monovalent organic group, a hydrogen atom, or a mixture thereof), and B1 represents an organic group from aromatic compound B having 120 or fewer carbon atoms, different from A1.] B1 in the above formula (SOC10-1) can be a group as shown in the following formula (SOC10-2).

[0459] It should be noted that the symbols and definitions of the groups in formula (SOC10-2) are limited to those in formula (SOC10-2), i.e., <<Organic Lower Membrane Forming Compound 10>>, unless otherwise specified.

[0460] [Chemistry 69]

[0461] In formula (SOOC10-2), C1 and C2 each independently represent an aromatic ring with 6 to 48 carbon atoms that may contain heteroatoms, or a hydrocarbon group containing an aromatic ring with 6 to 48 carbon atoms that may contain heteroatoms. Y represents a single bond, carbonyl group, sulfonyl group, or -CR group. 1 2-group, or -(CF3)C(CF3)-group, R 1 This indicates that it can be interrupted by an oxygen atom, carbonyl group, nitrogen atom, carbon-carbon double bond, or carbon-carbon triple bond. The carbon-carbon double bond or carbon-carbon triple bond can be bonded to a terminal alkyl group with 1 to 10 carbon atoms, a hydroxyl group, a hydrogen atom, a halogen, an aromatic hydrocarbon group with 6 to 20 carbon atoms, or -NR. 2 2, R 2 This indicates that it can be interrupted by a carbon-carbon double bond or a carbon-carbon triple bond. The carbon-carbon double bond or carbon-carbon triple bond can be bonded to a chain-like or cyclic alkyl group with 1 to 10 carbon atoms at the end. i is 0 or 1, The dashed line represents the bond with an oxygen atom. <<Organic Lower Membrane Forming Compound 11>> As the organic underlayer film-forming compound 11 (SOC11 compound), for example, a compound set forth in International Publication No. 2013 / 146670 (Japanese Patent No. 6094767) can be used. The entire disclosure of International Publication No. 2013 / 146670 (Japanese Patent No. 6094767) is incorporated herein by reference.

[0462] Specifically, for example, a polymer containing a unit structure represented by the following formula (SOC11-1) can be mentioned.

[0463] Note that the symbols of the groups in the formula (SOC11-1) defined below and the definitions of the symbols are limited only to the description in the formula (SOC11-1), i.e., the description of the "organic underlayer film-forming compound 11" unless specifically described.

[0464] [Chemical Formula 70]

[0465] [In the formula (SOC11-1), R 1 , R 2 , and R 3 is a substituent of a hydrogen atom of a ring, and is each independently a halogen atom, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof which can include an ether bond, a ketone bond, or an ester bond.

[0466] R 4 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination thereof which can include an ether bond, a ketone bond, or an ester bond.

[0467] R 5 is a hydrogen atom, or an aryl group having 6 to 40 carbon atoms which can be substituted with a halogen atom, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, a phenyl group, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group, or a heterocyclic group; R 6 is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group which can be substituted with a halogen atom, a nitro group, an amino group, a formyl group, a carboxyl group, a carboxylic acid alkyl ester group, or a hydroxyl group; or R 5 and R 6 may form a ring together with the carbon atom to which they are bonded.

[0468] Ring A and ring B each represent a benzene ring, a naphthalene ring, or an anthracene ring.

[0469] n1, n2, and n3 are each an integer of 0 or more and up to the maximum number of substituents that can be substituted on the ring. <<Organic underlayer film forming compound 12>> As the organic underlayer film forming compound 12 (SOC12 compound), for example, the compound set forth in International Publication No. 2014 / 030579 (Japanese Patent No. 6124025) can be used. The entire disclosure of International Publication No. 2014 / 030579 (Japanese Patent No. 6124025) is incorporated herein by reference.

[0470] Specifically, the phenol novolak resin obtained by reacting a compound having at least three phenol groups and the phenol groups having a structure bonded to a tertiary carbon atom, or the phenol groups having a structure bonded to a quaternary carbon atom to which a methyl group is bonded, with an aromatic aldehyde or an aromatic ketone in the presence of an acid catalyst can be mentioned.

[0471] More specifically, as the above-mentioned phenol novolak resin, a resin containing a unit structure of the following formula (SOC12-1), a unit structure of formula (SOC12-2), a unit structure of formula (SOC12-3), a unit structure of formula (SOC12-4), or a combination of these unit structures can be mentioned.

[0472] Note that the symbols of the groups in the following defined formulas (SOC12-1) to (SOC12-4) or formula (SOC12-5) are limited only to the description in the formulas (SOC12-1) to (SOC12-5), i.e., the description of <<Organic underlayer film forming compound 12>> unless otherwise specified.

[0473] [Chemical Formula 71]

[0474] [In formula (SOC12-1), formula (SOC12-2), formula (SOC12-3), formula (SOC12-4), A is an organic group having at least three phenol groups and the phenol groups having a structure bonded to a tertiary carbon atom, B 1 , B 2 , B 3 and B 4 respectively represent formula (SOC12-5): [Chemical Formula 72]

[0475] [In formula (SOC12-5), C 1 represents an aryl group or a heterocyclic group having a carbon number of 6 to 40 which can be substituted with a halogen atom, a nitro group, an amino group, or a hydroxyl group, C 2represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which can be substituted with a halogen atom, a nitro group, an amino group, or a hydroxyl group, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group having 1 to 20 carbon atoms, and C 1 and C 2 may form a ring together with the carbon atom to which they are bonded. <Organic underlayer film forming compound 13> As the organic underlayer film forming compound 13 (SOC13 compound), for example, the compounds set forth in International Publication No. 2006 / 132088 can be used. The entire disclosure of International Publication No. 2006 / 132088 is incorporated herein by reference.

[0476] Specifically, for example, a polymer containing any one of the unit structures represented by the following formulae (SOC13-1) to (SOC13-5) can be mentioned.

[0477] Note that the symbols of the groups in the formulae (SOC13-1) to (SOC13-5) defined below and the definitions of the symbols are limited only to the descriptions in the formulae (SOC13-1) to (SOC13-5), i.e., the descriptions of the <Organic underlayer film forming compound 13> unless otherwise specifically described.

[0478] [Formula 73]

[0479] [In the above formulae, A represents an organic group having an aromatic group, Ar1represents a substituted or unsubstituted aromatic group, Ar2represents an aromatic ring which is unsubstituted or substituted with a carboxylic acid, a carboxylic acid ester group, a hydroxyl group, an alkyl group, an alkoxy group, a sulfonic acid group, or a halogen atom, R1represents a hydroxyl group, an alkyl group, an alkoxy group, a halogen atom, a thiol group, an amino group, or an amide group, m1is the number of A substituted on the naphthalene ring and represents an integer of 1 to 6, m2is the number of R1substituted on the naphthalene ring and represents an integer of 0 to 5, the sum of m1and m2is an integer of 1 to 6, and the remaining part in the case other than 6 represents a hydrogen atom, n represents a repeating unit of 2 to 7000, X represents a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, a 2-valent hydrocarbon group having an ether bond having 2 to 10 carbon atoms, or a carbonyl group, Z represents a linking group represented by -O- or -OC(=O)-. <Organic underlayer film forming compound 14> As the organic underlayer film-forming compound 14 (SOC14 compound), the compounds set forth in International Publication No. 2016 / 072316 can be used. The entire disclosure of International Publication No. 2016 / 072316 is incorporated herein by reference.

[0480] Specifically, for example, a polymer containing a unit structure represented by the following formula (SOC14-1) can be mentioned.

[0481] Note that the symbols of the groups in the formula (SOC14-1) defined below and the definitions of the symbols are limited only to the description in the formula (SOC14-1), i.e., the description of the "organic underlayer film-forming compound 14" unless specifically described.

[0482] [Chemical Formula 74]

[0483] [In the formula (SOC14-1), R 1 ~R 4 each independently represents a hydrogen atom or a methyl group. X 1 represents a divalent organic group containing an alkyl group, an amino group, or at least one arylene group which can be substituted with a hydroxyl group. X in the formula (SOC14-1) 1 For example, it can be set to an organic group represented by the following formula (SOC14-2) (dotted line represents a bond).

[0484] Note that the symbols of the groups in the formula (SOC14-2) and the formula (SOC14-3) defined below and the definitions of the symbols are limited only to the description in the formula (SOC14-2) and the formula (SOC14-3), i.e., the description of the "organic underlayer film-forming compound 14" unless specifically described.

[0485] [Chemical Formula 75]

[0486] [In the formula (SOC14-2), A 1 represents a phenylene group or a naphthylene group. A 2 represents a phenylene group, a naphthylene group, or an organic group represented by the formula (SOC14-3): [Chemical Formula 76]

[0487] (In the formula (SOC14-3), A 3 and A 4 each independently represents a phenylene group or a naphthylene group. Dotted line represents a bond.) Specific examples of each group in the above formulae (SOC14-1) to (SOC14-3) are exemplified by the following.

[0488] The above arylene group preferably uses an arylene group derived from an aromatic compound having 6 to 40 carbon atoms. As the arylene group, for example, a phenylene group, a biphenylene group, a terphenylene group, a fluorene group, a naphthalene group, an anthracene group, a pyrene group, or a carbazole group, etc. can be exemplified.

[0489] As the above alkyl group, an alkyl group having 1 to 10 carbon atoms can be exemplified.

[0490] As the above amino group, a primary amino group, a secondary amino group, a tertiary amino group can be exemplified, and a secondary amino group can be preferably used.

[0491] <<Organic Underlayer Film Forming Compound 15>> As the organic underlayer film forming compound 15 (SOC15 compound), a novolak resin obtained by the reaction of an aromatic compound with an aldehyde having a formyl group bonded to a secondary carbon atom or a tertiary carbon atom of an alkyl group having 2 to 26 carbon atoms, such as the compounds exemplified in International Publication No. 2017 / 069063, can be used. The entire disclosure of International Publication No. 2017 / 069063 is incorporated herein by reference.

[0492] Specifically, for example, a polymer containing a unit structure represented by the following formula (SOC15-1), and a more specific polymer containing a unit structure represented by the following formula (SOC15-2) can be exemplified.

[0493] Note that the symbols of the groups in the above formulae (SOC15-1) and (SOC15-2) and the definitions of the symbols are limited only to the description in the above formulae (SOC15-1) and (SOC15-2), i.e., the description of the <<Organic Underlayer Film Forming Compound 15>> unless otherwise specifically described.

[0494] [Chemical Formula 77]

[0495] [In the formula (SOC15-1), A represents a divalent group derived from an aromatic compound having 6 to 40 carbon atoms, b 1 represents an alkyl group having 1 to 16 carbon atoms, b 2 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.] [Chemical Formula 78]

[0496] [In the formula (SOC15-2), a 1 and a 2 respectively represent a benzene ring or a naphthalene ring which can be substituted, R 1represents a secondary amino group or a tertiary amino group, a divalent hydrocarbon group having 1 to 10 carbon atoms which can be substituted, an arylene group, or a divalent group formed by arbitrarily linking these groups.

[0497] b 3 represents an alkyl group having 1 to 16 carbon atoms, b 4 represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. <Organic Underlayer Film-Forming Compound 16> As the organic underlayer film-forming compound 16 (SOC16 compound), for example, the compound set forth in International Publication No. 2017 / 094780 can be used. The entire disclosure of International Publication No. 2017 / 094780 is incorporated herein by reference.

[0498] Specifically, for example, a polymer containing a unit structure represented by the following formula (SOC16-1), particularly a polymer in which the group A in the formula (SOC16-1) is a divalent group derived from a compound represented by the following formula (SOC16-2), can be mentioned.

[0499] Note that the symbols of the groups in the formula (SOC16-1) and the formula (SOC16-2) defined below and the definitions of the symbols are limited only to the description in the formula (SOC16-1) and the formula (SOC16-2), that is, the description of the <Organic Underlayer Film-Forming Compound 16> unless specifically described.

[0500] [Compound 79]

[0501] [In the formula (SOC16-1), A is a divalent group having at least two amino groups, which is a group derived from a compound having a fused ring structure and having an aromatic group having a hydrogen atom on the fused ring substituted, B 1 , B 2 each independently represents a hydrogen atom, an alkyl group, a phenyl ring group, a fused ring group, or a combination thereof, or B 1 and B 2 may form a ring together with the carbon atom to which they are bonded. [Compound 80]

[0502] [In the formula (SOC16-2), R 1 and R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. <Organic Underlayer Film-Forming Compound 17> As the organic underlayer film-forming compound 17 (SOC 17 compound), for example, a compound set forth in Japanese Patent Application Publication No. 2005-128509 (Japanese Patent No. 4355943) can be used. The entire disclosure of Japanese Patent Application Publication No. 2005-128509 (Japanese Patent No. 4355943) is incorporated herein by reference.

[0503] Specifically, for example, a novolak resin having a repeating unit represented by the following formula (SOC 17-1a) or formula (SOC 17-1b) having a fluorene or tetrahydrospiroinden structure can be mentioned.

[0504] Note that the symbols of the groups in the formula (SOC 17-1a), formula (SOC 17-1b) defined below and the definitions of the symbols are limited only to the description in the formula (SOC 17-1a), formula (SOC 17-1b), i.e., the description of the < < organic underlayer film-forming compound 17 > > unless specifically described.

[0505] [Formula (SOC 17-1a), (SOC 17-1b)]

[0506] [In the formula (SOC 17-1a), (SOC 17-1b), R 1 , R 2 , R 6 , R 7 independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an allyl group, or a halogen atom, R 3 , R 4 , R 8 , R 9 independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a glycidyl group, R 5 , R 14 independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. n, m, p, q are integers from 1 to 3. R 10 ~ R 13 independently a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched, or cyclic alkoxy group having 1 to 6 carbon atoms. < < Organic underlayer film-forming compound 18 > > As the organic underlayer film-forming compound 18 (SOC 18 compound), for example, a compound set forth in Japanese Patent Application Publication No. 2006-259249 (Japanese Patent No. 4539845) can be used. The entire disclosure of Japanese Patent Application Publication No. 2006-259249 (Japanese Patent No. 4539845) is incorporated herein by reference.

[0507] Specifically, for example, a compound containing a bisphenol group represented by the following formula (SOC 18-1), and a resin having a repeating unit obtained by novolakization of a compound having a bisphenol group represented by the following formula (SOC 18-2) can be mentioned.

[0508] Note that the symbols of the groups in the formula (SOC 18-1), the formula (SOC 18-2) defined below, and the definitions of the symbols are limited only to the description in the formula (SOC 18-1), the formula (SOC 18-2), i.e., the description of the "organic underlayer film-forming compound 18" unless otherwise specifically noted.

[0509] [Chemical Formula 82]

[0510] [In the formula (SOC 18-1), (SOC 18-2), R 1 , R 2 are the same or different hydrogen atoms, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. R 3 , R 4 is a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an acetal group having 2 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or a glycidyl group, and Y is a divalent aliphatic or alicyclic hydrocarbon group having 4 to 30 carbon atoms, [Chemical Formula 83]

[0511] The ring represented by the formula can be a bridged ring, and a hetero atom can be present. R 5 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms "Organic underlayer film-forming compound 19" As the organic underlayer film-forming compound 19 (SOC 19 compound), for example, the compound set forth in Japanese Patent Application Publication No. 2006-259482 (Japanese Patent No. 4466854) can be used. The entire disclosure of Japanese Patent Application Publication No. 2006-259482 (Japanese Patent No. 4466854) is incorporated herein by reference.

[0512] Specifically, for example, the following compounds containing a plurality of bisphenol groups represented by the following formula (SOC 19-1), and resins having repeating units obtained by novolakizing the following compound having a bisphenol group represented by the following formula (SOC 19-2) can be mentioned.

[0513] Note that the symbols of the groups in the formula (SOC 19-1), the formula (SOC 19-2) defined below, and the definitions of the symbols are limited only to the description in the formula (SOC 19-1) and the formula (SOC 19-2), i.e., the description of the "organic underlayer film-forming compound 19" unless otherwise specified.

[0514] [Chemical Formula 84]

[0515] [In the formula (SOC 19-1), (SOC 19-2), R 1 is the same or different hydrogen atom, linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, or alkenyl group having 2 to 10 carbon atoms. R 2 is the same or different hydrogen atom or linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, aryl group having 6 to 10 carbon atoms, acetal group having 2 to 6 carbon atoms, acyl group having 2 to 6 carbon atoms, or glycidyl group, and n is an integer of 2 to 4. R 3 is hydrogen atom, linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or aryl group having 6 to 10 carbon atoms.

[0516] [Chemical Formula 85]

[0517] represents a 2n-valent hydrocarbon group having 4 to 30 carbon atoms, can contain one or two or more kinds of alicyclic hydrocarbon group, bridged cyclic hydrocarbon group, aromatic hydrocarbon group, condensed polycyclic hydrocarbon group, A represents a 4-valent hydrocarbon group bonded to [Chemical Formula 86]

[0518] bonded 4-valent hydrocarbon group, and A in [Chemical Formula 87]

[0519] n is present. In addition, [Chem. 88]

[0520] A heteroatom can be present. <<Organic Underlayer Film-Forming Compound 20>> As the organic underlayer film-forming compound 20 (SOC20 compound), for example, the compound set forth in Japanese Patent Application Publication No. 2007-199653 (Japanese Patent No. 4659678) can be used. The entire disclosure of Japanese Patent Application Publication No. 2007-199653 (Japanese Patent No. 4659678) is incorporated herein by reference.

[0521] Specifically, for example, a resin in which a compound having a bisnaphthol group represented by the following formula (SOC20-1) and a compound having a bisnaphthol group represented by the following formula (SOC20-2) are novolakized can be mentioned.

[0522] Note that the symbols of the groups in the formula (SOC20-1), the formula (SOC20-2) defined below and the definitions of the symbols are limited only to the description of the < < Organic Underlayer Film-Forming Compound 20 > > unless otherwise specified.

[0523] [Chem. 89]

[0524] [In the above formula (SOC20-1), (SOC20-2), R 1 and R 2 are independently the same or different hydrogen atom, linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, or alkenyl group having 2 to 10 carbon atoms, R 3 is a single bond, or alkylene group having 1 to 30 carbon atoms having a linear, branched, or cyclic structure, and can have a bridged cyclic hydrocarbon group, a double bond, a heteroatom such as sulfur, or an aromatic group having 6 to 30 carbon atoms, R 4 and R 5 are each independently hydrogen atom, or glycidyl group, R 6 is a single bond, or linear or branched alkylene group having 1 to 10 carbon atoms. n is an integer of 1 to 4. <<Organic Underlayer Film-Forming Compound 21>> As the organic underlayer film-forming compound 21 (SOC21 compound), for example, the compound set forth in Japanese Patent Application Publication No. 2010-170013 (Japanese Patent No. 5118073) can be used. The entire disclosure of Japanese Patent Application Publication No. 2010-170013 (Japanese Patent No. 5118073) is incorporated herein by reference as part of the disclosure of the present application.

[0525] Specifically, for example, the compound having a bisnaphthol group represented by the following formula (SOC21-1), and the resin in which the compound having a bisnaphthol group represented by the following formula (SOC21-2) is novolakized can be mentioned.

[0526] Note that the symbols of the groups in the formula (SOC21-1), the formula (SOC21-2) defined below, and the definitions of the symbols are limited only to the description in the formula (SOC21-1) and the formula (SOC21-2), i.e., the description of the "organic underlayer film-forming compound 21" unless otherwise specifically noted.

[0527] [Compound 90]

[0528] [In the formula (SOC21-1), the formula (SOC21-2), R 1 ~R 4 are the same or different hydrogen atoms, linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, R 5 ~R 8 are each hydrogen atoms, linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms, acyl groups, or glycidyl groups, R 9 are hydrogen atoms, linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms, alkoxy groups, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, halogen atoms, amino groups, alkylmethylamino groups having 1 to 4 carbon atoms, diarylamino groups having 6 to 10 carbon atoms, cyano groups, nitro groups, R 10 , R 11 are linear or branched alkylene groups having 1 to 10 carbon atoms, m, n, p, q, and r are integers of 0 to 6, and m+n+p+q is an integer of 2 to 10. <<Organic underlayer film-forming compound 22>> As the organic underlayer film-forming compound 22 (SOC22 compound), for example, the compound set forth in Japanese Patent Application Publication No. 2010-122656 (Japanese Patent No. 5336306) can be used. The entire disclosure of Japanese Patent Application Publication No. 2010-122656 (Japanese Patent No. 5336306) is incorporated herein by reference as part of the disclosure of the present application.

[0529] Specifically, for example, a compound having a bisnaphthol group represented by the following formula (SOC22-1), and a novolak resin obtained by novolaking a compound having a bisnaphthol group represented by the following formula (SOC22-2) can be mentioned.

[0530] Note that the symbols and definitions of the symbols of the groups in the formula (SOC22-1), the formula (SOC22-2) of the following definitions are limited only to the description in the formula (SOC22-1) and the formula (SOC22-2), i.e., the description of the < < organic underlayer film forming compound 22 > > unless otherwise specified.

[0531] [Chemical 91]

[0532] [In the formula (SOC22-1), R 1 , R 2 are the same or different hydrogen atoms, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms. R 3 , R 4 are each a hydrogen atom or a glycidyl group, R 5 is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, R 6 , R 7 are a benzene ring or a naphthalene ring. p and q are each 1 or 2. n is 0 < n < 1.

[0533] In the formula (SOC22-2), R 1 to R 7 , p, and q are as described above. R 8 , R 9 are a hydrogen atom, a hydroxyl group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a carbonyl group, an amino group, an imino group, a hydroxyl group substituted with an acid-labile group or a glycidyl group, or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. R 10 , R 11 are a benzene ring or a naphthalene ring, R 13 , R 14 are a hydrogen atom, a hydroxyl group, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, R 13 and R 14 may be bonded to form a ring. R 12 , R 15a straight-chain, branched-chain or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. R <<Organic underlayer film-forming compound 23>> As the organic underlayer film-forming compound 23 (SOC23 compound), for example, the compounds set forth in Japanese Patent Application Publication No. 2016-018051 (Japanese Patent No. 6196190) can be used. The entire disclosure of Japanese Patent Application Publication No. 2016-018051 (Japanese Patent No. 6196190) is incorporated herein by reference thereto.

[0534] Specifically, for example, a resin obtained by novolakization of a compound having a bisnaphthol group represented by the following formula (SOC23-1) can be mentioned.

[0535] Note that the symbols of the groups in formula (SOC23-1) defined below and the definitions of the symbols are limited only to the description in formula (SOC23-1), that is, the description of <<Organic underlayer film-forming compound 23>> unless specifically described.

[0536] [Compound 92]

[0537] [In formula (SOC23-1), R 1 , R 2 each independently is a hydrogen atom, a straight-chain, branched-chain or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. R 3 , R 4 each independently is a hydrogen atom or a glycidyl group. R 5 is a straight-chain or branched-chain alkylene group having 1 to 10 carbon atoms. R 6 , R 7 each independently is any one of a benzene ring, a naphthalene ring, and the hydrogen atom in the benzene ring, the naphthalene ring or the benzene ring can be substituted with a hydrocarbon group having 1 to 6 carbon atoms. p, q each independently is 1 or 2. <<Organic underlayer film-forming compound 24>> As the organic underlayer film-forming compound 24 (SOC24 compound), for example, the compounds set forth in Japanese Patent Application Publication No. 2009-014816 (Japanese Patent No. 4877101) can be used. The entire disclosure of Japanese Patent Application Publication No. 2009-014816 (Japanese Patent No. 4877101) is incorporated herein by reference thereto.

[0538] Specifically, for example, mention can be made of resins having a group represented by the following formula (SOC24-1) and an aromatic hydrocarbon group, and more specifically, mention can be made of resins having a structural unit represented by the following formula (SOC24-2).

[0539] It should be noted that the symbols and definitions of the symbols of the groups in the formula (SOC24-1), the formula (SOC24-2) defined below are limited only to the description of the formula (SOC24-1) and the formula (SOC24-2), i.e., the description of the "organic underlayer film-forming compound 24" unless otherwise specified.

[0540] [Chemical Formula 93]

[0541] [In the formula (SOC24-1), n represents 0 or 1. R 1 represents a substituted or unsubstituted methylene group, a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. R 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. [Chemical Formula 94]

[0542] [In the formula (SOC24-2), n represents 0 or 1. R 1 represents a substituted or unsubstituted methylene group, a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. R 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. 3 ~R 7 represents a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 carbon atoms, or a substituted or unsubstituted glycidyl ether group having 2 to 6 carbon atoms. R 9 represents a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched, or cyclic alkyl ether group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. <<Organic underlayer film-forming compound 25>> As the organic underlayer film-forming compound 25 (SOC25 compound), for example, the compound set forth in Japanese Patent Application Publication No. 2019-041059 (Japanese Patent No. 6726142) can be used. The entire disclosure of Japanese Patent Application Publication No. 2019-041059 (Japanese Patent No. 6726142) is incorporated herein by reference as part of the disclosure of the present application.

[0543] Specifically, for example, a polymer having a repeating unit represented by the following formula (SOC25-1) can be mentioned.

[0544] Note that the symbols of the groups in the formula (SOC25-1) and the formula (SOC25-2) defined below and the definitions of the symbols are limited only to the description in the formula (SOC25-1) and the formula (SOC25-2), i.e., the description of the < < organic underlayer film-forming compound 25 > > unless specifically described.

[0545] [Chemical Formula 95]

[0546] [In the formula (SOC25-1), AR1, AR2, and AR3 are a benzene ring, a naphthalene ring, or an anthracene ring which can have a substituent, and the carbon atoms on the aromatic rings of AR1 and AR2 or AR2 and AR3 can be directly bonded to each other or bonded via a linking group to form a bridged structure. R 1 , R 2 each independently is a hydrogen atom or an organic group having 1 to 30 carbon atoms, in the case where R 1 and R 2 are an organic group, R 1 and R 2 may be bonded within a molecule to form a cyclic organic group. Y is a group represented by the following formula (SOC25-2). [Chemical Formula 96]

[0547] [In the formula (SOC25-2), R 3 is a single bond or a 2-valent organic group having 1 to 20 carbon atoms, and R 4 is a hydrogen atom or a 1-valent organic group having 1 to 20 carbon atoms, and the dotted line represents a bond.] < < Organic underlayer film-forming compound 26 > > As the organic underlayer film-forming compound 26 (SOC26 compound), for example, the compound set forth in Japanese Patent Application Publication No. 2019-044022 (Japanese Patent No. 6940335) can be used. The entire disclosure of Japanese Patent Application Publication No. 2019-044022 (Japanese Patent No. 6940335) is incorporated herein by reference as part of the disclosure of the present application.

[0548] Specifically, for example, a polymer having a repeating unit represented by the following formula (SOC26-1) can be given.

[0549] Note that the symbols and definitions of the symbols of the groups in the formula (SOC26-1), and the formula (SOC26-2) and the formula (SOC26-3) defined below are limited only to the description of the formula (SOC26-1), the formula (SOC26-2) and the formula (SOC26-3), that is, the description of the “< < Organic underlayer film-forming compound 26 > >” unless otherwise specified.

[0550] [Chemical Formula 97]

[0551] [In the formula (SOC26-1), AR1, AR2are a benzene ring or a naphthalene ring which can have a substituent, R 1 , R 2 each independently is a hydrogen atom or an organic group having 1 to 30 carbon atoms, in the case where R 1 and R 2 are an organic group, R 1 and R 2 may also form a cyclic organic group by bonding within the molecule. n is 0 or 1, in the case where n = 0, AR1, AR2do not form a bridged structure between the aromatic rings of AR1and AR2via Z, in the case where n = 1, AR1, AR2form a bridged structure between the aromatic rings of AR1and AR2via Z, Z is a single bond or any one of the following formula (SOC26-2). Y is a group represented by the following formula (SOC26-3). [Chemical Formula 98]

[0552] [Chemical Formula 99]

[0553] [In the formula (SOC26-3), R 3 is a single bond or a 2-valent organic group having 1 to 20 carbon atoms, R 4 is a hydrogen atom or a 1-valent organic group having 1 to 20 carbon atoms, and the dotted line indicates a bond.] < < Organic underlayer film-forming compound 27 > > As the organic underlayer film-forming compound 27 (SOC27 compound), for example, the compound mentioned in Japanese Patent Application Publication No. 2021-015222 can be used. The entire disclosure of Japanese Patent Application Publication No. 2021-015222 is hereby incorporated by reference into the present application.

[0554] Specifically, for example, a polymer having a partial structure represented by the following formula (SOC27-1A) as a repeating unit can be given, and more specifically, a polymer having a partial structure represented by the following formula (SOC27-1B) as a repeating unit can be given.

[0555] Note that the symbols and definitions of the symbols of the groups of the formula (SOC27-1A) and the formula (SOC27-1B) defined below are limited only to the description of the formula (SOC27-1A) and the formula (SOC27-1B), that is, the description of the "organic underlayer film-forming compound 27" unless specifically described.

[0556] [Chemical Formula 100]

[0557] [In the above formula (SOC27-1A), (SOC27-1B), AR1, AR2 are a benzene ring or a naphthalene ring which can have a substituent, R is a hydrogen atom or a monovalent organic group having an unsaturated bond having 2 to 10 carbon atoms, R' is a single bond or W1, and W1 is a divalent organic group having 6 to 80 carbon atoms having one or more aromatic rings. "Organic underlayer film-forming compound 28" As the organic underlayer film-forming compound 28 (SOC28 compound), for example, the compounds exemplified in Japanese Patent Application Publication No. 2016-216367 (Japanese Patent No. 6372887) can be used. The entire disclosure of Japanese Patent Application Publication No. 2016-216367 (Japanese Patent No. 6372887) is incorporated herein by reference.

[0558] Specifically, for example, a compound represented by the following formula (SOC28-1) can be given.

[0559] Note that the symbols and definitions of the symbols of the groups of the formula (SOC28-1), the formula (SOC28-2), and the formula (SOC28-3) defined below are limited only to the description of the formula (SOC28-1), the formula (SOC28-2), and the formula (SOC28-3), that is, the description of the "organic underlayer film-forming compound 28" unless specifically described.

[0560] [Chemical Formula 101]

[0561] [In formula SOC28-1, n1 and n2 each independently represent 0 or 1, and W represents either a single bond or a structure represented by formula (SOC28-2) below. R1 is any one of structures represented by general formula (SOC28-3) below, and m1 and m2 each independently represent an integer of 0 to 7. Here, m1 + m2 is 1 or more and 14 or less.] [Chemical Formula 102]

[0562] [In formula (SOC28-2), 1 represents an integer of 0 to 3, and R a ~R f each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which can be substituted with fluorine, a phenyl group, or a phenylethyl group, and R a and R b may be bonded to form a cyclic compound.] [Chemical Formula 103]

[0563] [In formula (SOC28-3), represents a bonding site to an aromatic ring, and Q1 represents a linear, branched, saturated, or unsaturated hydrocarbon group having 1 to 30 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, or a substituted or unsubstituted phenyl group, naphthyl group, anthryl group, or pyrenyl group. In the case where Q1 represents a linear, branched, saturated, or unsaturated hydrocarbon group having 1 to 30 carbon atoms, a methylene group constituting Q1 can be substituted with an oxygen atom or a carbonyl group.] <cross-linking agent> The aforementioned organic underlayer film-forming composition can contain a cross-linking agent.

[0564] As the cross-linking agent, a melamine-based compound, a substituted urea-based compound, or a polymer-based compound thereof, or the like can be given. A cross-linking agent having at least two cross-linking-forming substituents such as a hydroxymethyl group, an alkoxymethyl group, or the like is preferable, and specifically, a methoxymethylated glycoluril, a butoxymethylated glycoluril, a methoxymethylated melamine, a butoxymethylated melamine, a methoxymethylated benzoguanamine, a butoxymethylated benzoguanamine, a methoxymethylated urea, a butoxymethylated urea, a methoxymethylated thiourea, or a butoxymethylated thiourea, or the like is preferable. In addition, a condensate of these compounds can also be used.

[0565] In addition, as the aforementioned cross-linking agent, a cross-linking agent having high heat resistance can be used. As the cross-linking agent having high heat resistance, a compound having a cross-linking-forming substituent having an aromatic ring (for example, a benzene ring, a naphthalene ring) in the molecule can be preferably used.

[0566] These compounds can be exemplified by compounds having a partial structure shown in the following formula (CLA1), or polymers or oligomers having a repeating unit shown in the following formula (CLA2).

[0567] [Chemical Formula 104]

[0568] In formula (CLA1), R CLA1 and R CLA2 each independently are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, n cla1 is an integer of 1 to 4, n cla2 is an integer of 1 to (5-n cla1 ), and (n cla1 +n cla2 ) represents an integer of 2 to 5.

[0569] In formula (CLA2), R CLA3 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R CLA4 is an alkyl group having 1 to 10 carbon atoms, n cla3 is an integer of 1 to 4, n cla4 is 0 to (4-n cla3 ), and (n cla3 +n cla4 ) represents an integer of 1 to 4.

[0570] The oligomers and polymers can be used in a range where the number of repeating unit structures is 2 to 100, or 2 to 50.

[0571] These alkyl groups and aryl groups, for example, can be exemplified by the alkyl groups and aryl groups exemplified in the following < <Organic Underlayer Film Forming Compound 1 (SOC Compound 1) >>.

[0572] The following exemplify compounds, polymers, and oligomers shown in formula (CLA1) and formula (CLA2).

[0573] [Chemical Formula 105]

[0574] [Chemical Formula 106]

[0575] [Chemical Formula 107]

[0576] The above compounds can be obtained as products of Asahi Organic Materials Industry Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the above crosslinking agents, the compound of formula (CLA-21) can be obtained as a product of Asahi Organic Materials Industry Co., Ltd. under the trade name TM-BIP-A.

[0577] The amount of crosslinking agent added in the organic lower layer film forming composition varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., and is 0.001 to 80% by mass relative to the total solids content, preferably 0.01 to 50% by mass, and more preferably 0.05 to 40% by mass.

[0578] These crosslinking agents sometimes undergo crosslinking reactions based on self-condensation, but when crosslinking substituents are present in the aforementioned organic lower film forming compounds 1 to 28 (SOC1 compounds to SOC28 compounds), they can undergo crosslinking reactions with these crosslinking substituents.

[0579] <<Acid or Acid-Generating Agent>> The above-mentioned organic lower layer film forming composition can contain an acid or an acid-generating agent as a catalyst for promoting the above-mentioned crosslinking reaction. That is, it can be combined with acidic compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, ammonium salts of trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, pyridinium p-phenolsulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthic acid, or / and thermal acid-generating agents such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic alkyl sulfonates.

[0580] The amount of these compounds relative to the total solids content of the organic lower layer film-forming composition is 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 3% by mass.

[0581] In addition to the aforementioned thermal acid-producing agents, photo-producing agents can also be cited as acid-producing agents.

[0582] Examples of photoacid-generating agents included in organic lower membrane forming compositions include onium salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds.

[0583] Examples of onionium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethane sulfonate, diphenyliodonium nonafluoron-butane sulfonate, diphenyliodonium perfluoron-octane sulfonate, diphenyliodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium camphor sulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethane sulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butane sulfonate, triphenylsulfonium camphor sulfonate, triphenylsulfonium trifluoromethane sulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride.

[0584] As the sulfonimide compound, for example, N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, and N- (trifluoromethanesulfonyloxy) naphthalene dicarboxylic imide, and the like can be mentioned.

[0585] As the disulfonyl diazomethane compound, for example, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (2, 4-dimethylphenylsulfonyl) diazomethane, and methylsulfonyl-p-toluenesulfonyl diazomethane, and the like can be mentioned.

[0586] The photoacid generator can be used singly, or two or more kinds can be used in combination.

[0587] In the case of using the photoacid generator, as the proportion thereof, 0.01 to 5 parts by mass, or 0.1 to 3 parts by mass, or 0.5 to 1 part by mass, relative to 100 parts by mass of the solid content of the organic underlayer film-forming composition.

[0588] <Other additives> In the above organic underlayer film-forming composition, in addition to the above components, a rheology modifier, an adhesion aid, a surfactant, and the like can be further added as needed. These can be added to the organic underlayer film-forming composition in various compounds and the like mentioned as the components that can be incorporated into the composition for forming a silicon-containing underlayer film, and the amount of incorporation.

[0589] <Formation of neutral film> The neutral film can be formed by applying the neutral film-forming composition described later on the underlayer film (silicon-containing underlayer film) using the above appropriate coating method, and then performing firing.

[0590] As the conditions for performing firing, 80 to 300°C, or 80 to 250°C, for the firing temperature, and 0.3 to 60 minutes, for the firing time, are appropriately selected. It is preferable that the firing temperature be 150 to 250°C, and the firing time be 0.5 to 2 minutes.

[0591] Here, as the film thickness of the formed neutral film, for example, 10 to 1000 nm, or 20 to 500 nm, or 10 to 300 nm, or 5 to 100 nm.

[0592] <Neutral film-forming composition> In the neutral film (NL film) used in the present application, a material hitherto used as an underlayer film for making it easy to arrange a self-assembled film into a desired pattern can be used. For example, a polymer containing a unit structure from an aromatic vinyl compound (neutral film-forming polymer 1), or a polymer having a unit structure including an aliphatic polycyclic structure from an aliphatic polycyclic compound in the main chain (neutral film-forming polymer 2), and the like can be used, but is not limited to these.

[0593] The composition for forming the above-mentioned neutral film (NL film) (referred to as a neutral film-forming composition) can contain the above-mentioned neutral film-forming polymer and a solvent described later, and in this case, the solid content in the neutral film-forming composition can be, for example, 0.01 to 20 mass%, or 0.01 to 15 mass%, or 0.1 to 15 mass%. Here, the solid content is the proportion remaining after removing the solvent and water from the neutral film-forming composition.

[0594] In addition, the proportion of the above-mentioned polymer (neutral film-forming polymer 1, neutral film-forming polymer 2) in the solid content is usually 50 to 100 mass%, in one mode 60 to 95 mass%, and in another mode 70 to 90 mass%.

[0595] <<Neutral film-forming polymer 1: polymer containing an aromatic vinyl compound>> The neutral film-forming composition used in the present application can contain, for example, a polymer (neutral film-forming polymer 1) which is a polymer having 20 mol% or more of a unit structure from an aromatic vinyl compound with respect to the total unit structure of the polymer, and having a unit structure from a polycyclic aromatic vinyl compound in a range of 1 mol% or more, or 20 mol% to 100 mol%, or 50 mol% to 100 mol% with respect to the total unit structure from the aromatic vinyl compound.

[0596] The above-mentioned aromatic vinyl compound preferably contains, respectively, a naphthyl vinyl compound, acenaphthene, or a vinyl carbazole, and the above-mentioned polycyclic aromatic vinyl compound is preferably a naphthyl vinyl compound, acenaphthene, or a vinyl carbazole.

[0597] The polymer used in the above-mentioned neutral film-forming composition must contain a unit structure from a polycyclic aromatic vinyl compound, and as a compound of the polycyclic aromatic vinyl compound as a higher concept, an aromatic vinyl compound exists.

[0598] As the above-mentioned polycyclic aromatic vinyl compound, a naphthyl vinyl compound, a vinyl anthracene compound, acenaphthene, a vinyl carbazole compound, and the like can be given. In addition, as other aromatic vinyl compounds, a styrene compound and the like can be given.

[0599] The above-mentioned aromatic vinyl compound preferably includes styrene which can be substituted and vinyl naphthalene, acenaphthylene or vinyl carbazole each of which can be substituted, and in this case, the polycyclic aromatic vinyl compound can be provided as vinyl naphthalene, acenaphthylene or vinyl carbazole each of which can be substituted.

[0600] Further, the above-mentioned aromatic vinyl compound preferably includes styrene which can be substituted and vinyl naphthalene, acenaphthylene or vinyl carbazole each of which can be substituted, and in this case, the polycyclic aromatic vinyl compound can be provided as vinyl naphthalene, acenaphthylene or vinyl carbazole each of which can be substituted.

[0601] Further, in the case where the above-mentioned aromatic vinyl compound includes only the polycyclic aromatic vinyl compound, the above-mentioned aromatic vinyl compound can be provided as vinyl naphthalene, acenaphthylene or vinyl carbazole each of which can be substituted.

[0602] In this case, it is preferable to provide a polymer having 60 to 95 mole% of the unit structure from the aromatic vinyl compound with respect to the total unit structure of the above-mentioned polymer.

[0603] The above-mentioned aromatic vinyl compound and the polycyclic aromatic vinyl compound can be copolymerized to produce a polymer.

[0604] As the substituent of the aromatic ring in the above-mentioned aromatic vinyl compound and polycyclic aromatic vinyl compound, an alkyl group, a hydroxyl group, a carboxyl group, a halogen group (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), and the like can be mentioned. As the above-mentioned alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, a 1-methyln-butyl group, a 2-methyln-butyl group, a 3-methyln-butyl group, a 1,1-dimethyln-propyl group, a 1,2-dimethyln-propyl group, a 2,2-dimethyln-propyl group, a 1-ethyln-propyl group, an n-hexyl group, a 1-methyln-pentyl group, a 2-methyln-pentyl group, a 3-methyln-pentyl group, a 4-methyln-pentyl group, a 1,1-dimethyln-butyl group, a 1,2-dimethyln-butyl group, a 1,3-dimethyln-butyl group, a 2,2-dimethyln-butyl group, a 2,3-dimethyln-butyl group, a 3,3-dimethyln-butyl group, a 1-ethyln-butyl group, a 2-ethyln-butyl group, a 1,1,2-trimethyln-propyl group, a 1,2,2-trimethyln-propyl group, a 1-ethy l-1-methyln-propyl group, a 1-ethy l-2-methyln-propyl group, and the like can be mentioned. In addition, as the above-mentioned alkyl group, a cyclic alkyl group can also be used, and for example, as a cyclic alkyl group having 1 to 10 carbon atoms, a cyclopropyl group, a cyclobutyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a cyclopentyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 3-methylcyclobutyl group, a 1,2-dimethylcyclopropyl group, a 2,3-dimethylcyclopropyl group, a 1-ethy lcyclopropyl group, a 2-ethy lcyclopropyl group, a cyclohexyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 1-ethy lcyclobutyl group, a 2-ethy lcyclobutyl group, a 3-ethy lcyclobutyl group, a 1,2-dimethylcyclobutyl group, a 1,3-dimethylcyclobutyl group, a 2,2-dimethylcyclobutyl group, a 2,3-dimethylcyclobutyl group, a 2,4-dimethylcyclobutyl group, a 3,3-dimethylcyclobutyl group, a 1-n-propylcyclopropyl group, a 2-n-propylcyclopropyl group, a 1-iso-propylcyclopropyl group, a 2-iso-propylcyclopropyl group, a 1,2,2-trimethylcyclopropyl group, a 1,2,3-trimethylcyclopropyl group, a 2,2,3-trimethylcyclopropyl group, a 1-ethy l-2-methy lcyclopropyl group, a 2-ethy l-1-methy lcyclopropyl group, a 2-ethy l-2-methy lcyclopropyl group, a 2-ethy l-3-methy lcyclopropyl group, and the like can be mentioned.

[0605] The above-mentioned polymer can further have a unit structure having a cross-linking-forming group as a copolymerization component. In the case where the above-mentioned polymer has the unit structure having a cross-linking-forming group, the polymer can have the unit structure having a cross-linking-forming group at a proportion of 1 to 80 mol%, preferably 5 to 40 mol%, with respect to the total unit structure of the polymer.

[0606] The above-mentioned cross-linking-forming group can be a hydroxyl group, an epoxy group, a protected hydroxyl group, or a protected carboxyl group.

[0607] As the monomer having a hydroxyl group, for example, a vinyl group-containing hydroxyl group such as a hydroxyalkyl (meth)acrylate, a vinyl alcohol, and the like, or a phenolic hydroxyl group such as a hydroxystyrene can be mentioned. The alkyl group can be mentioned as the above-mentioned alkyl group, and for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and the like can be mentioned. Note that, in the present specification, (meth)acrylate refers to both methacrylate and acrylate.

[0608] As the monomer having an epoxy group, for example, a vinyl group-containing epoxy group such as an epoxy (meth)acrylate, a glycidyl (meth)acrylate, and the like can be mentioned.

[0609] As the monomer having a protected hydroxyl group, for example, a monomer in which a hydroxyl group of a hydroxystyrene is protected with a tert-butoxy group (4-tert-butoxystyrene) can be mentioned. Alternatively, a monomer in which a phenolic hydroxyl group of a hydroxystyrene or the like is protected by reacting with a vinyl ether compound, a monomer in which an alcoholic hydroxyl group of a hydroxyethyl methacrylate or the like is protected by reacting with a vinyl ether compound, and the like can be mentioned. The vinyl ether compound can be mentioned as, for example, aliphatic vinyl ether compounds having an alkyl chain having 1 to 10 carbon atoms and a vinyl ether group such as a methyl vinyl ether, an ethyl vinyl ether, an isopropyl vinyl ether, a n-butyl vinyl ether, a 2-ethylhexyl vinyl ether, a tert-butyl vinyl ether, a cyclohexyl vinyl ether, and the like; cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, 2,3-dihydro-4H-pyran, and the like.

[0610] As the monomer having a protected carboxyl group, for example, a monomer in which a carboxyl group of a (meth)acrylic acid, a vinylbenzoic acid, or the like is protected by reacting with a vinyl ether compound can be mentioned. As the vinyl ether compound used here, the above-mentioned vinyl ether compounds can be exemplified.

[0611] As the neutral membrane-forming polymer 1, in addition to the unit structure from the above-mentioned aromatic vinyl compound, the unit structure from the above-mentioned polycyclic aromatic vinyl compound, and the unit structure having the above-mentioned crosslinking-forming group, a polymer in which a vinyl compound is copolymerized can also be used. In the case where the above-mentioned neutral membrane-forming polymer 1 has a unit structure from the vinyl compound, the polymer can have a unit structure from the vinyl compound in a proportion of 1 to 80 mol%, preferably 5 to 40 mol% with respect to the total unit structure of the polymer.

[0612] As these vinyl compounds, mention can be made of methyl (meth)acrylate, ethyl (meth)acrylate, n-hexyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, anthryl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trichloroethyl (meth)acrylate, 2-bromoethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, butoxy(2-ethyl) (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-benzyl (meth)acrylamide, N-phenyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-anthryl (meth)acrylamide, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, and the like.

[0613] The weight average molecular weight of the neutral film-forming polymer 1 used in the neutral film-forming composition can be used in the range of 1000 to 200000, or 1000 to 100000, or 1000 to 50000.

[0614] The above weight average molecular weight can be measured by GPC, and the measurement conditions of GPC can be, for example, using a GPC device (trade name HLC-8220GPC, manufactured by Tosoh Corporation), GPC columns (trade name Shodex KF 803L, KF802, KF801, manufactured by Showa Denko K.K.), column temperature of 40°C, eluent (elution solvent) of tetrahydrofuran, flow rate of 1.0 ml / minute, and standard sample of polystyrene (manufactured by Showa Denko K.K.).

[0615] <<Neutral film-forming polymer 2: polymer having a unit structure including an aliphatic polycyclic structure of an aliphatic polycyclic compound in a main chain>> The neutral film-forming composition used in the present application can include, for example, a polymer (neutral film-forming polymer 2) having a unit structure including an aliphatic polycyclic structure from an aliphatic polycyclic compound in a main chain.

[0616] The above neutral film-forming polymer 2 can be a polymer having a unit structure including an aliphatic polycyclic structure from an aliphatic polycyclic compound in a main chain of a polymerization chain, and a unit structure including an aromatic ring structure from a compound containing an aromatic ring in a main chain of a polymerization chain.

[0617] Further, the above polymer can be a polymer having a unit structure including an aliphatic polycyclic structure from an aliphatic polycyclic compound in a main chain of a polymerization chain and a unit structure of a polymerization chain including a vinyl group from a compound containing a vinyl group in the main chain.

[0618] The compound containing a vinyl group can be exemplified by olefins such as ethylene and propylene, acrylic esters such as methyl acrylate and methyl methacrylate, and methacrylic esters.

[0619] The above polymer has, for example, a structure represented by the following formula (11).

[0620] [Chemical Formula 108]

[0621] In formula (11), Q is a single bond, a divalent group having a structure from a compound containing a vinyl group as a polymerization chain, or a divalent group having an aromatic ring-containing structure from a compound containing an aromatic ring as a polymerization chain, and T is a divalent group having an aliphatic polycyclic structure from an aliphatic polycyclic compound as a polymerization chain.

[0622] In the above formula (11), when Q is a divalent group having an aromatic ring-containing structure from a compound containing an aromatic ring as a polymerization chain and T is a divalent group having an aliphatic polycyclic structure from an aliphatic polycyclic compound as a polymerization chain, a polymer corresponding to a novolak resin is obtained.

[0623] In the above formula (11), the group T is a divalent group having an aliphatic polycyclic structure from an aliphatic polycyclic compound as a polymerization chain, and the aliphatic polycyclic compound preferably has at least two double bonds in the ring, and can be typically a diene compound having 2 to 6 rings. These diene compounds can be exemplified by bicyclic compounds, tricyclic compounds, tetracyclic compounds, pentacyclic compounds, and hexacyclic compounds.

[0624] The above aliphatic polycyclic compound can be exemplified by 2,5- norbornadiene, 3a,4,7,7a-tetrahydroinden, 1,3a,4,6a-tetrahydro-pentaene, and bicyclopentadiene, and is preferably 2,5-norbornadiene or bicyclopentadiene.

[0625] The aliphatic polycyclic compound can have an arbitrary substituent, and as the substituent, for example, an alkyl group, a phenyl group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a halogen atom, and the like can be exemplified.

[0626] In the formula (11), in the case where Q is a divalent group that takes the aromatic ring-containing structure from the aromatic ring-containing compound as a polymer chain, as the aromatic ring-containing compound, a monocyclic compound (also referred to as a carbocyclic compound) or a heterocyclic compound can be given. The monocyclic compound can be given benzene which can be substituted, or naphthalene which can be substituted, and the heterocyclic compound can be given carbazole which can be substituted, or phenothiazine which can be substituted.

[0627] The aromatic ring-containing compound can be given a compound having a hydroxyl group, an amino group as an electron-donating organic group.

[0628] The aromatic ring-containing compound can be given, for example, phenol, cresol, 4-phenylphenol, 1-naphthol, o-dihydroxybenzene, m-dihydroxybenzene, p-dihydroxybenzene, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 2,2-bis(hydroxyphenyl)propane, 1,5-dihydroxynaphthalene, o-phenylalanine, m-phenylalanine, aniline, carbazole, phenyl-1-naphthylamine, triphenylamine, 2-phenylindole, phenothiazine, and the like, and is preferably phenol, carbazole, or phenothiazine.

[0629] In the formula (11), the novolak resin in which Q is a divalent group that takes the aromatic ring-containing structure from the aromatic ring-containing compound as a polymer chain and T is a divalent group that takes the aliphatic polycyclic structure from the aliphatic polycyclic compound as a polymer chain is a novolak resin obtained by condensation reaction of the aromatic ring-containing compound and the aliphatic polycyclic compound. In the condensation reaction, the aliphatic polycyclic compound having a diene structure can be used in a proportion of 0.1 to 10 equivalents relative to 1 equivalent of the phenyl group in the aromatic ring-containing compound that participates in the reaction.

[0630] As the acid catalyst used in the above condensation reaction, for example, inorganic acids such as sulfuric acid, phosphoric acid, perchloric acid, and the like; organic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, and the like; carboxylic acids such as formic acid, oxalic acid, and the like can be used. The amount of the acid catalyst used is variously selected depending on the kind of the acid used. Generally, the acid is 0.001 to 10000 parts by mass, preferably 0.01 to 1000 parts by mass, and more preferably 0.1 to 100 parts by mass, relative to 100 parts by mass of the total of the aromatic ring-containing compound and the aliphatic polycyclic compound having a diene.

[0631] The above condensation reaction can also be performed without a solvent, and is generally performed using a solvent. As the solvent, all can be used as long as the reaction is not hindered. For example, toluene, 1,4-dioxane, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, butyl cellosolve, and the like can be given. In addition, if the acid catalyst used is a liquid acid catalyst such as formic acid, the function as a solvent can also be fulfilled.

[0632] The reaction temperature at the time of condensation is usually from 40°C to 200°C. The reaction time is variously selected depending on the reaction temperature, and is usually from 30 minutes to about 50 hours.

[0633] The weight average molecular weight Mw of the novolak resin obtained above is usually from 500 to 1,000,000, or from 600 to 200,000.

[0634] The above-mentioned novolak resin, for example, can be exemplified by a resin having a structural unit represented by the following formulae (11-1) to (11-19).

[0635] [Chemical Formula 9]

[0636] [Chemical Formula 10]

[0637] The above-mentioned novolak resin can have an epoxy group.

[0638] As the above-mentioned novolak resin having an epoxy group, there can be mentioned an epoxy phenol-dicyclopentadiene resin, an epoxy cresol-dicyclopentadiene resin, an epoxy phenol-norbornadiene resin, an epoxy naphthol-dicyclopentadiene resin, an epoxy dihydroxynaphthalene-dicyclopentadiene resin, and the like, and in particular, the epoxy phenol-dicyclopentadiene resin is known as a commercial product (dicyclopentadiene type epoxy resin, trade name: EPICLON HP-7200H, manufactured by DIC Corporation).

[0639] The above-mentioned novolak resin having an epoxy group, for example, can be exemplified by a resin having a structural unit represented by the following formulae (12-1) to (12-5).

[0640] [Chemical Formula 11]

[0641] Further, the above-mentioned novolak resin having an epoxy group can have added thereto an organic compound Z which reacts with the epoxy group. As such an organic compound Z, there can be mentioned a carboxylic acid, a phenol, an amine, an imide compound, and the like.

[0642] As the organic compound Z, for example, benzoic acid, 4-tolylbenzoic acid, 4-tert-butylbenzoic acid, 4-phenylbenzoic acid, salicylic acid, 4-hydroxybenzoic acid, 4-methoxycarboxylic acid, 4-tert-butoxybenzoic acid, 4-fluorobenzoic acid, 4-chlorobenzoic acid, 1-naphthoic acid, 9-anthracene carboxylic acid, n-butyric acid, n-hexanoic acid, n-octanoic acid, pivalic acid, cyclohexane carboxylic acid, 1-methylcyclohexane carboxylic acid, adamantane carboxylic acid, cinnamic acid, succinic anhydride, phthalic anhydride, phenol, cresol, anisole, 4-tert-butylphenol, 4-phenylphenol, 1-naphthol, N-butylamine, N-dibutylamine, piperidine, aniline, succinimide, maleimide, phthalimide, diallylisocyanuric acid, and the like can be exemplified. Particularly preferably, 4-tert-butylbenzoic acid, 4-phenylbenzoic acid, 1-naphthoic acid, 9-anthracene carboxylic acid, n-butyric acid, n-hexanoic acid, n-octanoic acid, pivalic acid, cyclohexane carboxylic acid, 1-methylcyclohexane carboxylic acid, cinnamic acid, 1-naphthol, 4-phenylphenol can be exemplified.

[0643] The above reaction of the above-mentioned novolak resin containing an epoxy group with the organic compound Z capable of adding to the epoxy group can be carried out in a ratio of 0.1 to 1 equivalent of the organic compound Z per 1 equivalent of the epoxy group contained in the above-mentioned novolak resin containing an epoxy group, and two or more kinds of the organic compound Z can be used in combination.

[0644] As the catalyst for activating the epoxy group used in the above-mentioned addition reaction, a quaternary phosphonium salt such as ethyltriphenylphosphonium bromide, a quaternary ammonium salt such as benzyltriethylammonium chloride, and the like can be exemplified. Generally, 0.001 to 1 equivalent of the catalyst per 1 equivalent of the epoxy group contained in the above-mentioned novolak resin is used.

[0645] The above-mentioned addition reaction can be carried out without a solvent, and is generally carried out using a solvent. As the solvent, all kinds of solvents can be used as long as the reaction is not inhibited. For example, alcohols such as propylene glycol monomethyl ether, esters such as propylene glycol monomethyl ether acetate, ethyl lactate, ketones such as cyclohexanone, and the like are highly soluble in novolak resins, and are more preferably used.

[0646] The reaction temperature in the addition reaction is generally 40°C to 200°C. The reaction time is variously selected depending on the reaction temperature, and is generally about 30 minutes to 50 hours.

[0647] The weight average molecular weight Mw of the novolak resin obtained above is generally 500 to 1,000,000, or 600 to 200,000.

[0648] As the novolak resin of the adduct of the above-mentioned novolak resin having an epoxy group and the organic compound Z, for example, a resin having a structural unit represented by the following formulae (13-1) to (13-12) can be exemplified.

[0649] [Chemical Formula 112]

[0650] Note that the above-mentioned neutral film-forming polymer 1 or neutral film-forming polymer 2 can include other polymers in the neutral film-forming composition, within a range not impairing the effects of the present application.

[0651] In the case of including other polymers, the other polymers can be included in a proportion of 0.1 to 100 mass%, preferably 5 to 100 mass%, and further preferably 10 to 100 mass%, relative to the mass of all the polymers in the neutral film-forming composition, depending on the coating solvent used, the firing conditions of the neutral film-forming composition, the firing conditions of the self-assembled film formed on the upper layer, the substrate used, and the like.

[0652] << Cross-linking agent component >> The above-mentioned neutral film-forming composition can include a cross-linking agent component.

[0653] As the cross-linking agent, a melamine-based compound, a substituted urea-based compound, or a polymer-based compound thereof, or the like can be given. A cross-linking agent having at least two cross-linking-forming substituents such as a hydroxymethyl group, an alkoxy methyl group, or the like is preferred, and specifically, a methoxymethylated glycoluril, a butoxymethylated glycoluril, a methoxymethylated melamine, a butoxymethylated melamine, a methoxymethylated benzoguanamine, a butoxymethylated benzoguanamine, a methoxymethylated urea, a butoxymethylated urea, a methoxymethylated thiourea, or a butoxymethylated thiourea, or the like can be given. In addition, condensates of these compounds can also be used.

[0654] Further, the cross-linking agent can be the cross-linking agent given in the description of the organic underlayer film-forming composition.

[0655] The amount of the cross-linking agent added in the neutral film-forming composition varies depending on the coating solvent used, the substrate used, the solution viscosity required, the film shape required, and the like, and is 0.001 to 80 mass%, preferably 0.01 to 50 mass%, and further preferably 0.05 to 40 mass%, relative to the total solid content.

[0656] These cross-linking agents sometimes undergo cross-linking reactions based on self-condensation, but in the case where cross-linking substituents are present in the above-mentioned polymers (neutral film-forming polymer 1, neutral film-forming polymer 2), cross-linking reactions can occur with these cross-linking substituents.

[0657] << Acid or acid generator >> The above neutral film-forming composition can contain an acid or an acid generator as a catalyst for promoting the above cross-linking reaction, i.e., an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalene carboxylic acid, or / and a thermal acid generator such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, other alkyl esters of organic sulfonic acids, and the like.

[0658] The amount of these to be combined is 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 3% by mass, relative to the total solid content of the neutral film-forming composition.

[0659] In addition, as the above acid generator, not only the above thermal acid generator but also a photo acid generator can be mentioned.

[0660] A photo acid generator generates an acid upon exposure of a resist. Therefore, the acidity of the neutral film can be adjusted. This is one method for matching the acidity of the neutral film with that of the self-assembled film of the upper layer. In addition, by adjusting the acidity of the neutral film, the pattern shape of the self-assembled film formed in the upper layer can be adjusted.

[0661] As the photo acid generator to be contained in the neutral film-forming composition, onium salt compounds, sulfonylimine compounds, and disulfonyl diazomethane compounds, and the like can be mentioned.

[0662] As the onium salt compounds, iodonium salt compounds such as diphenyl iodonium hexafluorophosphate, diphenyl iodonium triflate, diphenyl iodonium nonafluoro-n-butanesulfonate, diphenyl iodonium perfluoro-n-octanesulfonate, diphenyl iodonium camphorsulfonate, bis(4-tert-butylphenyl) iodonium camphorsulfonate, and bis(4-tert-butylphenyl) iodonium triflate, and sulfonium salt compounds such as triphenyl sulfonium hexafluoroantimonate, triphenyl sulfonium nonafluoro-n-butanesulfonate, triphenyl sulfonium camphorsulfonate, triphenyl sulfonium triflate, triphenyl sulfonium nitrate, triphenyl sulfonium trifluoroacetate, triphenyl sulfonium maleate, and triphenyl sulfonium chloride, and the like can be mentioned.

[0663] As the sulfonylimine compounds, for example, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalene dicarboxylic acid imide, and the like can be mentioned.

[0664] As the disulfonyl diazomethane compounds, for example, bis(trifluoromethylsulfonyl) diazomethane, bis(cyclohexylsulfonyl) diazomethane, bis(phenylsulfonyl) diazomethane, bis(p-toluenesulfonyl) diazomethane, bis(2,4-dimethylphenylsulfonyl) diazomethane, and methylsulfonyl-p-toluenesulfonyl diazomethane, and the like can be mentioned.

[0665] Photo-acid generators can be used in isolation or in combination of two or more.

[0666] When using a photoacid generator, the proportion thereof is 0.01 to 5 parts by weight, or 0.1 to 3 parts by weight, or 0.5 to 1 part by weight relative to 100 parts by weight of the solid component of the neutral film-forming composition.

[0667] <<Other Additives>> In addition to the aforementioned components, rheology modifiers, adhesive aids, surfactants, etc., can be further added to the neutral film-forming composition as needed. These can be added to the neutral film-forming composition in various compounds, including those that can be incorporated into the silicon-containing underlayer film-forming composition, and in appropriate amounts.

[0668] <Patterning of Neutral Membranes> In one method for inducing microphase separation structures with a desired pattern, a self-assembled patterning template film consisting of a neutral film and a brush film (described later) can be formed. In this case, pattern forming using a photoresist can be employed to form the desired pattern on the neutral film.

[0669] In pattern formation using photoresist, firstly, a layer of photoresist material (resist film) is formed on the aforementioned neutral film. The resist film can be formed using a known method, namely, coating a coating-type resist material (e.g., a photoresist film forming composition) onto the neutral film and then firing it. Firing conditions can be, for example, set to a firing temperature of 70 to 150°C and a firing time of 0.5 to 5 minutes.

[0670] The thickness of the resist film is, for example, 10nm to 10000nm, or 100nm to 2000nm, or 200nm to 1000nm, or 30nm to 200nm.

[0671] As the photoresist material used in the above-mentioned resist film, there is no particular limitation as long as it is a material that is photosensitive to light used in exposure (for example, a KrF excimer laser, an ArF excimer laser, or the like), and either of a negative photoresist material and a positive photoresist material can be used. For example, there are a positive photoresist material containing a novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester; a chemically amplified photoresist material containing a binder having a group that is decomposed by the action of an acid to increase the alkali dissolution rate and a photoacid generator; a chemically amplified photoresist material containing a low molecular compound that is decomposed by the action of an acid to increase the alkali dissolution rate of the photoresist material, an alkali-soluble binder, and a photoacid generator; and a chemically amplified photoresist material containing a binder having a group that is decomposed by the action of an acid to increase the alkali dissolution rate, a low molecular compound that is decomposed by the action of an acid to increase the alkali dissolution rate of the photoresist material, and a photoacid generator, and the like.

[0672] As specific examples that can be obtained in the form of a commercial product, there are, for example, APEX-E manufactured by Shipley Co., Ltd., PAR710 manufactured by Sumitomo Chemical Co., Ltd., AR2772JN manufactured by JSR Co., Ltd., and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd., but are not limited thereto. In addition, for example, there are fluorine atom-containing polymer-based photoresist materials described in Proc. SPIE, Vol. 3999, 330-334 (2000); Proc. SPIE, Vol. 3999, 357-364 (2000); Proc. SPIE, Vol. 3999, 365-374 (2000).

[0673] In addition, the above-mentioned resist film can be replaced with an electron beam lithography resist film (also referred to as an electron beam resist film) or an EUV lithography resist film (also referred to as an EUV resist film) instead of a photoresist film.

[0674] As the electron beam resist material described above, both a negative type material and a positive type material can be used. As specific examples thereof, there are: a chemically amplified resist material including an acid generator and a binder having a group that changes in alkali dissolution rate upon decomposition by the action of acid; a chemically amplified resist material including an alkali-soluble binder, an acid generator, and a low-molecular compound that changes in alkali dissolution rate of the resist material upon decomposition by the action of acid; a chemically amplified resist material including an acid generator, a binder having a group that changes in alkali dissolution rate upon decomposition by the action of acid, and a low-molecular compound that changes in alkali dissolution rate of the resist material upon decomposition by the action of acid; a non-chemically amplified resist material including a binder having a group that changes in alkali dissolution rate upon decomposition by the action of an electron beam; a non-chemically amplified resist material including a binder having a site that changes in alkali dissolution rate upon cleavage by an electron beam; and the like. In the case of using these electron beam resist materials, a pattern of a resist film can also be formed as in the case of using a photoresist material with an electron beam as the irradiation source.

[0675] In addition, as the EUV resist material described above, a methacrylate resin-based resist material can be used.

[0676] Next, the formed resist film is exposed through a prescribed mask (reticle). The exposure can use a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), EUV (wavelength 13.5 nm), an electron beam, or the like.

[0677] After exposure, post exposure bake can also be performed as needed. The post exposure bake is performed under conditions appropriately selected from a heating temperature of 70°C to 150°C and a heating time of 0.3 minutes to 10 minutes.

[0678] Next, development is performed using a developing solution (for example, an alkali developing solution). Thereby, for example in the case of using a positive type photoresist film, the photoresist film of the exposed portion is removed, and a pattern of the photoresist film is formed.

[0679] As the developing solution (alkali developing solution), examples include an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide; an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, or choline; an aqueous amine solution such as ethanolamine, propylamine, or ethylenediamine; and the like. Furthermore, a surfactant or the like can also be added to these developing solutions. As the conditions for development, the temperature can be appropriately selected from 5°C to 50°C, and the time can be appropriately selected from 10 seconds to 600 seconds.

[0680] In addition, an organic solvent can be used as the developer, and the exposed resist film is developed with the developer (solvent) after exposure. Thus, for example, in the case of using a negative resist film, the unexposed portion of the resist film is removed, and a pattern of the resist film is formed.

[0681] As the developer (organic solvent), for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl 3-methoxypropionate, and the like can be exemplified. Furthermore, a surfactant or the like can be added to these developers. As the conditions for development, the temperature can be appropriately selected from 5°C to 50°C, and the time can be appropriately selected from 10 seconds to 600 seconds.

[0682] Next, the neutral film is etched using the pattern of the resist film as a protective film, and the neutral film is patterned.

[0683] The removal (patterning) of the neutral film is performed by dry etching using an oxygen-based gas (oxygen, oxygen / nitrogen (N2) mixed gas, or the like). This is because the silicon atom-containing lower layer film provided under the neutral film, which contains a large amount of silicon atoms, is not easily removed by dry etching using an oxygen-based gas.

[0684] Then, the resist film (pattern) as a protective film is removed by etching or peeling, and a patterned neutral film is obtained.

[0685] The resist film is removed by plasma or ozone etching, or a conventional resist peeling solution can be used in conjunction with the type of photoresist described above.

[0686] <Formation of a self-assembled pattern template film composed of a neutral film and a brush film> In the formation of the self-assembled pattern template film described above, first, a brush film is formed on the entire surface of the substrate by coating a brush film-forming material (brush layer-forming composition) on the patterned neutral film on the silicon-containing underlayer film obtained in the above process, i.e., on the underlayer film (exposed portions) and the patterned neutral film on the underlayer film, by the appropriate coating method described above, and then by firing.

[0687] As the conditions for the firing, the firing temperature can be appropriately selected from 80°C to 300°C, or 80°C to 250°C, and the firing time can be appropriately selected from 0.3 to 60 minutes. The firing temperature is preferably 80°C to 100°C, and the firing time is preferably 0.5 to 2 minutes.

[0688] The thickness of the film formed here can be any thickness that can cover the patterned neutral film described above.

[0689] The brush film is a film that is provided so as not to exhibit self-assembled patterns other than the target, and in order to achieve such a function, it is required to be a film that has the property of being sufficiently attached to the silicon-containing underlayer film and not attached to the neutral film.

[0690] <Brush layer-forming composition> The brush layer-forming composition, for example, contains a brush polymer and a solvent.

[0691] The brush layer-forming composition, for example, is a composition that contains a polymer chain that can directly bond to the surface of a substrate. A film or layer in which polymer chains are arranged in a brush shape on a substrate is sometimes referred to as a brush layer.

[0692] The brush layer-forming composition, for example, is a lower layer film-forming composition for forming a lower layer film that contains a block copolymer.

[0693] In addition, the film formed from the brush layer-forming composition, for example, functions to control the position at which a polymer phase formed by self-assembly is generated. For example, the film formed from the brush layer-forming composition has a concave-convex structure and is a side wall of a concave portion in grapho-epitaxy for forming a microphase separation pattern in the concave portion. In addition, for example, the film formed from the brush layer-forming composition is chemical-epitaxy that controls the position at which a microphase separation pattern is formed based on the difference in surface energy of the lower layer of the self-assembly material.

[0694] Brush-like polymer As the brush-like polymer, there is no particular limitation as long as it is a brush-like polymer used for forming the underlayer film.

[0695] As one example of the brush-like polymer, for example, a polymer contained in a neutral wetting base surface described in Japanese Patent Application Laid-Open No. 2011-515537 can be given. As such a polymer, for example, a random copolymer described in claim 15, a blend of a plurality of homopolymers grafted described in claim 16, and the like of Japanese Patent Application Laid-Open No. 2011-515537 can be given. The content of Japanese Patent Application Laid-Open No. 2011-515537 is incorporated in the present specification to the same extent as the entire description.

[0696] As another example of the brush-like polymer, for example, a random copolymer described in Japanese Patent Application Laid-Open No. 2011-518652 can be given. One example of the random copolymer described in Japanese Patent Application Laid-Open No. 2011-518652 is a random PS-r-PMMA capable of photo-crosslinking described in paragraph

[0028] . The content of Japanese Patent Application Laid-Open No. 2011-518652 is incorporated in the present specification to the same extent as the entire description.

[0697] As another example of the brush-like polymer, for example, a resin in which 20 mol% to 80 mol% of the entire structural unit is a structural unit from a monomer containing an aromatic ring can be given. Such a resin is, for example, a resin component contained in a base agent described in International Publication No. 2012 / 036121. The content of International Publication No. 2012 / 036121 is incorporated in the present specification to the same extent as the entire description.

[0698] As another example of the brush-like polymer, for example, a random copolymer described in claim 1 of Japanese Patent Application Laid-Open No. 2013-166934 can be given. The content of Japanese Patent Application Laid-Open No. 2013-166934 is incorporated in the present specification to the same extent as the entire description.

[0699] As another example of the brush-like polymer, for example, a polymer having a unit structure of a polycyclic aromatic vinyl compound of 0.2 mol% or more with respect to the entire unit structure can be given. Such a polymer is, for example, a polymer contained in an underlayer film forming composition described in International Publication No. 2014 / 097993. The content of International Publication No. 2014 / 097993 is incorporated in the present specification to the same extent as the entire description.

[0700] As another example of the brush-like polymer, for example, a polymer contained in the brush back film composition described in Japanese Patent Application Publication No. 2015-130496 (JP 2015-130496 A) can be given. The content of Japanese Patent Application Publication No. 2015-130496 (JP 2015-130496 A) is incorporated in the specification to the same extent as the entire written description.

[0701] As another example of the brush-like polymer, for example, an addition polymer described in claim 1 of Japanese Patent Application Publication No. 2016-148024 (JP 2016-148024 A) can be given. The content of Japanese Patent Application Publication No. 2016-148024 (JP 2016-148024 A) is incorporated in the specification to the same extent as the entire written description.

[0702] As another example of the brush-like polymer, for example, a polymer contained in the pinning material described in claim 1 of Japanese Patent Application Publication No. 2016-528713 (JP 2016-528713 A) can be given. As such a polymer, for example, a polymer described in claim 3 of Japanese Patent Application Publication No. 2016-528713 (JP 2016-528713 A) can be given. The content of Japanese Patent Application Publication No. 2016-528713 (JP 2016-528713 A) is incorporated in the specification to the same extent as the entire written description.

[0703] As another example of the brush-like polymer, for example, an acid-sensitive copolymer containing an acid-decomposable group, an additional group, and a functional group described in claim 1 of Japanese Patent Application Publication No. 2018-139007 (JP 2018-139007 A) can be given. The content of Japanese Patent Application Publication No. 2018-139007 (JP 2018-139007 A) is incorporated in the specification to the same extent as the entire written description.

[0704] As another example of the brush-like polymer, for example, a hydrophobic polymer brush precursor described in claim 1 of Japanese Patent Application Publication No. 2018-503241 (JP 2018-503241 A) can be given. The content of Japanese Patent Application Publication No. 2018-503241 (JP 2018-503241 A) is incorporated in the specification to the same extent as the entire written description.

[0705] The brush-like polymer preferably has a functional group capable of bonding to a substrate.

[0706] As the functional group capable of bonding to a substrate, for example, a hydroxyl group, an amino group, a sulfonic acid group, and the like can be given.

[0707] The brush-like polymer can have a functional group capable of bonding to a substrate at the terminal of the polymer chain, or can have a functional group capable of bonding to a substrate at a site other than the terminal of the polymer chain.

[0708] As a method of introducing a functional group capable of bonding to a substrate to the terminal of the polymer chain, there is no particular limitation, and, for example, in the case of an addition polymerization-type polymer, a method in which a compound having a functional group capable of bonding to a substrate is used in a polymerization initiator, a chain transfer agent, and the like can be given.

[0709] The brush polymer is preferably a polymer of the addition polymerization type.

[0710] The polymer of the addition polymerization type can be obtained, for example, by polymerizing one or more radical polymerizable monomers.

[0711] The radical polymerizable monomer is not particularly limited, and examples thereof include (meth)acrylic compounds, aromatic group-containing vinyl compounds, and the like.

[0712] The (meth)acrylic compound includes, for example, (meth)acrylic acid, (meth)acrylate, and the like. The (meth)acrylate includes, for example, methyl (meth)acrylate, ethyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, and the like.

[0713] The aromatic group-containing vinyl compound includes, for example, styrene, α - methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-t-butylstyrene, 4-n-octylstyrene, 2,4,6-trimethylstyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-hydroxystyrene, 4-nitrostyrene, 3-nitrostyrene, 4-chlorostyrene, 4-fluorostyrene, 4-acetoxyvinylstyrene, vinylcyclohexane, 4-vinylbenzyl chloride, 1-vinylnaphthalene, 4-vinylbiphenyl, 1-vinyl-2-pyrrolidone, 9-vinylanthracene, vinylpyridine, and the like.

[0714] The brush polymer is preferably a polymer (P) containing the following structural units (A) and (B). From the viewpoint of being able to induce a microphase separation structure of the block copolymer vertically with respect to the substrate, the brush polymer is preferably a polymer (P) containing the following structural units (A) and (B).

[0715] Structural unit (A): a structural unit derived from a (meth)acrylic compound having a (meth)acryloyl group and a functional group capable of bonding to a substrate, Structural unit (B): a structural unit derived from an aromatic group-containing vinyl compound.

[0716] The molar ratio of the structural unit (A) with respect to the total structural units in the polymer (P) is more than 0% and 5% or less.

[0717] By ensuring that the molar ratio of structural unit (A) to all structural units (P) in the polymer is greater than 0% and less than 5%, a film inducing a microphase separation structure of the block copolymer perpendicularly to the substrate can be formed. If the molar ratio of structural unit (A) to all structural units in the polymer (P) exceeds 5%, the arrangement of the microphase separation structure of the block copolymer is disordered, and the microphase separation structure of the block copolymer cannot be induced perpendicularly to the substrate.

[0718] As for the polymer (P), there are no particular limitations as long as it contains structural units (A) and (B), but addition polymers obtained by polymerization of compounds having polymerizable unsaturated groups are preferred. Examples of polymerizable unsaturated groups include olefinic unsaturated groups. Examples of olefinic unsaturated groups include vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimide, nadicimide, (meth)acryloyl, etc.

[0719] The polymer (P) is, for example, a random copolymer.

[0720] The polymer (P) may contain structural units other than structural units (A) and (B).

[0721] Structural unit (A) is a structural unit derived from (meth)acrylic acid compounds.

[0722] (Meth)acrylic acid compounds have (meth)acryloyl groups.

[0723] (Meth)acrylic acid compounds have functional groups that can bond with a substrate.

[0724] (Meth)acryloyl is a designation representing acryloyl and methacryloyl. Acryloyl refers to the group represented by CH2=CH-CO-, and methacryloyl refers to the group represented by CH2=C(CH3)-CO-.

[0725] There are no particular limitations on the functional groups that can bond with the substrate; examples include hydroxyl, amino, and sulfonic acid groups.

[0726] The number of functional groups in structural unit (A) that can bond with the substrate can be one or more, but one is preferred.

[0727] The (meth)acryloyl group in the (meth)acrylic acid compound can be one or more, preferably one.

[0728] Structural unit (A) is a different structural unit from structural unit (B). Therefore, structural unit (B) does not have an aromatic ring.

[0729] The structural unit (A) in the polymer (P) can be one or two or more.

[0730] As the structural unit (A), a structural unit (A-1) represented by the following formula (1) is preferable.

[0731] [Chemical Formula 113]

[0732] (In formula (1), X represents -O- or -NH-. Y represents a hydroxyl group, an amino group, or a sulfonic acid group. R 1 represents an alkylene group having 1 to 10 carbon atoms which can be substituted with a halogen atom. R 2 represents a hydrogen atom or a methyl group. As the amino group, a primary amino group or a secondary amino group is preferable.

[0733] The primary amino group refers to a monovalent functional group (-NH2) obtained by removing a hydrogen atom from ammonia.

[0734] The secondary amino group refers to a monovalent functional group (-NHR (in which R represents an organic group)) obtained by removing a hydrogen atom from a primary amine. R represents, for example, an alkyl group having 1 to 6 carbon atoms.

[0735] The alkylene group having 1 to 10 carbon atoms which can be substituted with a halogen atom can be linear, branched, or cyclic.

[0736] As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom can be mentioned.

[0737] The number of halogen atoms in the alkylene group having 1 to 10 carbon atoms which can be substituted with a halogen atom can be one or two or more.

[0738] As the alkylene group having 1 to 10 carbon atoms, a linear or branched alkylene group can be mentioned, and examples include a methylene group, an ethylene group, a 1,3- propylene group (trimethylene group), a 1-methylethylene group (1,2-propylene group), a 1,4- butylene group, a 1-ethylethylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,5-pentylene group, a 1-methylbutylene group, a 2-methylbutylene group, a 1,1- dimethylpropylene group, a 1,2-dimethylpropylene group, a 1-ethylpropylene group, a 2- ethylpropylene group, a 1,6-hexylene group, a 1,4-cyclohexylene group, a 1,8-octylene group, a 2- ethyloctylene group, a 1,9-nonylene group, a 1,10-decylene group, and the like.

[0739] The molar ratio of the structural unit (A) with respect to the total structural units in the polymer (P) is more than 0% and 5% or less, preferably 0.1% or more and 5% or less, more preferably 0.3% or more and 4.5% or less, particularly preferably 0.5% or more and 4.0% or less.

[0740] As the (meth)acrylic compound, for example, a compound represented by the following formula (1-1) can be given.

[0741] [Chemical Formula 114]

[0742] (In formula (1-1), X represents -O- or -NH-. Y represents a hydroxyl group, an amino group, or a sulfonic acid group. R 1 represents an alkylene group having 1 to 10 carbon atoms which can be substituted with a halogen atom. R 2 represents a hydrogen atom or a methyl group.) As the (meth)acrylic compound, for example, a compound represented by the following formula (1-1) can be given.

[0743] As the (meth)acrylic compound, for example, a compound represented by the following formula (1-1) can be given.

[0744] As the (meth)acrylic compound, for example, a compound represented by the following formula (1-1) can be given.

[0745] As the (meth)acrylic compound, for example, a compound represented by the following formula (1-1) can be given.

[0746] As the (meth)acrylic compound, for example, a compound represented by the following formula (1-1) can be given.

[0747] As the (meth)acrylic compound, for example, a compound represented by the following formula (1-1) can be given.

[0748] As the (meth)acrylic compound, for example, a compound represented by the following formula (1-1) can be given.

[0749] The structural unit (B) is a structural unit from an aromatic group-containing vinyl compound.

[0750] The aromatic ring of the vinyl compound containing an aromatic group can be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring.

[0751] Examples of the aromatic hydrocarbon ring include benzene rings, naphthalene rings, anthracene rings, and the like.

[0752] The vinyl compound containing an aromatic group, for example, does not have a functional group capable of bonding to a substrate.

[0753] The vinyl compound containing an aromatic group, for example, does not have a hydroxyl group, an amino group, and a sulfonic acid group.

[0754] The structural unit (B), for example, does not have a functional group capable of bonding to a substrate.

[0755] The structural unit (B), for example, does not have a hydroxyl group, an amino group, and a sulfonic acid group.

[0756] The structural unit (B) in the polymer (P) can be one or two or more.

[0757] As the structural unit (B), it is preferable to include a structural unit (B-1) represented by the following formula (2).

[0758] As the structural unit (B), it is preferable to include a structural unit (B-2) represented by the following formula (3).

[0759] [Chemical Formula 115]

[0760] (In formula (2), each of n Ys independently represents a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a thioalkyl group, and n represents an integer of 0 to 7.) [Chemical Formula 116]

[0761] (In formula (3), R 3 ~R 5 each independently represents a hydrogen atom or a tert-butyl group. Among them, one or two of R 3 ~R 5 represent a tert-butyl group.) As the halogen atom in Y in formula (2), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be given.

[0762] As the alkyl group in Y in formula (2), an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is further more preferable, and an alkyl group having 1 to 3 carbon atoms is particularly preferable. The alkyl group can be linear, branched, or cyclic.

[0763] As for the alkoxy group in formula (2), it is preferred to be an alkoxy group with 1 to 15 carbon atoms, more preferably an alkoxy group with 1 to 10 carbon atoms, even more preferably an alkoxy group with 1 to 6 carbon atoms, and particularly preferably an alkoxy group with 1 to 3 carbon atoms. The alkyl group in the alkoxy group can be straight-chain, branched, or cyclic.

[0764] As for the alkoxycarbonyl group in formula (2), it is preferred to be an alkoxycarbonyl group with 2 to 15 carbon atoms, more preferably an alkoxycarbonyl group with 2 to 10 carbon atoms, even more preferably an alkoxycarbonyl group with 2 to 6 carbon atoms, and particularly preferably an alkoxycarbonyl group with 2 to 3 carbon atoms. The alkyl group in the alkoxycarbonyl group can be linear, branched, or cyclic.

[0765] As the alkylthio group in Y in formula (2), examples can be the group formed by replacing the -O- of the above-mentioned alkoxy group with -S-.

[0766] There are no particular limitations on the molar ratio of structural unit (B) to all structural units in polymer (P), but it is preferably 80% or more and less than 100%, more preferably 90% or more and less than 100%, and particularly preferably more than 95% and less than 100%.

[0767] The molar ratio of structural unit (A) to structural unit (B) in polymer (P) is not particularly limited, but is preferably 1:200 to 1:10, and more preferably 1:150 to 1:20.

[0768] When the polymer (P) contains the structural unit (B-1) shown in formula (2), the molar ratio of structural unit (A) to structural unit (B-1) in the polymer (P) (structural unit (A): structural unit (B-1)) is not particularly limited, but is preferably 1:100 to 1:5, and more preferably 1:75 to 1:10.

[0769] When the polymer (P) contains the structural unit (B-2) shown in formula (3), there is no particular limitation on the molar ratio (structural unit (A): structural unit (B-2)) of structural unit (A): structural unit (B-2) in the polymer (P), which is preferably 1:100 to 1:5, and more preferably 1:75 to 1:10.

[0770] In the case where the polymer (P) contains the structural unit (B-1) represented by formula (2) and the structural unit (B-2) represented by formula (3), the molar ratio of the structural unit (B-1) to the structural unit (B-2) in the polymer (P) (structural unit (B-1) : structural unit (B-2)) is not particularly limited, and is preferably 1.0 : 0.1 to 0.1 : 1.0, more preferably 1.0 : 0.5 to 0.5 : 1.0, and particularly preferably 1.0 : 0.7 to 0.7 : 1.0.

[0771] As the vinyl compound containing an aromatic group, for example, a compound represented by the following formula (2-1) or a compound represented by the following formula (3-1) can be mentioned.

[0772] [Chemical Formula 117]

[0773] (In formula (2-1), each of n Y's independently represents a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or an alkylthio group, and n represents an integer of 0 to 7.) [Chemical Formula 118]

[0774] (In formula (3-1), R 3 ~R 5 each independently represents a hydrogen atom or a tert-butyl group. Among them, one or two of R 3 ~R 5 represent a tert-butyl group.) The weight average molecular weight of the brush-shaped polymer determined by the Gel Permeation Chromatography (GPC) method is not particularly limited, and is, for example, 1000 to 50000, preferably 2000 to 20000, in terms of polystyrene.

[0775] < Method for producing brush-shaped polymer > > The method for producing the brush-shaped polymer is not particularly limited.

[0776] For example, in the case where the brush-shaped polymer is an addition polymerization type polymer, it can be produced by polymerizing monomers by a conventional method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Solution polymerization is particularly preferable, and in this case, for example, a desired monomer can be added to a solvent to which a polymerization initiator has been added and polymerized.

[0777] For example, in the case where the brush-shaped polymer is an addition polymerization type random copolymer, it can be produced by copolymerizing various monomers in a suitable molar ratio by a conventional method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization.

[0778] As such polymerization, for example, radical polymerization can be cited.

[0779] The manufacturing method of the brush-like polymer can also be a manufacturing method using a polymerization method other than radical polymerization. For example, it can be a manufacturing method using ionic (anionic, cationic) addition polymerization, or a manufacturing method using polycondensation, polyaddition reaction.

[0780] The polymer (P) can be manufactured, for example, by solution polymerization of a monomer mixture containing a (meth)acrylic compound having a (meth)acryloyl group and a functional group capable of bonding to a substrate, and a vinyl compound containing an aromatic group.

[0781] [Polymerization initiator] As the polymerization initiator, an organic peroxide, a diazo compound can be used.

[0782] As the organic peroxide, for example, diacyl peroxide-based, peroxydicarbonate-based, peroxyester-based, peroxy sulfonate-based, and the like can be cited.

[0783] As the diacyl peroxide-based, for example, diacetyl peroxide, diisobutyl peroxide, didecanoyl peroxide, benzoyl peroxide, succinyl peroxide, and the like can be cited.

[0784] As the peroxydicarbonate-based, for example, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diallyl peroxydicarbonate, and the like can be cited.

[0785] As the peroxyester-based, for example, tert-butyl peroxyisobutyrate, tert-butyl neodecanate, cumyl peroxyneodecanate, and the like can be cited.

[0786] As the peroxy sulfonate-based, for example, acetyl cyclohexyl sulfonyl peroxide, and the like can be cited.

[0787] As the diazo compound, for example, 2,2'-azobis(isobutyronitrile), 4,4'-azobis(4-cyanopentanoic acid), 2,2'-azobis(4-methoxy-2,4-dimethoxyvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), and the like can be cited.

[0788] In the case where it is intended to end the polymerization in a short time, it is preferable to use a polymerization initiator having a half-life of 10 hours or less at 80°C. As such a polymerization initiator, benzoyl peroxide, 2,2'-azobis(isobutyronitrile) are preferable, and 2,2'-azobis(isobutyronitrile) is more preferable.

[0789] The amount of the polymerization initiator used is, for example, 0.0001 to 0.2 equivalents, preferably 0.0005 to 0.1 equivalents, relative to the monomers used as a whole.

[0790] [Solvent] As the solvent used in the polymerization, there is no particular limitation as long as it does not participate in the polymerization reaction and is compatible with the resulting brush-shaped polymer, and examples thereof include aromatic hydrocarbons, alicyclic hydrocarbons, aliphatic hydrocarbons, ketones, ethers, esters, amides, sulfoxides, alcohols, polyhydric alcohol derivatives, and the like.

[0791] As the aromatic hydrocarbons, for example, benzene, toluene, xylene, and the like can be given.

[0792] As the alicyclic hydrocarbons, for example, cyclohexane and the like can be given.

[0793] As the aliphatic hydrocarbons, for example, n-hexane, n-octane, and the like can be given.

[0794] As the ketones, for example, acetone, methyl ethyl ketone, cyclohexanone, and the like can be given.

[0795] As the ethers, for example, tetrahydrofuran, dioxane, and the like can be given.

[0796] As the esters, for example, ethyl acetate, butyl acetate, and the like can be given.

[0797] As the amides, for example, N,N-dimethylformamide, N,N-dimethylacetamide, and the like can be given.

[0798] As the sulfoxides, for example, dimethyl sulfoxide and the like can be given.

[0799] As the alcohols, for example, methanol, ethanol, and the like can be given.

[0800] As the polyhydric alcohol derivatives, for example, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and the like can be given.

[0801] They can be used alone or in combination of two or more.

[0802] The polymerization temperature is not particularly limited as long as it is a temperature range in which the monomers are consumed and the polymerization is completed without causing side reactions such as migration reaction and termination reaction, and it is preferably a temperature range of -100°C or higher and lower than the boiling point of the solvent.

[0803] In addition, the concentration of the monomers with respect to the solvent is not particularly limited, and it is usually 1 to 40% by mass, and preferably 10 to 30% by mass.

[0804] The polymerization time can be appropriately selected, and it is usually in the range of 2 hours to 50 hours.

[0805] <<Solvent>> As the solvent contained in the brush layer-forming composition, there is no particular limitation as long as it is a solvent that dissolves the brush-shaped polymer.

[0806] As the solvent, for example, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monopropyl ether, methyl ethyl ketone, ethyl lactate, cyclohexanone, N,N-2-trimethylpropionamide, gamma - butyrolactone, N-methyl-2-pyrrolidone, methyl 2-hydroxyisobutyrate, ethyl 3-ethoxypropionate, and the like.

[0807] They can be used alone or in combination of two or more.

[0808] The content of the solvent in the brush layer-forming composition is not particularly limited, and is, for example, 90% by mass or more and 99.9% by mass or less.

[0809] <<<Other Components>>> The brush layer-forming composition preferably does not contain a crosslinking agent. For example, by allowing the brush-shaped polymer to react with the substrate, the film obtained from the brush layer-forming composition becomes a film that is not dissolved in the solvent contained in the self-assembly film-forming composition containing the block copolymer. Therefore, the brush layer-forming composition does not need to contain a crosslinking agent.

[0810] In the present application, "does not contain a crosslinking agent" can also include containing a small amount of a crosslinking agent to the extent that the crosslinking agent does not sufficiently function as a crosslinking agent. As a manner in which the brush layer-forming composition does not contain a crosslinking agent, the content of the crosslinking agent in the brush layer-forming composition is preferably less than 0.1% by mass, more preferably 0.01% by mass or less, and particularly preferably 0.001% by mass or less, with respect to the brush-shaped polymer.

[0811] As the crosslinking agent, for example, a nitrogen-containing compound having two to four nitrogen atoms substituted with a methylol group or an alkoxymethyl group can be mentioned.

[0812] As the crosslinking agent, for example, hexamethoxymethyl melamine, tetramethoxymethyl glycoluril, tetramethoxymethyl benzoguanamine, 1,3,4,6-tetra(methoxymethyl) glycoluril, 1,3,4,6-tetra(butoxymethyl) glycoluril, 1,3,4,6-tetra(hydroxymethyl) glycoluril, 1,3-bis(hydroxymethyl) urea, 1,1,3,3-tetra(butoxymethyl) urea, and 1,1,3,3-tetra(methoxymethyl) urea, and the like can be mentioned.

[0813] The brush layer-forming composition can contain a surfactant. The surfactant is an additive for improving the coatability to the substrate.

[0814] As the surfactant, a known surfactant such as a nonionic surfactant, a fluorine-based surfactant, etc. can be used.

[0815] As the content of the surfactant in the brush layer-forming composition, for example, 0.1 to 5 mass% relative to the brush polymer can be mentioned.

[0816] In the brush layer-forming composition, if the components other than the solvent are defined as solid components, the solid components include the brush polymer and the additives added as necessary.

[0817] As the concentration of the solid components in the brush layer-forming composition, there is no particular limitation, and fo...

Claims

1. A composition for forming a silicon-containing lower layer film, characterized in that, The silicon-containing lower film is used to form self-assembled patterns. The composition for forming a silicon-containing lower layer film contains: [A] Polysiloxane, [B] A strong acid additive comprising 0 to less than 2 parts by weight of the polysiloxane relative to 100 parts by weight, and [C] solvent, The polysiloxane comprises structural units derived from a hydrolyzable silane (A) represented by the following formula (A-1). In equation (A-1), a represents an integer from 1 to 3. b represents an integer from 0 to 2. a+b represents an integer from 1 to 3. R 1 This indicates an organic group having a ring structure other than that of aromatic hydrocarbons. R 2 This indicates a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted haloalkyl group, a substituted or unsubstituted haloaryl group, a substituted or unsubstituted alkoxyalkyl group, a substituted or unsubstituted alkoxyaryl group, a substituted or unsubstituted alkoxyaralkyl group, or a substituted or unsubstituted alkenyl group; or, R 2 This refers to an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more of these groups. X represents an alkoxy, arylalkoxy, acyloxy, or halogen atom. In R 1 R 2 When X and R are multiple, multiple R 1 R 2 Same as or different from X.

2. The composition for forming a silicon-containing lower layer film according to claim 1, wherein, The strong acid additive is a strong acid additive whose first acid dissociation constant in water is less than 1.

3. The composition for forming a silicon-containing lower layer film according to claim 1, wherein, The strong acid additive is a photoacid generator.

4. The composition for forming a silicon-containing lower layer film according to claim 1, wherein, The R 1 The ring structure described herein contains heteroatoms.

5. The composition for forming a silicon-containing lower layer film according to claim 1, wherein, The proportion of Q units in all structural units of the [A] component is less than 65 mol%.

6. A method for manufacturing a substrate with a self-assembling pattern, characterized in that, include: The process of forming a lower layer film on a substrate using the silicon-containing lower layer film formation composition according to any one of claims 1 to 5, and The process of forming a self-assembly film on the upper side of the lower film to form a self-assembly pattern.

7. A method for manufacturing a substrate with a self-assembling pattern, characterized in that, include: The process of forming a lower layer film on a substrate using the silicon-containing lower layer film forming composition according to any one of claims 1 to 5. The process of forming a neutral film on the lower layer film, and The process of forming a self-assembly film and forming a self-assembly pattern on the neutral film.

8. A method for manufacturing a substrate with a self-assembling pattern, characterized in that, include: The process of forming a lower layer film on a substrate using the silicon-containing lower layer film forming composition according to any one of claims 1 to 5. In the process of forming a neutral film on a portion of the lower film, The steps of forming a brush film on the lower film where the neutral film has not been formed, forming a template film for self-assembling patterns formed by the neutral film and the brush film, and... The process of forming a self-assembly film on the template film for the self-assembly pattern to obtain a self-assembly pattern.

9. A method for manufacturing a substrate with a self-assembling pattern, characterized in that, include: The process of forming an organic lower layer film on a substrate. The process of forming a lower layer film on the organic lower layer film using the silicon-containing lower layer film forming composition according to any one of claims 1 to 5. In the process of forming a neutral film on a portion of the lower film, The steps of forming a brush film on the lower film where the neutral film has not been formed, forming a template film for self-assembling patterns formed by the neutral film and the brush film, and... The process of forming a self-assembly film on the template film for the self-assembly pattern to obtain a self-assembly pattern.

10. A method for manufacturing a substrate with a self-assembling pattern, characterized in that, include: The process of forming an organic lower layer film on a substrate. The process of forming a lower layer film on the organic lower layer film using the silicon-containing lower layer film forming composition according to any one of claims 1 to 5. In the process of forming a neutral film on the lower film, The process of forming a resist film on the neutral film, The process of exposing and developing the resist film to obtain the resist pattern. The process of using the resist pattern as a mask to etch the neutral film. The process of etching or stripping the resist pattern to obtain a patterned neutral film on the underlying film. The process of forming a brush film on the lower layer film and the patterned neutral film on the lower layer film. The process of etching or peeling off the brush film on the patterned neutral film to expose the neutral film, forming a self-assembling pattern template film composed of the neutral film and the brush film, and... The process of forming a self-assembly film on the template film for the self-assembly pattern to obtain a self-assembly pattern.

11. The method for manufacturing a substrate with a self-assembling pattern according to claim 6, wherein, The manufacturing method is used to form self-assembled patterns through directional self-assembly, i.e., DSA.

12. A method for manufacturing a semiconductor device, characterized in that, include: (1) The process of forming a lower layer film on a substrate using the silicon-containing lower layer film forming composition according to any one of claims 1 to 5, (2) The step of forming a layer comprising a block copolymer on the lower film. (3) The process of separating the block copolymer phase. (4) The process of removing a portion of the phase-separated block copolymer, and (5) The process of etching the substrate.

Images