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

Abstract

Disclosed is a composition for forming a silicon-containing underlayer film for the formation of a self-assembled pattern, the composition containing [A] a polysiloxane, [B] not less than 0 part by mass but less than 2 parts by mass of a strongly acidic additive with respect to 100 parts by mass of the polysiloxane, and [C] a solvent, wherein the polysiloxane contains a structural unit that is derived from a hydrolyzable silane (A) represented by formula (A-1). (In formula (A-1), a represents an integer of 1 to 3;　b represents an integer of 0 to 2;　(a + b) represents an integer of 1 to 3;　R1 represents an organic group having a ring structure other than an aromatic hydrocarbon ring; and　R2 represents a specific group.)

Description

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

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

[0002] Thermosetting self-assembled films with nanoscale repeating structures are known to have properties different from those of ordinary homogeneous films, and self-assembled films with nanoscale repeating structures using block copolymers have been proposed. For example, a pattern formation method has been disclosed in which multiple segments constituting a block polymer are regularly arranged to form a pattern in a block polymer layer (Patent Document 1). Furthermore, a composition for forming a thermosetting self-assembled film has been disclosed (Patent Document 2), which contains a block copolymer, a crosslinking agent, and an organic solvent.

[0003] In recent years, with the further miniaturization of large-scale integrated circuits (LSIs), techniques for processing ever more delicate structures are required. In response to this demand, attempts have been made to form ever finer patterns by utilizing phase-separated structures formed by the self-assembly of block copolymers, in which mutually incompatible polymers are bonded together. For example, a pattern formation method has been proposed in which an underlayer film is formed to facilitate the alignment of a self-assembled monolayer into a desired vertical pattern, a self-assembled monolayer containing a block copolymer in which two or more polymers are bonded to the underlayer film is formed on the underlayer film, the block copolymer in the self-assembled monolayer is phase-separated, and at least one polymer phase of the polymers constituting the block copolymer is selectively removed. Examples of materials for forming the underlayer film include an underlayer film-forming composition containing a polymer containing a unit structure of a polycyclic aromatic vinyl compound in its main chain (Patent Document 3), and an underlayer film-forming composition for a self-assembled monolayer containing a polymer having a unit structure containing an aliphatic polycyclic structure of an aliphatic polycyclic compound in its main chain (Patent Document 4). It has also been disclosed that in order to arrange a self-assembled pattern at a desired position, ultraviolet rays or radiation are irradiated onto the underlayer film so as to overlap with the arrangement position, thereby causing changes in the unevenness and surface energy (hydrophilicity / hydrophobicity) of the surface of the underlayer film (see Patent Document 2, etc.).

[0004] On the other hand, in the field of semiconductor device manufacturing, a technique is widely used in which a fine pattern is formed on a substrate by lithography, and the substrate is processed by etching according to this pattern. As the lithography technique advances, finer patterns are being developed and the wavelength of the actinic rays used is becoming shorter, a method of providing an underlayer film containing silicon or the like, called an anti-reflection film, is widely used in order to suppress the influence of the actinic rays reflected from the semiconductor substrate (Patent Document 5, etc.).

[0005] The present applicant has proposed a composition for forming a silicon-containing underlayer film of a self-assembled film, which contains [A] a polysiloxane and [B] a solvent, but does not contain a strongly acidic additive (Patent Document 6).

[0006] JP 2009-234114 A JP 2011-122081 A WO 2014 / 097993 WO 2015 / 041208 JP 2007-163846 A WO 2022 / 210960

[0007] There is a strong demand for a technology that can realize a desired self-assembled pattern (a pattern structure that forms a self-assembled film, also called a microphase-separated structure), i.e., a technology that can induce a microphase-separated structure in a layer containing a block copolymer perpendicular to the substrate.

[0008] The present invention relates to a silicon-containing underlayer film provided between a substrate and a self-assembled film containing a block copolymer, and aims to provide a composition for forming the underlayer film that contributes to inducing a microphase-separated structure in a layer containing the block copolymer perpendicular to the substrate. The present invention also relates to a method for forming a self-assembled pattern using the underlayer film-forming composition.

[0009] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, and have completed the present invention having the following gist.

[0010] That is, the present invention encompasses the following: [1] A composition for forming a silicon-containing underlayer film for forming a self-assembled pattern, comprising: [A] a polysiloxane; [B] a strongly acidic additive in an amount of 0 parts by mass or more and less than 2 parts by mass per 100 parts by mass of the polysiloxane; and [C] a solvent, wherein the polysiloxane contains a structural unit derived from a hydrolyzable silane (A) represented by the following formula (A-1): (In formula (A-1), a represents an integer of 1 to 3. b represents an integer of 0 to 2. a+b represents an integer of 1 to 3. R １ represents an organic group having a ring structure other than an aromatic hydrocarbon ring. ２ represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or 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 thereof. X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. R １ , R ２ and when X is plural, a plurality of R １ , R ２ and X may be the same or different.) [2] The composition for forming a silicon-containing underlayer film according to [1], wherein the strongly acidic additive is a strongly acidic additive having a first acid dissociation constant in water of 1 or less. [3] The composition for forming a silicon-containing underlayer film according to [1] or [2], wherein the strongly acidic additive is a photoacid generator. [4] The composition for forming a silicon-containing underlayer film according to [1] or [2], wherein the R １

[0014] The composition for forming a silicon-containing underlayer film according to any one of [1] to [3], wherein the ring structure in the formula (I) contains a heteroatom. [5] The composition for forming a silicon-containing underlayer film according to any one of [1] to [4], wherein a proportion of Q units in all structural units of the component [A] is 65 mol % or less. [6] A method for manufacturing a substrate having a self-assembled pattern, comprising: forming an underlayer film on a substrate using the composition for forming a silicon-containing underlayer film according to any one of [1] to [5], and forming a self-assembled film above the underlayer film to form a self-assembled pattern. [7] A method for manufacturing a substrate having a self-assembled pattern, comprising: forming an underlayer film on a substrate using the composition for forming a silicon-containing underlayer film according to any one of [1] to [5], forming a neutral film on the underlayer film, and forming a self-assembled film on the neutral film to form a self-assembled pattern. [8] A method for manufacturing a substrate having a self-assembled 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 portion of the underlayer film; a step of forming a brush film on the underlayer film where the neutral film is not formed, to form a template film for the self-assembled pattern formed from the neutral film and the brush film; and a step of forming a self-assembled film on the template film for the self-assembled pattern, to obtain a self-assembled pattern.[9] 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 a portion of the underlayer film; a step of forming a brush film on the underlayer film where the neutral film is not formed, to form a template film for the self-assembled pattern formed from the neutral film and the brush film; and a step of forming a self-assembled film on the template film for the self-assembled pattern, to obtain a self-assembled pattern.

[10] A method for manufacturing a substrate having a self-assembled pattern, comprising: forming an organic underlayer film on a substrate; 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]; forming a neutral film on the underlayer film; forming a resist film on the neutral film; exposing and developing the resist film to obtain a resist pattern; etching the neutral film using the resist pattern as a mask; etching or stripping the resist pattern to obtain a patterned neutral film on the underlayer film; forming a brush film on the underlayer film and the patterned neutral film on the underlayer film; etching or stripping the brush film on the patterned neutral film to expose the neutral film and form a template film for the self-assembled pattern composed of the neutral film and the brush film; and forming a self-assembled film on the template film for the self-assembled pattern to obtain a self-assembled pattern.

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

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

[0011] According to the present invention, it is possible to provide a composition for forming a silicon-containing underlayer film, which is capable of forming a self-assembled film in which a desired vertical pattern is induced.

[0012] FIG. 1A is a schematic diagram showing one embodiment of self-assembled pattern formation (part 1). FIG. 1B is a schematic diagram showing one embodiment of self-assembled pattern formation (part 2). FIG. 1C is a schematic diagram showing one embodiment of self-assembled pattern formation (part 3). FIG. 1D is a schematic diagram showing one embodiment of self-assembled pattern formation (part 4). FIG. 1E is a schematic diagram showing one embodiment of self-assembled pattern formation (part 5). FIG. 1F is a schematic diagram showing one embodiment of self-assembled pattern formation (part 6). FIG. 1G is a schematic diagram showing one embodiment of self-assembled pattern formation (part 7). FIG. 1H is a schematic diagram showing one embodiment of self-assembled pattern formation (part 8). FIG. 1I is a schematic diagram showing one embodiment of self-assembled pattern formation (part 9). FIG. 1J is a schematic diagram showing one embodiment of self-assembled pattern formation (part 10). FIG. 2 is a photograph showing the microphase-separated structure of the self-assembled monolayer prepared in Example 17. FIG. 3 is a photograph showing the microphase-separated structure of the self-assembled monolayer prepared in Comparative Example 2.

[0013] In order to arrange the self-assembled patterns at the desired positions, the underlying film can be patterned using lithography techniques known in the field of semiconductor device manufacturing as one means of providing contrast in the surface roughness and surface energy of the underlying film. When the underlying film is patterned, a step is created between the patterned underlying film portion and the exposed portion of the underlying layer (substrate, etc.) that is not covered by the underlying film. This step can cause poor alignment of the self-assembled film. Furthermore, if the layer below the patterned underlying film is a silicon-containing film, the exposed portion of the silicon-containing film (the portion where the underlying film for pattern alignment is not present) is highly hydrophilic due to the silanol groups contained in the silicon-containing film. However, if the exposed portion is too hydrophilic, when a self-assembled film is formed using a block copolymer, as described below, the block copolymer may not be aligned in the desired vertical pattern, resulting in poor alignment. To eliminate these step differences and hydrophilic / hydrophobic problems, one method is to embed a brush material made of a high molecular weight polymer in the exposed portion of the silicon-containing film. The brush material is provided to prevent the self-assembled pattern from appearing in unintended areas, but if the brush material is present on top of the patterned underlayer film, which serves as the starting point for the vertical alignment of the block copolymer in the self-assembled film, it can actually cause poor alignment of the self-assembled film.

[0014] The present inventors have investigated the above-mentioned problems and found that excessive leaching of the acidic additive contained in the underlayer film or the silicon-containing film disposed thereunder disrupts the hydrophilic / hydrophobic properties of the surface of the underlayer film, resulting in the adhesion of the brush material to the underlayer film, which in turn leads to poor alignment of the block copolymers that make up the self-assembled film. Based on this finding, the present inventors have investigated the composition of the silicon-containing film and have completed a composition for forming a silicon-containing underlayer film, and a pattern formation method using the composition, which are capable of forming a self-assembled film that induces a desired vertical pattern.

[0015] In addition, the present inventors have proposed a composition for forming a silicon-containing underlayer film of a self-assembled film that does not contain a strongly acidic additive in WO 2022 / 210960, but after further investigation, the present inventors have found that a self-assembled film that induces a desired vertical pattern can be formed if the amount of the acidic additive is small. The present invention will be described below.

[0016] [Composition for forming a silicon-containing underlayer film] The composition for forming a silicon-containing underlayer film of the present invention contains: [A] a polysiloxane; [B] a strongly acidic additive in an amount of 0 parts by mass or more and less than 2 parts by mass per 100 parts by mass of the polysiloxane; and [C] a solvent. The polysiloxane [A] contains a structural unit derived from a hydrolyzable silane (A) represented by the following formula (A-1): (In formula (A-1), a represents an integer of 1 to 3. b represents an integer of 0 to 2. a+b represents an integer of 1 to 3. R １ represents an organic group having a ring structure other than an aromatic hydrocarbon ring. ２ represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or 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 thereof. X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. R １ , R ２ and when X is plural, a plurality of R １ , R ２ and X may be the same or different.

[0017] In addition, R ２is not an organic group having an unsaturated bond and a ring structure. In the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0018] <<R in formula (A-1) １ >> R １ represents an organic group having a ring structure other than an aromatic hydrocarbon ring.

[0019] The ring structure may or may not have a heteroatom, such as a nitrogen atom or an oxygen atom.

[0020] R １ The ring structure in may be an aliphatic hydrocarbon ring or a heterocycle. Examples of atoms other than carbon atoms constituting the heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. The ring structure may be an aromatic heterocycle or a non-aromatic ring. Examples of the ring structure include a 3- to 10-membered ring. Specific examples include a 3-, 4-, 5-, 6-, 7-, and 8-membered ring. Among these, a 5- to 7-membered ring is preferable. The ring structure may be a monocyclic structure or a polycyclic structure. Examples of the polycyclic structure include a bicyclic structure or a tricyclic structure. The manner in which the rings in the polycycle are bonded to each other includes, for example, the following three ways.・Sharing of one atom: For example, spirocyclic compounds ・Sharing of two atoms: When two rings share two atoms, as in decalin ・Bridged structure: When two rings can be considered to share three or more atoms, as in norbornane In the case of polycyclic rings, the number of atoms that make up the ring is the number of ring members. For example, norbornane is a seven-membered ring. R １ The number of ring structures contained in R may be one or more. １ The number of ring structures that the group has may be, for example, 1 to 3, or 1 to 2.

[0021] R １ For example, R does not have an Si—O group. １ The number of carbon atoms in R is not particularly limited.１ The number of carbon atoms in R is preferably 4 to 30, and more preferably 4 to 20. １ usually has a hydrogen atom. １ In addition to carbon atoms and hydrogen atoms, R may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom. １ may or may not have an ionic bond. １ When R has an ionic bond, １ may have an ionic bond in the row of atoms connecting the ring structure and the silicon atom, or may have an ionic bond in the row of atoms branching from the row of atoms connecting the ring structure and the silicon atom.

[0022] R in formula (A-1) １ is preferably represented by the following formula (A-2a):

[0023] (In formula (A-2a), R １１ represents a single bond or a divalent organic group which may have an ionic bond. １２ represents a group having a ring structure other than an aromatic hydrocarbon ring. * represents a bond.

[0024] R １１ is a divalent organic group which may have an ionic bond, R １１ The number of carbon atoms in R is not particularly limited. １１ The number of carbon atoms is preferably 1 to 25, and more preferably 1 to 15.

[0025] R １２ In order to obtain the effects of the present invention, R is preferably any one of the following formulas (A-2c-1) to (A-2c-7). １２ From the viewpoint of suitably obtaining the effects of the present invention, it is preferable that the compound represented by formula (A-2c-1) to formula (A-2c-7) below be used. (In formula (A-2c-1), R １ｂ ~R ｂ１０ R each independently represents a hydrogen atom, a halogen atom, or a monovalent group. ｂ１and R ｂ８ may be taken together to form a methylene group or a 1,2-ethylene group. １ｂ ~R ｂ１０ One of the groups is R in formula (A-2a). １１ In formula (A-2c-2), X represents a bond bonded to １ ~X ５ represents N or CR (wherein each R independently represents a hydrogen atom, a halogen atom, or a monovalent group). １ ~X ５ At least one of the following is N. * represents a bond. １１ represents 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. ｃ１ ~R ｃ５ One of the groups is R in formula (A-2a). １１ In formula (A-2c-4), X represents a bond bonded to ２１ represents O or S. ｄ１ ~R ｄ４ each independently represents a hydrogen atom, a halogen atom, or a monovalent group. ｄ１ ~R ｄ４ One of the groups is R in formula (A-2a). １１ In formula (A-2c-5), R ｅ１ ~R ｅ４ each independently represents a hydrogen atom, a halogen atom, or a monovalent group. ｅ１ ~R ｅ４ One of the groups is R in formula (A-2a). １１ In formula (A-2c-6), X represents a bond bonded to ３１ is -C(=O)-N(R ｆ３ )-, -C(=O)-C(R ｆ４ ) (R ｆ５ ) - or -C(R ｆ６ ) (R ｆ７ )-. ｆ１ ~R ｆ７each independently represents a hydrogen atom, a halogen atom, or a monovalent group. ｆ１ and R ｆ２ One of the groups is R in formula (A-2a). １１ In formula (A-2c-7), * represents a bond.

[0026] R １ｂ ~R ｂ１０ , R ｃ１ ~R ｃ５ , R ｄ１ ~R ｄ４ , R ｅ１ ~R ｅ４ , R ｆ１ ~R ｆ７and the monovalent group in R of CR includes, for example, a monovalent organic group having 1 to 10 carbon atoms. Examples of the monovalent organic group having 1 to 10 carbon atoms include 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. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n- Propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, a 1- ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,Examples of such alkyl groups include a 3-dimethylcyclobutyl group, a 1-n-propylcyclopropyl group, a 2-n-propylcyclopropyl group, a 1-i-propylcyclopropyl group, a 2-i-propylcyclopropyl group, a 1,2,2-trimethylcyclopropyl group, a 1,2,3-trimethylcyclopropyl group, a 2,2,3-trimethylcyclopropyl group, a 1-ethyl-2-methylcyclopropyl group, a 2-ethyl-1-methylcyclopropyl group, a 2-ethyl-2-methylcyclopropyl group, a 2-ethyl-3-methylcyclopropyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icodecyl group. Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, an -methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,Examples thereof include a 2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, a 1-ethyl-2-methyl-n-propoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a norbornyloxy group, an adamantyloxy group, an adamantanemethyloxy group, an adamantaneethyloxy group, a tetracyclodecanyloxy group, and a tricyclodecanyloxy group. Examples of the alkenyl group having 2 to 10 carbon atoms include 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, and 1-n-propylethenyl. nyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2 -propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butyl azathenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl Examples of the alkyl group include methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group. In this specification, "i" means "iso", "s" means "sec", and "t" means "tert".

[0027] Examples of formula (A-2c-2) include the following formula (A-2c-2-1): Examples of formula (A-2c-6) include the following formulas (A-2c-6-1) to (A-2c-6-3): (In formula (A-2c-2-1), each R independently represents a hydrogen atom, a halogen atom, or a monovalent group. * represents a bond. In formulas (A-2c-6-1) to (A-2c-6-3), R ｆ１ ~R ｆ７ each independently represents a hydrogen atom, a halogen atom, or a monovalent group. ｆ１ and R ｆ２ One of the groups is R in formula (A-2a). １１ represents the bond that bonds to

[0028] <<<R １１ >>> R １１ is preferably a single bond or a divalent organic group represented by the following formulae (A-2-1) to (A-2-4). (In formula (A-2-1), R ２１ represents an alkylene group having 1 to 6 carbon atoms. ３１ represents an alkylene group having 1 to 6 carbon atoms. ３２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ３３ represents a single bond or an alkylene group having 1 to 6 carbon atoms. ４１ represents an alkylene group having 1 to 6 carbon atoms. ４２ represents a single bond or an alkylene group having 1 to 6 carbon atoms. ５１ represents an alkylene group having 1 to 6 carbon atoms. ５２ and R ５３ R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ５４ represents a single bond or an alkylene group having 1 to 6 carbon atoms. In formulas (A-2-1) to (A-2-4), *1 represents a bond bonded to Si. *2 represents R １２ represents the bond that bonds to

[0029] In the silicon-containing underlayer film-forming composition and underlayer film, the amino group (—N(R ３２ For example, when nitric acid is added to the composition for forming a silicon-containing underlayer film, the amino group (—N(R ３２)-) may be cationized to form a nitrate.

[0030] R ２１ , R ３１ , R ３３ , R ４１ , R ４２ , and R ５１ The alkylene group having 1 to 6 carbon atoms in the formula (I) may be either linear or branched. Examples of the alkylene group having 1 to 6 carbon atoms include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene. Of these, methylene, ethylene, trimethylene, and tetramethylene are preferred.

[0031] R ３２ , R ５２ , and R ５３ The alkyl group having 1 to 4 carbon atoms in R may be either linear or branched. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and a t-butyl group. ３２ , R ５２ , and R ５３ is preferably a hydrogen atom, a methyl group, or an ethyl group.

[0032] <<R in formula (A-1) ２>> The alkyl group may be linear, branched, or cyclic, and the number of carbon atoms therein 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. Specific examples of linear or branched alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-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 ... 1-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group.

[0033] Specific examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a 1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a 3-ethyl-cyclobutyl group, a 1,2-dimethyl-cyclobutyl group, a 1,3-dimethyl-cyclobutyl group, a 2,2-dimethyl-cyclobutyl group, a 2,3-dimethyl-cyclobutyl group, a 2,4- Examples include cycloalkyl groups such as dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group; and bridged ring cycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group.

[0034] The aryl group may be any of a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused-ring aromatic hydrocarbon compound, and a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound, and the number of carbon atoms therein is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. For example, the aryl group may be an aryl group having 6 to 20 carbon atoms, such as 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-naphthacenyl group, a 2-naphthacenyl group, a 5-naphthacenyl group, a 2-chrysenyl group, a 1-pyrenyl group, and a 2-pyrenyl group. , pentacenyl group, benzopyrenyl group, triphenylenyl group; biphenyl-2-yl group (o-biphenylyl group), biphenyl-3-yl group (m-biphenylyl group), biphenyl-4-yl group (p-biphenylyl group), para-terphenyl-4-yl group, meta-terphenyl-4-yl group, ortho-terphenyl-4-yl group, 1,1'-binaphthyl-2-yl group, 2,2'-binaphthyl-1-yl group and the like, but are not limited to these.

[0035] An aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups include those described above. The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of aralkyl groups include, but are not limited to, a phenylmethyl group (benzyl group), a 2-phenylethylene 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, an 8-phenyl-n-octyl group, a 9-phenyl-n-nonyl group, and a 10-phenyl-n-decyl group.

[0036] The halogenated alkyl group, halogenated aryl group, and halogenated aralkyl group are alkyl groups, aryl groups, and aralkyl groups, respectively, substituted with one or more halogen atoms. Specific examples of such alkyl groups, aryl groups, and aralkyl groups include those described above. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0037] The number of carbon atoms in the halogenated alkyl group 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. Specific examples of halogenated alkyl groups include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 2-chloro-1,1,2-trifluoroethyl group, a pentafluoroethyl group, a 3-bromopropyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,2,3,3,3-hexafluoropropyl group, a 1,1,1,3,3,3-hexafluoropropan-2-yl group, a 3-bromo-2-methylpropyl group, a 4-bromobutyl group, and a perfluoropentyl group, but are not limited to these.

[0038] The number of carbon atoms in the halogenated aryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of the halogenated aryl group include a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, a 2,3-difluorophenyl group, a 2,4-difluorophenyl group, a 2,5-difluorophenyl group, a 2,6-difluorophenyl group, a 3,4-difluorophenyl group, a 3,5-difluorophenyl group, a 2,3,4-trifluorophenyl group, a 2,3,5-trifluorophenyl group, a 2,3,6-trifluorophenyl group, a 2,4,5-trifluorophenyl group, a 2,4,6-trifluorophenyl group, a 3,4,5-trifluorophenyl group, a 2,3,4,5-tetrafluorophenyl group, a 2,3,4,6-tetrafluorophenyl group, a 2,3,5,6-tetrafluorophenyl group, a pentafluorophenyl group, a 2-fluoro-1-naphthyl group, a 3-fluorophenyl group, a 2-fluoro-1-naphthyl ... Examples of the fluorocarbon include 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, and heptafluoro-2-naphthyl. Examples of the fluorocarbon include, but are not limited to, 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 (iodine group).

[0039] The number of carbon atoms in the halogenated aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of the halogenated aralkyl group include 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, 2,4-difluorobenzyl group, 2,5-difluorobenzyl group, 2,6-difluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzyl group, 2,3,4-trifluorobenzyl group, 2,3,5-trifluorobenzyl group, 2,3,6-trifluorobenzyl group, 2,4,5-trifluorobenzyl group, 2,4,5-trifluorobenzyl group, 2,5-trifluorobenzyl group, 2,6-trifluorobenzyl group, 2,4,5-trifluorobenzyl group, 2 ... Examples of the fluorobenzyl group include a 2,4,6-trifluorobenzyl group, a 2,3,4,5-tetrafluorobenzyl group, a 2,3,4,6-tetrafluorobenzyl group, a 2,3,5,6-tetrafluorobenzyl group, and a 2,3,4,5,6-pentafluorobenzyl group, and also include 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), but are not limited to these.

[0040] The alkoxyalkyl group, alkoxyaryl group, and alkoxyaralkyl group are, respectively, alkyl groups, aryl groups, and aralkyl groups substituted with one or more alkoxy groups, and specific examples of such alkyl groups, aryl groups, and aralkyl groups are the same as those described above.

[0041] Examples of the alkoxy group as a substituent include linear, branched, and cyclic alkoxy groups having at least one alkyl moiety and having 1 to 20 carbon atoms. Examples of the linear or branched alkoxy group include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyl ... 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, 1,1-dimethyl-n-propoxy, Examples include a methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, and a 1-ethyl-2-methyl-n-propoxy group.Examples of cyclic alkoxy groups include cyclopropoxy, cyclobutoxy, 1-methylcyclopropoxy, 2-methylcyclopropoxy, cyclopentyloxy, 1-methylcyclobutoxy, 2-methylcyclobutoxy, 3-methylcyclobutoxy, 1,2-dimethylcyclopropoxy, 2,3-dimethylcyclopropoxy, 1-ethylcyclopropoxy, 2-ethylcyclopropoxy, cyclohexyloxy, 1-methylcyclopentyloxy, 2-methylcyclopentyloxy, 3-methylcyclopentyloxy, 1-ethylcyclobutoxy, 2-ethylcyclobutoxy, 3-ethylcyclobutoxy, 1,2-dimethylcyclobutoxy, 1,3 dimethylcyclobutoxy group, 2,2-dimethylcyclobutoxy group, 2,3-dimethylcyclobutoxy group, 2,4-dimethylcyclobutoxy group, 3,3-dimethylcyclobutoxy group, 1-n-propylcyclopropoxy group, 2-n-propylcyclopropoxy group, 1-i-propylcyclopropoxy group, 2-i-propylcyclopropoxy group, 1,2,2-trimethylcyclopropoxy group, 1,2,3-trimethylcyclopropoxy group, 2,2,3-trimethylcyclopropoxy group, 1-ethyl-2-methylcyclopropoxy group, 2-ethyl-1-methylcyclopropoxy group, 2-ethyl-2-methylcyclopropoxy group, and 2-ethyl-3-methylcyclopropoxy group.

[0042] Specific examples of alkoxyalkyl groups include, but are not limited to, lower (about 5 carbon atoms or less) alkyloxy-lower (about 5 carbon atoms or less) alkyl groups such as methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, and ethoxymethyl groups. Specific examples of alkoxyaryl groups include, but are not limited to, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(1-ethoxy)phenyl, 3-(1-ethoxy)phenyl, 4-(1-ethoxy)phenyl, 2-(2-ethoxy)phenyl, 3-(2-ethoxy)phenyl, 4-(2-ethoxy)phenyl, 2-methoxynaphthalen-1-yl, 3-methoxynaphthalen-1-yl, 4-methoxynaphthalen-1-yl, 5-methoxynaphthalen-1-yl, 6-methoxynaphthalen-1-yl, and 7-methoxynaphthalen-1-yl groups. Specific examples of the alkoxyaralkyl group include, but are not limited to, a 3-(methoxyphenyl)benzyl group and a 4-(methoxyphenyl)benzyl group.

[0043] The alkenyl group may be either linear or branched, and the number of carbon atoms therein 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. Specific examples of the alkenyl group include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1- methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl- 4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group Examples of such alkyl groups include 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, and 1-i-propyl-2-propenyl group.

[0044] Furthermore, examples of the substituents in the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyaralkyl group, and alkenyl group include alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkoxyalkyl group, aryloxy group, alkoxyaryl group, alkoxyaralkyl group, alkoxy group, and aralkyloxy group. Specific examples of these and their preferred numbers of carbon atoms include those described above or below. Furthermore, the aryloxy group exemplified as a substituent is a group in which an aryl group is bonded via an oxygen atom (—O—), and specific examples of such aryl groups include those described above. The number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples include, but are not limited to, a phenoxy group and a naphthalene-2-yloxy group. When two or more substituents are present, the substituents may be bonded to each other to form a ring.

[0045] Examples of organic groups containing an acryloyl group include an acryloyloxymethyl group, an acryloyloxyethyl group, and an acryloyloxypropyl group. Examples of organic groups containing a methacryloyl group include a methacryloyloxymethyl group, a methacryloyloxyethyl group, and a methacryloyloxypropyl group. Examples of organic groups containing a mercapto group include a mercaptoethyl group, a mercaptobutyl group, a mercaptohexyl group, and a mercaptooctyl group. Examples of organic groups containing an amino group include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, a dimethylaminoethyl group, and a dimethylaminopropyl group. Organic groups containing an amino group will be described in more detail below. Examples of organic groups containing an alkoxy group include, but are not limited to, a methoxymethyl group and a methoxyethyl group. However, groups in which the alkoxy group is directly bonded to a silicon atom are excluded. Examples of organic groups containing a sulfonyl group include, but are not limited to, a sulfonylalkyl group. Examples of organic groups containing a cyano group include, but are not limited to, a cyanoethyl group, a cyanopropyl group, and a thiocyanate group.

[0046] The organic group having an amino group can be an organic group having at least one of a primary amino group, a secondary amino group, and a tertiary amino group.Preferably, a hydrolysis condensate obtained by hydrolyzing a hydrolyzable silane having a tertiary amino group with a strong acid to form a counter cation having a tertiary ammonium group can be used.In addition, the organic group can contain heteroatoms such as oxygen atoms and sulfur atoms in addition to the nitrogen atoms constituting the amino group.

[0047] A preferred example of the organic group having an amino group is a group represented by the following formula (A1).

[0048] In formula (A1), R １０１ and R １０２are each independently a hydrogen atom or a hydrocarbon group, and L are each independently an alkylene group which may be substituted. * represents a bond. Examples of hydrocarbon groups include, but are not limited to, alkyl groups and alkenyl groups. Specific examples of these alkyl groups and alkenyl groups include R ２ Examples of the alkylene group include the same groups as those described above in the above. The alkylene group may be either linear or branched, and the number of carbon atoms is usually 1 to 10, preferably 1 to 5. Examples include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene. Examples of organic groups having an amino group include, but are not limited to, amino, aminomethyl, aminoethyl, dimethylaminoethyl, and dimethylaminopropyl groups.

[0049] <<X in Formula (A-1)>> Examples of the alkoxy group in X include R ２ Examples of the halogen atom in X include the alkoxy groups exemplified in the description of R ２ Examples of the halogen atoms include those exemplified in the explanation of the above.

[0050] An aralkyloxy group is a monovalent group derived by removing a hydrogen atom from the hydroxy group of an aralkyl alcohol, and specific examples of the aralkyl group in the aralkyloxy group include those described above. The number of carbon atoms in the aralkyloxy group is not particularly limited, but can be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less. Specific examples of the aralkyloxy group include, but are not limited to, a phenylmethyloxy group (benzyloxy group), a 2-phenylethyleneoxy group, a 3-phenyl-n-propyloxy group, a 4-phenyl-n-butyloxy group, a 5-phenyl-n-pentyloxy group, a 6-phenyl-n-hexyloxy group, a 7-phenyl-n-heptyloxy group, an 8-phenyl-n-octyloxy group, a 9-phenyl-n-nonyloxy group, and a 10-phenyl-n-decyloxy group.

[0051] An acyloxy group is a monovalent group derived by removing a hydrogen atom from a carboxyl group (—COOH) of a carboxylic acid compound, and typical examples include, but are not limited to, alkylcarbonyloxy groups, arylcarbonyloxy groups, and aralkylcarbonyloxy groups derived by removing a hydrogen atom from the carboxyl group of an alkylcarboxylic acid, arylcarboxylic acid, or aralkylcarboxylic acid. Specific examples of the alkyl group, aryl group, and aralkyl group in such alkylcarboxylic acid, arylcarboxylic acid, and aralkylcarboxylic acid are the same as those described above.Specific examples of the acyloxy group include acyloxy groups having 2 to 20 carbon atoms, such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, an n-butylcarbonyloxy group, an i-butylcarbonyloxy group, an s-butylcarbonyloxy group, a t-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, an n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy group, a n-hexylcarbonyloxy group, a 1-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pent ...2-methyl-n-pentylcarbonyloxy group, a 2-methyl-n-pentylcarbonyloxy group carbonyloxy group, 3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group, 1,1-dimethyl-n-butylcarbonyloxy group, 1,2-dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1,1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, 1-ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, and tosylcarbonyloxy group.

[0052] Specific examples of the hydrolyzable silane (A) represented by formula (A-1) include, for example, the following compounds, but the hydrolyzable silane (A) represented by formula (A-1) is not limited to these compounds. In the formula, T represents X in formula (A-1). T represents, for example, a methoxy group or an ethoxy group. Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ac represents an acetyl group.

[0053] [A] The amount of hydrolyzable silane (A) used in synthesizing a polysiloxane containing a structural unit derived from hydrolyzable silane (A) represented by formula (A-1) 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 hydrolyzable silanes used in synthesizing the polysiloxane, from the viewpoint of more fully achieving the effects of the present invention.

[0054] <Component [A]: Polysiloxane> The polysiloxane as the component [A] is not particularly limited as long as it is a polymer that contains a structural unit derived from the hydrolyzable silane (A) represented by formula (A-1) and has a siloxane bond.

[0055] The polysiloxane may be a modified polysiloxane in which some of the silanol groups have been modified, such as a polysiloxane modified product in which some of the silanol groups have been alcohol-modified or acetal-protected. The polysiloxane may also be, for example, a hydrolysis condensation product of a hydrolyzable silane, or a modified product in which at least some of the silanol groups of the hydrolysis condensation product have been alcohol-modified or acetal-protected (hereinafter, sometimes referred to as a "modification product of the hydrolysis condensation product"). The hydrolyzable silane in the hydrolysis condensation product may contain one or more hydrolyzable silanes. The polysiloxane as component [A] may have a cage, ladder, linear, or branched main chain structure. Furthermore, commercially available polysiloxanes may be used as the polysiloxane as component [A'].

[0056] In the present invention, the "hydrolyzed condensate" of a hydrolyzable silane, i.e., the product of hydrolysis and condensation, includes not only polyorganosiloxane polymers that are condensates in which condensation has been completely completed, but also polyorganosiloxane polymers that are partial hydrolyzed condensates in which condensation has not been completely completed. Like the condensates in which condensation has been completely completed, such partial hydrolyzed condensates are polymers obtained by the hydrolysis and condensation of a hydrolyzable silane, but the hydrolysis has only partially stopped and the condensation has not been completed, and therefore Si—OH groups remain. Furthermore, in addition to the hydrolyzed condensate, the composition for forming a silicon-containing underlayer film may also contain uncondensed hydrolyzates (complete hydrolyzates, partial hydrolyzates) and monomers (hydrolyzable silanes). In this specification, "hydrolyzable silanes" may also be simply referred to as "silane compounds."

[0057] Examples of polysiloxanes as component [A] include hydrolysis condensates of hydrolyzable silanes, including hydrolyzable silane (A) represented by formula (A-1), and modified products thereof.

[0058] Examples of polysiloxanes as component [A] include hydrolyzable silane (A) represented by formula (A-1) and a hydrolyzed silane condensate containing at least one hydrolyzable silane represented by the following formula (1), or a modified product thereof:

[0059] <<Formula (1)>>

[0060] In formula (1), R １ are groups bonded to silicon atoms, and each independently represents an optionally substituted alkyl group, an optionally substituted alkyl halide, an optionally substituted alkoxyalkyl group, or an optionally substituted alkenyl group, or 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 thereof. ２are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. a represents an integer of 0 to 3.

[0061] R in formula (1) １ Specific examples of the groups and atoms in the formula (A-1) and the preferred number of carbon atoms therein are: ２ The groups and the number of carbon atoms mentioned above for R in formula (1) can be mentioned. ２ Specific examples of each group and atom in the formula (A-1) and their suitable numbers of carbon atoms include the groups, atoms, and numbers of carbon atoms described above for X in the formula (A-1).

[0062] <<<<Specific Examples of Hydrolyzable Silanes Represented by Formula (1)>>> Specific examples of hydrolyzable silanes represented by formula (1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltrippropoxysilane, methyltributoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, and methyltrimethylsilane. Triphenethyloxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyltrichlorosilane, Vinyltriacetoxysilane, Methylvinyldimethoxysilane, Methylvinyldiethoxysilane, Methylvinyldichlorosilane, Methylvinyldiacetoxysilane, Dimethylvinylmethoxysilane, Dimethylvinylethoxysilane, Dimethylvinylchlorosilane, Dimethylvinylacetoxysilane, Divinyldimethoxysilane, Divinyldiethoxysilane, Divinyl vinyldichlorosilane, divinyldiacetoxysilane, aryltrimethoxysilane, aryltriethoxysilane, aryltrichlorosilane, aryltriacetoxysilane, arylmethyldimethoxysilane, arylmethyldiethoxysilane, arylmethyldichlorosilane, arylmethyldiacetoxysilane, aryldimethylmethoxysilane, aryldimethylethoxysilane, aryldimethylchlorosilane, aryldimethylacetoxysilane, diaryldimethoxysilane, diaryldiethoxysilane, diaryldichlorosilane, diaryldiacetoxysilane, 3-arylaminopropyltrimethoxysilane, 3-arylaminopropyltriethoxysilane, p-styryltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane,Phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiacetoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylacetoxysilane, triphenylchlorosilane, 3-phenylaminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane triethoxysilane, dimethoxymethyl-3-(3-phenoxypropylthiopropyl)silane, triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, benzyldimethylchlorosilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltrichlorosilane, phenethyltriacetoxysilane, Phenethylmethyldimethoxysilane, phenethylmethyldiethoxysilane, phenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane silane, methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, i-propoxyphenyltrimethoxysilane, i-propoxyphenyltriethoxysilane, i-propoxyphenyltriacetoxysilane,i-propoxyphenyltrichlorosilane, i-propoxybenzyltrimethoxysilane, i-propoxybenzyltriethoxysilane, i-propoxybenzyltriacetoxysilane, i-propoxybenzyltrichlorosilane, t-butoxyphenyltrimethoxysilane, t-butoxyphenyltriethoxysilane, t-butoxyphenyltriacetoxysilane, t-butoxyphenyltrichlorosilane, t-butoxybenzyltrimethoxysilane, t-butoxybenzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t- Butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ- Methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, thiocyanatopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyl diarylisocyanurate, bicyclo[2,2,1]heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane, benzenesulfonamidopropyltriethoxysilane, dimethylaminopropyltriethoxysilane trimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, andExamples include, but are not limited to, silanes represented by the following formula:

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085] In the formula, T independently represent an alkoxy group, an acyloxy group, or a halogen group, for example, preferably a methoxy group or an ethoxy group.

[0086] Examples of the polysiloxane [A] include a hydrolyzable silane (A) represented by formula (A-1) and a hydrolyzable silane hydrolyzed condensate thereof, or a modified product thereof, containing a hydrolyzable silane represented by formula (2): Examples of the polysiloxane [A] include a hydrolyzable silane (A) represented by formula (A-1), a hydrolyzable silane represented by formula (1), and a hydrolyzable silane represented by formula (2):

[0087] <Formula (2)>

[0088] In formula (2), R ３ are groups bonded to silicon atoms, and each independently represent an optionally substituted alkyl group, an optionally substituted halogenated alkyl group, an optionally substituted alkoxyalkyl group, or an optionally substituted alkenyl group, or 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 thereof. ４ are groups or atoms bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. ５ are groups bonded to a silicon atom, and each independently represents an alkylene group or an arylene group; b represents 0 or 1; and c represents 0 or 1.

[0089] R ３ Specific examples of the groups and atoms in the formula (A-1) and the preferred number of carbon atoms therein are: ２ The groups and carbon atom numbers described above for R can be mentioned. ４Specific examples of the groups and atoms in R and the preferred numbers of carbon atoms therefor include the groups, atoms, and numbers of carbon atoms described above for X in formula (A-1). ５ Specific examples of the alkylene group in the formula (I) include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; Examples of alkanetriyl groups include, but are not limited to, alkane-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, and 2-methylpropane-1,1,3-triyl groups. ５Specific examples of the arylene group in the formula (I) include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group; a 1,5-naphthalenediyl group, a 1,8-naphthalenediyl group, a 2,6-naphthalenediyl group, a 2,7-naphthalenediyl group, a 1,2-anthracenediyl group, a 1,3-anthracenediyl group, a 1,4-anthracenediyl group, a 1,5-anthracenediyl group, a 1,6-anthracenediyl group, a 1,7-anthracenediyl group, a 1,8-anthracenediyl group, a 2,3- Examples of the aryl group include, but are not limited to, groups derived by removing two hydrogen atoms on the aromatic ring of a fused-ring aromatic hydrocarbon compound such as an anthracenediyl group, a 2,6-anthracenediyl group, a 2,7-anthracenediyl group, a 2,9-anthracenediyl group, a 2,10-anthracenediyl group, or a 9,10-anthracenediyl group; and groups derived by removing two hydrogen atoms on the aromatic ring of a ring-linked aromatic hydrocarbon compound such as a 4,4'-biphenyldiyl group or a 4,4''-paraterphenyldiyl group. b is preferably 0. c is preferably 1.

[0090] Specific examples of the hydrolyzable silane represented by formula (2) include, but are not limited to, methylene bistrimethoxysilane, methylene bistrichlorosilane, methylene bistriacetoxysilane, ethylene bistriethoxysilane, ethylene bistrichlorosilane, ethylene bistriacetoxysilane, propylene bistriethoxysilane, butylene bistrimethoxysilane, phenylene bistrimethoxysilane, phenylene bistriethoxysilane, phenylene bismethyldiethoxysilane, phenylene bismethyldimethoxysilane, naphthylene bistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, and bismethyldimethoxydisilane.

[0091] Examples of the polysiloxane [A] include a hydrolyzable silane (A) represented by formula (A-1), and a hydrolyzed condensate of a hydrolyzable silane or a modified product thereof, which contains the hydrolyzable silane represented by formula (1) and / or the hydrolyzable silane represented by formula (2) as well as other hydrolyzable silanes listed below.

[0092] <<Silane Compound Having an Onium Group in the Molecule (Hydrolyzable Organosilane)>> A silane compound having an onium group in the molecule is expected to be able to effectively and efficiently promote the crosslinking reaction of a hydrolyzable silane.

[0093] A suitable example of the silane compound having an onium group in the molecule is represented by formula (3).

[0094]

[0095] R １１ R is a group bonded to a silicon atom and represents an onium group or an organic group having an onium group. １２ are groups bonded to silicon atoms, and each independently represents an optionally substituted alkyl group, an optionally substituted halogenated alkyl group, an optionally substituted alkoxyalkyl group, or an optionally substituted alkenyl group, or 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 thereof. １３ are groups or atoms bonded to a silicon atom, and each independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, f represents 1 or 2, and g represents 0 or 1, and 1≦f+g≦2 is satisfied.

[0096] Specific examples of alkyl groups, halogenated alkyl groups, alkoxyalkyl groups, alkenyl groups, organic groups having an epoxy group, organic groups having an acryloyl group, organic groups having a methacryloyl group, organic groups having a mercapto group, organic groups having an amino group, organic groups having a cyano group, alkoxy groups, aralkyloxy groups, acyloxy groups, and halogen atoms, and specific examples of substituents of alkyl groups, halogenated alkyl groups, alkoxyalkyl groups, and alkenyl groups, and their preferred numbers of carbon atoms, include R １２ Regarding the formula (A-1), R ２ The above-mentioned with respect to R １３ With regard to X, those mentioned above with respect to X in formula (A-1) can be mentioned.

[0097] More specifically, specific examples of the onium group include a cyclic ammonium group or a chain ammonium group, with a tertiary ammonium group or a quaternary ammonium group being preferred. That is, suitable specific examples of the onium group or the organic group having the onium group include a cyclic ammonium group or a chain ammonium group, or an organic group having at least one of these, with a tertiary ammonium group or a quaternary ammonium group or an organic group having at least one of these being preferred. Note that when the onium group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as an atom constituting the ring. In this case, there are cases where the nitrogen atom constituting the ring and the silicon atom are bonded directly or via a divalent linking group, and cases where the carbon atom constituting the ring and the silicon atom are bonded directly or via a divalent linking group.

[0098] In one preferred embodiment, R １１ can be a heteroaliphatic cyclic ammonium group represented by the following formula (S2):

[0099]

[0100] In formula (S2), A ５ , A ６ , A ７ and A ８ are each independently a group represented by any one of the following formulas (J4) to (J6), ５ ~A ８ At least one of the silicon atoms in formula (3) is a group represented by the following formula (J5): ５ ~A ８ A is bonded to the ring so that the resulting ring exhibits non-aromaticity. ５ ~A ８ The bond between each atom and the adjacent atom that together constitutes the ring is determined to be a single bond or a double bond. * represents a bond.

[0101]

[0102] In formulas (J4) to (J6), R １０are each independently a single bond, a hydrogen atom, an alkyl group, or a halogenated alkyl group, and specific examples of the alkyl group and the halogenated alkyl group and their suitable numbers of carbon atoms are the same as those described above. * represents a bond.

[0103] In formula (S2), R １５ each independently represents an alkyl group, a halogenated alkyl group, or a hydroxy group; R １５ If there are two or more R １５ may be bonded to each other to form a ring, and two R １５ The ring formed by may be a bridged ring structure, and in such a case, the cyclic ammonium group has an adamantane ring, a spiro ring, etc. Specific examples of the alkyl group and the halogenated alkyl group and their suitable numbers of carbon atoms are the same as those described above.

[0104] In formula (S2), n ２ is an integer from 1 to 8, and m ３ is 0 or 1, m ４ is a positive integer from 0 or 1 to the maximum number of substitutions possible on a monocyclic or polycyclic ring. ３ If is 0, A ５ ~A ８ (4+n ２ That is, an n-membered ring is formed. ２ is 1, a five-membered ring; ２ is 2, a 6-membered ring, ２ is 3, a 7-membered ring, ２ is 4, an 8-membered ring, ２ is 5, a 9-membered ring; ２ When n is 6, it is a 10-membered ring. ２ When n is 7, it is an 11-membered ring. ２ When m is 8, a 12-membered ring is formed. ３ If is 1, then A ５ ~A ７ (4+n ２ )-membered ring and A ８ A fused ring is formed by condensing with a 6-membered ring containing A. ５ ~A ８may or may not have a hydrogen atom on an atom constituting the ring, depending on which of formulas (J4) to (J6) it is. ５ ~A ８ has a hydrogen atom on an atom constituting the ring, the hydrogen atom is １５ Also, A may be replaced by ５ ~A ８ A ring-constituting atom other than the ring-constituting atom in １５ For this reason, as described above, m ４ is selected from 0 or an integer from 1 to the maximum number of substitutions possible on a monocyclic or polycyclic ring.

[0105] The bond of the heteroaliphatic cyclic ammonium group represented by formula (S2) is present on any carbon atom or nitrogen atom present in such a single ring or fused ring, and is directly bonded to a silicon atom, or is bonded to a linking group to form an organic group having a cyclic ammonium, which is then bonded to a silicon atom. Examples of such linking groups include alkylene groups, and specific examples of alkylene groups and their preferred numbers of carbon atoms are the same as those described above.

[0106] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (3) having the heteroaliphatic cyclic ammonium group represented by formula (S2) include, but are not limited to, silanes represented by the following formulas:

[0107]

[0108]

[0109] In yet another example, R １１ can be a chain ammonium group represented by the following formula (S3).

[0110] In formula (S3), R １０are each independently a hydrogen atom, an alkyl group, a halogenated alkyl group, or an alkenyl group, and specific examples of the alkyl group, halogenated alkyl group, and alkenyl group and their suitable numbers of carbon atoms are the same as those described above. * represents a bond.

[0111] The chain ammonium group represented by formula (S3) is directly bonded to a silicon atom, or is bonded to a linking group to form an organic group having the chain ammonium group, which is then bonded to a silicon atom. Examples of such linking groups include alkylene groups and alkenylene groups, and specific examples of the alkylene group and alkenylene group are the same as those described above.

[0112] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (3) having a chain ammonium group represented by formula (S3) include, but are not limited to, silanes represented by the following formulas:

[0113]

[0114]

[0115] The proportion of Q units in all structural units of the polysiloxane [A] (component [A]) is not particularly limited, but is preferably 65 mol% or less. When the proportion of Q units in all structural units of the polysiloxane [A] (component [A]) is 65 mol% or less, the polysiloxane [A] preferably has at least one of a hydroxyl group, a carboxyl group, and an isocyanuric acid structure. By doing so, even when the proportion of Q units in the polysiloxane [A] is relatively small, the coatability of the silicon-containing underlayer film-forming composition is improved.

[0116] The term "total structural units" refers to the sum of M units, D units, T units, and Q units constituting the polysiloxane. The polysiloxane does not necessarily have to have all of the M units, D units, T units, and Q units. The term "M units" refers to (R) ３ SiO １／２Here, each R independently represents a hydrogen atom or an organic group. The number (here, 3) after (R) means that three hydrogen atoms or organic groups are bonded to the silicon atom. In other words, the M unit is a siloxy unit consisting of one silicon atom, three hydrogen atoms or organic groups, and one oxygen atom O. ＊ More specifically, the M unit has three hydrogen atoms or organic groups bonded to one silicon atom, and one oxygen atom O bonded to one silicon atom. ＊ The D unit has (R) ２ SiO ２／２ (each R independently represents a hydrogen atom or an organic group). That is, the D unit has one silicon atom, two hydrogen atoms or organic groups bonded to the silicon atom, and an oxygen atom O bonded to another silicon atom. ＊ The T unit is a unit having two RSiO ３／２ (R represents a hydrogen atom or an organic group). That is, the T unit has one silicon atom, one hydrogen atom or an organic group bonded to the silicon atom, and an oxygen atom O bonded to another silicon atom. ＊ The Q unit is a unit having three SiO ２ That is, the Q unit has one silicon atom and an oxygen atom O bonded to another silicon atom. ＊ It is a unit that has four of these.

[0117] On the other hand, for example, when the amount of the strongly acidic additive is 0 part by mass per 100 parts by mass of the polysiloxane [A], the proportion of Q units in all structural units of the polysiloxane [A] (component [A]) may be 60 mol % or more, or may be 65 mol % or more.

[0118] The polysiloxane (A) may be a hydrolysis condensation product of a hydrolyzable silane containing a silane compound other than the above-mentioned examples, or a modified product thereof, as long as the effects of the present invention are not impaired.

[0119] As described above, the polysiloxane [A] can be a modified product in which at least a portion of the silanol groups of the hydrolysis condensate have been modified. For example, a modified product in which some of the silanol groups have been alcohol-modified or acetal-protected can be used. Examples of the modified polysiloxane include a reaction product obtained by reacting at least a portion of the silanol groups of the hydrolysis condensate of the hydrolyzable silane with hydroxy groups of an alcohol, a dehydration reaction product of the condensate with an alcohol, and a modified product in which at least a portion of the silanol groups of the condensate have been protected with acetal groups.

[0120] The alcohol may be a monohydric alcohol, such as methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, or 1-hexanol. Examples of suitable alcohols include 2-methyl-1-pentanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, and cyclohexanol. Further, for example, alkoxy group-containing alcohols such as 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), and propylene glycol monobutyl ether (1-butoxy-2-propanol) can be used.

[0121] The reaction between the silanol groups of the hydrolysis condensate and the hydroxyl groups of the alcohol can be carried out by contacting the hydrolysis condensate with the alcohol and reacting for 0.1 to 48 hours, for example, 24 hours, at a temperature of 40 to 160° C., for example, 60° C., to obtain a modified product in which the silanol groups are capped. In this case, the alcohol capping agent can be used as a solvent in the composition containing the polysiloxane.

[0122] Furthermore, a dehydration reaction product of a hydrolysis condensate of a hydrolyzable silane with an alcohol can be produced by reacting the hydrolysis condensate with an alcohol in the presence of an acid catalyst, capping the silanol groups with the alcohol, and removing the water produced by dehydration from the reaction system. The acid can be an organic acid having an acid dissociation constant (pKa) of -1 to 5, preferably 4 to 5. Examples of the acid include trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, and acetic acid, among others. Furthermore, the acid can have a boiling point of 70 to 160°C, such as trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid. Thus, the acid preferably has an acid dissociation constant (pKa) of 4 to 5 or a boiling point of 70 to 160°C. That is, either a weak acidity or a strong acidity but a low boiling point can be used. The acid can have any properties, depending on the acid dissociation constant and boiling point.

[0123] Acetal protection of the silanol groups in the hydrolysis condensate can be achieved using a vinyl ether, for example, a vinyl ether represented by the following formula (5). By this reaction, a partial structure represented by the following formula (6) can be introduced into the polysiloxane.

[0124] In formula (5), R １ａ , R ２ａ , and R ３ａ each represents 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, and R ２ａ and R ４ａ may be bonded to each other to form a ring. Examples of the alkyl group include those mentioned above. In formula (6), R １ ', R ２ ', and R ３ Each of R ′ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; ４ ' represents an alkyl group having 1 to 10 carbon atoms, and R ２ ' and R ４In formula (6), * indicates a bond to an adjacent atom. The adjacent atom may be, for example, an oxygen atom of a siloxane bond, an oxygen atom of a silanol group, or R in formula (1). １ Examples of the alkyl group include the carbon atoms derived from the following.

[0125] Examples of the vinyl ether represented by formula (5) include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, and cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran. In particular, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, and 2,3-dihydrofuran are preferably used.

[0126] Acetal protection of the silanol groups can be carried out using the hydrolysis condensate, a vinyl ether, and an aprotic solvent such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, or 1,4-dioxane, and using a catalyst such as pyridium paratoluenesulfonate, trifluoromethanesulfonic acid, paratoluenesulfonic acid, methanesulfonic acid, hydrochloric acid, or sulfuric acid.

[0127] The capping of the silanol groups with an alcohol or the acetal protection may be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silane described below.

[0128] The weight-average molecular weight of the hydrolyzed condensate of hydrolyzable silane or its modified product can be, for example, 500 to 1,000,000. From the viewpoint of suppressing precipitation of the hydrolyzed condensate or its modified product in the composition, the weight-average molecular weight can be preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of achieving both storage stability and coatability, the weight-average molecular weight can be preferably 700 or more, more preferably 1,000 or more. The weight-average molecular weight is the molecular weight obtained by GPC analysis in terms of polystyrene. The GPC analysis can be performed using, for example, a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, tetrahydrofuran as an eluent (elution solvent), a flow rate (flow rate) of 1.0 mL / min, and polystyrene (Shodex (registered trademark) manufactured by Showa Denko K.K.) as a standard sample.

[0129] The hydrolysis condensate of hydrolyzable silane can be obtained by hydrolyzing and condensing the aforementioned silane compound (hydrolyzable silane). The aforementioned silane compound (hydrolyzable silane) contains an alkoxy group, aralkyloxy group, acyloxy group, or halogen atom directly bonded to a silicon atom, i.e., an alkoxysilyl group, aralkyloxysilyl group, acyloxysilyl group, or halogenated silyl group (hereinafter referred to as a hydrolyzable group). To hydrolyze these hydrolyzable groups, typically 0.1 to 100 moles, for example, 0.5 to 100 moles, and preferably 1 to 10 moles, of water are used per mole of hydrolyzable group. During the hydrolysis and condensation, a hydrolysis catalyst may be used, or the hydrolysis and condensation may be carried out without the use of a hydrolysis catalyst, for example, to promote the reaction. When a hydrolysis catalyst is used, typically 0.0001 to 10 moles, preferably 0.001 to 1 mole, of the hydrolysis catalyst can be used per mole of hydrolyzable group. The reaction temperature during hydrolysis and condensation is usually in the range of room temperature or higher and the reflux temperature at normal pressure of the organic solvent that can be used for hydrolysis, and can be, for example, 20 to 110°C, or, for example, 20 to 80°C. The hydrolysis may be complete, i.e., all hydrolyzable groups are converted to silanol groups, or partial, i.e., unreacted hydrolyzable groups may remain. Examples of hydrolysis catalysts that can be used during hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0130] Examples of metal chelate compounds as hydrolysis catalysts include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-i-propoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, di -i-propoxy bis(acetylacetonate)titanium, di-n-butoxy bis(acetylacetonate)titanium, di-sec-butoxy bis(acetylacetonate)titanium, di-t-butoxy bis(acetylacetonate)titanium, monoethoxy tris(acetylacetonate)titanium, mono-n-propoxy tris(acetylacetonate)titanium, mono-i-propoxy tris(acetylacetonate)titanium, mono-n-butoxy tris(acetylacetonate)titanium, mono-sec-butoxy tris(acetylacetonate) titanium acetate), mono-t-butoxy tris(acetylacetonate) titanium, tetrakis(acetylacetonate) titanium, triethoxy mono(ethylacetoacetate) titanium, tri-n-propoxy mono(ethylacetoacetate) titanium, tri-i-propoxy mono(ethylacetoacetate) titanium, tri-n-butoxy mono(ethylacetoacetate) titanium, tri-sec-butoxy mono(ethylacetoacetate) titanium, tri-t-butoxy mono(ethylacetoacetate) titanium, diethoxy bis(ethoxy di-n-propoxy bis(ethylacetoacetate) titanium, di-i-propoxy bis(ethylacetoacetate) titanium, di-n-butoxy bis(ethylacetoacetate) titanium, di-sec-butoxy bis(ethylacetoacetate) titanium, di-t-butoxy bis(ethylacetoacetate) titanium, monoethoxy tris(ethylacetoacetate) titanium, mono-n-propoxy tris(ethylacetoacetate) titanium, mono-i-propoxy tris(ethylacetoacetate) titanium,Titanium chelate compounds such as mono-n-butoxy tris(ethylacetoacetate)titanium, mono-sec-butoxy tris(ethylacetoacetate)titanium, mono-t-butoxy tris(ethylacetoacetate)titanium, tetrakis(ethylacetoacetate)titanium, mono(acetylacetonate)tris(ethylacetoacetate)titanium, bis(acetylacetonate)bis(ethylacetoacetate)titanium, and tris(acetylacetonate)mono(ethylacetoacetate)titanium; triethoxy mono(acetylacetonate) tri-n-propoxy mono(acetylacetonate) zirconium, tri-i-propoxy mono(acetylacetonate) zirconium, tri-n-butoxy mono(acetylacetonate) zirconium, tri-sec-butoxy mono(acetylacetonate) zirconium, tri-t-butoxy mono(acetylacetonate) zirconium, diethoxy bis(acetylacetonate) zirconium, di-n-propoxy bis(acetylacetonate) zirconium, di-i-propoxy bis(acetylacetonate) zirconium cetylacetonate) zirconium, di-n-butoxy bis(acetylacetonate) zirconium, di-sec-butoxy bis(acetylacetonate) zirconium, di-t-butoxy bis(acetylacetonate) zirconium, monoethoxy tris(acetylacetonate) zirconium, mono-n-propoxy tris(acetylacetonate) zirconium, mono-i-propoxy tris(acetylacetonate) zirconium, mono-n-butoxy tris(acetylacetonate) zirconium, mono-sec- Butoxy tris(acetylacetonate)zirconium, mono-t-butoxy tris(acetylacetonate)zirconium, tetrakis(acetylacetonate)zirconium, triethoxy mono(ethylacetoacetate)zirconium, tri-n-propoxy mono(ethylacetoacetate)zirconium, tri-i-propoxy mono(ethylacetoacetate)zirconium, tri-n-butoxy mono(ethylacetoacetate)zirconium, tri-sec-butoxy mono(ethylacetoacetate)zirconium,Tri-t-butoxy mono(ethylacetoacetate)zirconium, diethoxy bis(ethylacetoacetate)zirconium, di-n-propoxy bis(ethylacetoacetate)zirconium, di-i-propoxy bis(ethylacetoacetate)zirconium, di-n-butoxy bis(ethylacetoacetate)zirconium, di-sec-butoxy bis(ethylacetoacetate)zirconium, di-t-butoxy bis(ethylacetoacetate)zirconium, monoethoxy tris(ethylacetoacetate)zirconium, mono-n-propoxy tris(ethylacetoacetate)zirconium, mono-i-propoxy tris(ethylacetoacetate)zirconium, mono-n-butoxy Examples of the chelate compounds include, but are not limited to, zirconium chelate compounds such as tris(ethylacetoacetate)zirconium, mono-sec-butoxy tris(ethylacetoacetate)zirconium, mono-t-butoxy tris(ethylacetoacetate)zirconium, tetrakis(ethylacetoacetate)zirconium, mono(acetylacetonato)tris(ethylacetoacetate)zirconium, bis(acetylacetonato)bis(ethylacetoacetate)zirconium, and tris(acetylacetonato)mono(ethylacetoacetate)zirconium; and aluminum chelate compounds such as tris(acetylacetonato)aluminum and tris(ethylacetoacetate)aluminum.

[0131] Examples of organic acids that can be used as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butanoic acid, pentanoic 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, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

[0132] Examples of inorganic acids that can be used as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0133] Examples of organic bases as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicycloctane, diazabicyclononane, diazabicyclondecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide.

[0134] Examples of inorganic bases as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and the like.

[0135] Of these catalysts, metal chelate compounds, organic acids and inorganic acids are preferred, and these may be used alone or in combination of two or more.

[0136] Among these, in the present invention, nitric acid can be preferably used as the hydrolysis catalyst. The use of nitric acid can improve the storage stability of the reaction solution after hydrolysis and condensation, and in particular, can suppress changes in the molecular weight of the hydrolysis condensate or its modified product. It has been found that the stability of the hydrolysis condensate or its modified product in the solution depends on the pH of the solution. As a result of extensive investigation, it has been found that the pH of the solution falls within a stable range when an appropriate amount of nitric acid is used. Furthermore, as described above, nitric acid can also be used when obtaining a modified product of the hydrolysis condensate, for example, when capping silanol groups with alcohol, and is therefore preferred from the viewpoint of being able to contribute to both the hydrolysis and condensation of hydrolyzable silanes and the alcohol capping of the hydrolysis condensate.

[0137] When carrying out the hydrolysis and condensation, an organic solvent may be used as the solvent, and specific examples thereof include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-propylbenzene, and the like. Aromatic hydrocarbon solvents such as butylbenzene, triethylbenzene, di-i-propylbenzene, and n-amylnaphthalene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, and 2-ethylbutanol , n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, Monoalcohol-based solvents such as phenylmethylcarbinol, diacetone alcohol, and cresol; and polyhydric alcohol-based solvents such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 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, and glycerin;Ketone solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, and ethylene glycol dibutyl ether-based solvents such as ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-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, and 2-methyltetrahydrofuran;Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl 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 mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol acetate Examples of solvents include, but are not limited to, ester-based solvents such as methyl ether, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglyceride, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These solvents can be used alone or in combination of two or more. ;

[0138] After completion of the hydrolysis and condensation reactions, the reaction solution can be used as is or after dilution or concentration, neutralized, and treated with an ion exchange resin to remove the hydrolysis catalyst, such as an acid or a base, used in the hydrolysis and condensation. Before or after such treatment, by-product alcohol and water, the hydrolysis catalyst, etc., can be removed from the reaction solution by vacuum distillation or the like.

[0139] The hydrolysis condensate or modified product thereof (hereinafter also referred to as polysiloxane) obtained in this manner is obtained in the form of a polysiloxane varnish dissolved in an organic solvent, which can be used directly in the preparation of a silicon-containing underlayer film-forming composition. That is, the reaction solution can be used as is (or diluted) in the preparation of a silicon-containing underlayer film-forming composition. At this time, the hydrolysis catalyst used in the hydrolysis and condensation, by-products, etc., may remain in the reaction solution as long as they do not impair the effects of the present invention. For example, the hydrolysis catalyst or the nitric acid used in alcohol-capping silanol groups may remain in the polymer varnish solution at approximately 100 ppm to 5,000 ppm. The obtained polysiloxane varnish may be subjected to solvent substitution or diluted with an appropriate solvent. If the storage stability of the obtained polysiloxane varnish is not poor, the organic solvent can be distilled off to achieve a film-forming component concentration of 100%. The film-forming component refers to the components of the composition excluding the solvent component. The organic solvent used for solvent substitution or dilution of the polysiloxane varnish may be the same as or different from the organic solvent used in the hydrolysis and condensation reaction of the hydrolyzable silane. This dilution solvent is not particularly limited, and one or more solvents may be selected and used as desired.

[0140] <Component [C]: Solvent> The solvent as the component [C] can be any solvent that can dissolve and mix with the component [A] and, if necessary, other components contained in the composition for forming a silicon-containing underlayer film, without any particular limitation.

[0141] The solvent [C] is preferably an alcohol-based solvent, more preferably an alkylene glycol monoalkyl ether that is an alcohol-based solvent, and even more preferably a propylene glycol monoalkyl ether. These solvents also serve as capping agents for the silanol groups in the hydrolysis condensate, so that the silicon-containing underlayer film-forming composition can be prepared from the solution obtained by preparing the polysiloxane [A] without the need for solvent substitution or the like. Examples of alkylene glycol monoalkyl ethers include 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, and propylene glycol monobutyl ether.

[0142] Specific examples of other solvents [C] include 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, 2-hydroxy-2-methyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 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, acetic acid Methyl, 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,Examples of the solvent include 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, and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

[0143] The silicon-containing underlayer film-forming composition of the present invention may contain water as a solvent. When water is contained as a solvent, the content of water can be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less, based on the total mass of the solvents contained in the composition.

[0144] [Strong Acidic Additive] The composition for forming a silicon-containing underlayer film contains 0 parts by mass or more and less than 2 parts by mass of a strong acidic additive per 100 parts by mass of the polysiloxane [A]. That is, embodiments of the composition for forming a silicon-containing underlayer film include those in which the content of the strong acidic additive is 0% by mass.

[0145] The strongly acidic additive may be a compound having a first acid dissociation constant in water of 1 or less. The strongly acidic additive may also be an acid generator, such as a photoacid generator. In the present invention, the strongly acidic additive may be an additive that decomposes into an acidic substance upon external stimulation (e.g., light, heat, etc.). Such an additive may be referred to as a latent strongly acidic additive. Typical examples of latent strongly acidic additives are thermal acid generators and photoacid generators.

[0146] Examples of the photoacid generator include onium salt compounds, sulfonimide compounds, disulfonyldiazomethane compounds, etc. Specific examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, and bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride. Specific examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide. Specific examples of disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane. Furthermore, examples of acid generators that can be used include thermal acid generators such as tetramethylammonium nitrate.

[0147] [Preparation of Composition for Forming Silicon-Containing Underlayer Film] The composition for forming a silicon-containing underlayer film can be produced by mixing the polysiloxane [A], the solvent [C], and, if other components are included, the other components. In this case, a solution containing the polysiloxane [A] may be prepared in advance, and this solution may be mixed with the solvent [C] and other components. Alternatively, the reaction solution used to prepare the polysiloxane [A] may be used as is to prepare the composition for forming a silicon-containing underlayer film. The order of mixing is not particularly limited. For example, the solvent [C] may be added to and mixed with the solution containing the polysiloxane [A], and the other components may then be added to the mixture. Alternatively, the solution containing the polysiloxane [A], the solvent [C], and the other components may be mixed simultaneously. If necessary, additional solvent [C] may be added at the end, or some components that are relatively soluble in the solvent [C] may be omitted from the mixture and added at the end. However, from the viewpoint of suppressing aggregation or separation of the constituent components and reproducibly preparing a composition with excellent uniformity, it is preferable to prepare a solution in which the polysiloxane [A] is well dissolved in advance and use this to prepare the composition. Note that the polysiloxane [A] may aggregate or precipitate when mixed with other components, depending on the type and amount of the solvent [C] to be mixed with them, as well as the amounts and properties of the other components. In addition, when preparing a composition using a solution in which the polysiloxane [A] is dissolved, it is also important to note that the concentration and amount of the solution of the polysiloxane [A] must be determined so that the desired amount of polysiloxane [A] is contained in the final composition. In preparing the composition, heating may be performed as appropriate within a range that does not cause the components to decompose or deteriorate.

[0148] In the present invention, the composition for forming a silicon-containing underlayer film may be filtered using a submicrometer-order filter or the like during the production process or after all components have been mixed. The type of material for the filter used here is not important, and examples that can be used include nylon filters and fluororesin filters.

[0149] The concentration of the solids 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, relative to the total mass of the composition. The solids refer to the total components of the composition excluding the solvent component [C]. The content of the polysiloxane [A] in the solids is typically 20% by mass to 100% by mass. However, from the viewpoint of reproducibly achieving the effects of the present invention, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and even more preferably 80% by mass, and the upper limit is preferably 99% by mass, with the remainder being made up of additives, as described below. The silicon-containing underlayer film-forming composition preferably has a pH of 2 to 5, more preferably 3 to 4.

[0150] As will be described later, the silicon-containing underlayer film-forming composition of the present invention can be suitably used as a composition for forming an underlayer film for forming a self-assembled pattern using directed self-assembly, in particular as a composition for forming an underlayer film provided as a lower layer of a neutral film that enhances the alignment of a self-assembled film.

[0151] [Other Additives] Various additives can be blended into the silicon-containing underlayer film-forming composition of the present invention, as long as they do not impair the effects of the present invention. Examples of the additives include curing catalysts (ammonium salts, phosphines, phosphonium salts, sulfonium salts, nitrogen-containing silane compounds, etc.), crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymer compounds, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc.), pH adjusters, metal oxides, rheology adjusters, adhesion promoters, and other known additives blended into materials (compositions) for forming various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, anti-reflective films, and pattern reversal films. Examples of various additives are listed below, but are not limited to these. As mentioned above, the silicon-containing underlayer film-forming composition of the present invention does not contain a strongly acidic additive. For example, compounds having a first acid dissociation constant of 1 or less in water and acid generators, particularly compounds that function as photoacid generators, are excluded from the various additives that can be blended into the composition of the present invention.

[0152] <Curing Catalyst> The silicon-containing underlayer film-forming composition of the present invention may contain a curing catalyst, or may be a composition that does not contain a curing catalyst. The curing catalyst may be an ammonium salt, a phosphine, a phosphonium salt, a sulfonium salt, or the like. The following salts, which are listed as examples of curing catalysts, may be added in the form of a salt, or may form a salt in the composition (a compound that is added as a separate compound and forms a salt in the system).

[0153] The ammonium salt is represented by the formula (D-1): (In the formula, m ａ is an integer from 2 to 11, n ａ is an integer of 2 or 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): (In the formula, R ２２ , R２３ , R ２４ and R ２５ represents an alkyl group or an aryl group, N represents a nitrogen atom, Y represents a － represents an anion, and R ２２ , R ２３ , R ２４ , and R ２５ are each bonded to a nitrogen atom), a quaternary ammonium salt having a structure represented by formula (D-3): (In the formula, R ２６ and R ２７ represents an alkyl group or an aryl group, N represents a nitrogen atom, Y represents a － represents an anion), a quaternary ammonium salt having a structure represented by formula (D-4): (In the formula, R ２８ represents an alkyl group or an aryl group, N represents a nitrogen atom, Y represents a － represents an anion), a quaternary ammonium salt having a structure represented by formula (D-5): (In the formula, R ２９ and R ３０ represents an alkyl group or an aryl group, N represents a nitrogen atom, Y represents a － represents an anion), a quaternary ammonium salt having a structure represented by formula (D-6): (In the formula, m ａ is an integer from 2 to 11, n ａ represents an integer of 2 or 3, H represents a hydrogen atom, N represents a nitrogen atom, Y － represents an anion).

[0154] The phosphonium salt may also be a compound represented by the formula (D-7): (In the formula, R ３１ , R ３２ , R ３３ , and R ３４ represents an alkyl group or an aryl group, P represents a phosphorus atom, Y represents a － represents an anion, and R ３１ , R ３２ , R ３３ , and R ３４ are each bonded to a phosphorus atom).

[0155] The sulfonium salt may also be a compound represented by the formula (D-8): (In the formula, R ３５ , R ３６ , and R ３７ represents 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 each bonded to a sulfur atom).

[0156] The compound of the above formula (D-1) is a quaternary ammonium salt derived from an amine, m ａ represents an integer from 2 to 11, and n ａ represents an integer of 2 or 3. R of this quaternary ammonium salt ２１ represents an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and examples thereof include linear alkyl groups such as ethyl, propyl, and butyl, as well as benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl groups. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － ) and the like.

[0157] The compound of the above formula (D-2) is R ２２ R ２３ R ２４ R ２５ N ＋ Y － The R of this quaternary ammonium salt is ２２ , R ２３ , R ２４ and R ２５is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － The quaternary ammonium salt is commercially available, and examples thereof include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0158] The compound of the above formula (D-3) is a quaternary ammonium salt derived from a 1-substituted imidazole, and R ２６ and R ２７ has 1 to 18 carbon atoms, and R ２６ and R ２７ The total number of carbon atoms in R is preferably 7 or more. ２６ represents a methyl group, an ethyl group, a propyl group, a phenyl group, or a benzyl group, R ２７ Examples of the anion (Y － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － Although this compound is commercially available, it can also be produced by reacting an imidazole compound such as 1-methylimidazole or 1-benzylimidazole with an alkyl halide or aryl halide such as benzyl bromide or methyl bromide.

[0159] The compound of the above formula (D-4) is a quaternary ammonium salt derived from pyridine, and 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. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － ) and other acid groups. This compound is commercially available, but can also be produced by reacting pyridine with an alkyl halide or aryl halide, such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0160] The compound of the above formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine, such as picoline, and R ２９ R 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, and a benzyl group. ３０ is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and in the case of a quaternary ammonium group derived from, for example, picoline, R ３０ is a methyl group. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ －), alcoholate (-O － ) and other acid groups. This compound is commercially available, but can also be produced by reacting a substituted pyridine such as picoline with an alkyl halide or aryl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, or benzyl bromide. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.

[0161] The compound of the above formula (D-6) is a tertiary ammonium salt derived from an amine, m ａ represents an integer from 2 to 11, and n ａ represents an integer of 2 or 3. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － The compound can be produced by reacting an amine with a weak acid such as a carboxylic acid or phenol. Examples of the carboxylic acid include formic acid and acetic acid. When formic acid is used, an anion (Y － ) is (HCOO － ) and when acetic acid is used, the anion (Y － ) is (CH ３ COO － ) When phenol is used, the anion (Y － ) is (C ６ H ５ O － )

[0162] The compound of the above formula (D-7) is R ３１ R ３２ R ３３ R ３４ P ＋ Y － It is a quaternary phosphonium salt having the structure: R ３１ , R３２ , R ３３ , and R ３４ is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, and preferably R ３１ ~R ３４ Three of the four substituents are phenyl groups or substituted phenyl groups, such as phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O － ) and other acid groups. This compound is commercially available, and examples thereof include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylbenzylphosphonium halides, tetraphenylphosphonium halides, tritolylmonoarylphosphonium halides, and tritolylmonoalkylphosphonium halides (all of which the halogen atom is a chlorine atom or a bromine atom). In particular, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide, tritolylmonoarylphosphonium halides such as tritolylmonophenylphosphonium halide, and tritolylmonoalkylphosphonium halides (the halogen atom is a chlorine atom or a bromine atom) are preferred.

[0163] Examples of phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0164] The compound of the above formula (D-8) is R ３５ R ３６ R ３７ S ＋ Y － It is a tertiary sulfonium salt having the structure: R ３５ , R ３６ , and R ３７ is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms, preferably R ３５ ~R ３７ Two of the three substituents are phenyl groups or substituted phenyl groups, such as phenyl groups and tolyl groups, and the remaining one is an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. － ) is a chloride ion (Cl － ), bromine ion (Br － ), iodine ion (I － ) and carboxylate ions (-COO － ), sulfonato (-SO ３ － ), alcoholate (-O －Examples of suitable acid groups include trialkylsulfonium halides such as tri-n-butylsulfonium halides and tri-n-propylsulfonium halides, dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halides, diphenylmonoalkylsulfonium halides such as diphenylmethylsulfonium halides and diphenylethylsulfonium halides, triphenylsulfonium halides (all of which the halogen atom is a chlorine atom or a bromine atom), trialkylsulfonium carboxylates such as tri-n-butylsulfonium carboxylate and tri-n-propylsulfonium carboxylate, dialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylate, diphenylmonoalkylsulfonium carboxylates such as diphenylmethylsulfonium carboxylate and diphenylethylsulfonium carboxylate, and triphenylsulfonium carboxylate. Furthermore, triphenylsulfonium halides and triphenylsulfonium carboxylates are preferably used.

[0165] In the present invention, a nitrogen-containing silane compound can be added as a curing catalyst, such as an imidazole ring-containing silane compound, such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0166] When a curing catalyst is used, its amount is 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, or 0.01 to 3 parts by mass, per 100 parts by mass of the polysiloxane (A).

[0167] <Stabilizer> The stabilizer may be added for purposes such as stabilizing the hydrolysis condensate of the hydrolyzable silane mixture. Specific examples of the stabilizer include organic acids, water, alcohols, and combinations thereof. Examples of the organic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. Among these, oxalic acid and maleic acid are preferred. When an organic acid is added, the amount added is 0.1 to 5.0% by mass relative to the mass of the hydrolysis condensate of the hydrolyzable silane mixture. These organic acids can also function as pH adjusters. Examples of the water that can be used include pure water, ultrapure water, and ion-exchanged water. When used, the amount added can be 1 to 20 parts by mass per 100 parts by mass of the silicon-containing underlayer film-forming composition. The alcohol is preferably one that easily evaporates (volatilizes) upon heating after application, such as methanol, ethanol, propanol, i-propanol, and butanol. When alcohol is added, the amount added can be 1 to 20 parts by mass per 100 parts by mass of the composition for forming the silicon-containing underlayer film.

[0168] <Organic Polymer> The organic polymer compound can be added to the silicon-containing underlayer film-forming composition to adjust the dry etching rate (amount of film thickness reduction per unit time), attenuation coefficient, refractive index, etc. of the film (underlayer film) formed from the composition. The organic polymer compound is not particularly limited and can be appropriately selected from various organic polymers (condensation polymerization polymers and addition polymerization polymers) depending on the purpose of addition. Specific examples include addition polymerization polymers and condensation polymerization polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate. In the present invention, organic polymers containing aromatic rings or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing moieties can also be suitably used when such a function is required. Specific examples of such organic polymer compounds include, but are not limited to, addition polymerization polymers containing, as structural units, addition-polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthrylmethyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide, and condensation polymerization polymers such as phenol novolac and naphthol novolac.

[0169] When an addition polymerization polymer is used as the organic polymer compound, the polymer compound may be either a homopolymer or a copolymer. An addition polymerizable monomer is used to produce the addition polymerization polymer, and specific examples of such addition polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0170] Specific examples of acrylic acid ester compounds include methyl acrylate, ethyl acrylate, normal hexyl acrylate, i-propyl 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-hydroxynorbornene-2-carboxylic-6-lactone, 3-acryloxypropyltriethoxysilane, glycidyl acrylate, and the like, but are not limited to these.

[0171] Specific examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, normal hexyl methacrylate, i-propyl 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-hydroxynorbornene-2-carboxylic-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, and the like, but are not limited to these.

[0172] Specific examples of the acrylamide compound include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthrylacrylamide.

[0173] Specific examples of methacrylamide compounds include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthrylmethacrylamide, but are not limited to these.

[0174] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetate, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, and vinylanthracene.

[0175] Specific examples of styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0176] Examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0177] When a condensation polymerization polymer is used as the polymer, examples of such a polymer include a condensation polymerization polymer of a glycol compound and a dicarboxylic acid compound. Examples of glycol compounds include diethylene glycol, hexamethylene glycol, butylene glycol, etc. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, maleic anhydride, etc. Examples of polyesters, polyamides, and polyimides such as polypyromellitimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate, but are not limited to these. When the organic polymer compound contains a hydroxy group, this hydroxy group may undergo a crosslinking reaction with a hydrolysis condensate or the like.

[0178] The weight-average molecular weight of the organic polymer compound can usually be 1,000 to 1,000,000. When an organic polymer compound is incorporated, from the viewpoint of suppressing precipitation in the composition while fully obtaining the functional effect of the polymer, the weight-average molecular weight can be, for example, 3,000 to 300,000, or 5,000 to 300,000, or 10,000 to 200,000. Such organic polymer compounds may be used alone or in combination of two or more.

[0179] When the composition for forming a silicon-containing underlayer film of the present invention contains an organic polymer compound, its content cannot be generally defined because it is determined appropriately in consideration of the function and the like of the organic polymer compound. However, it can usually be in the range of 1 to 200% by mass relative to the mass of the polysiloxane (A). From the viewpoint of suppressing precipitation in the composition, it can be, for example, 100% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less. From the viewpoint of fully obtaining the effect, it can be, for example, 5% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more.

[0180] <Surfactant> The surfactant is effective in suppressing the occurrence of pinholes, striations, etc. when the silicon-containing underlayer film-forming composition is applied to a substrate. Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, and UV-curable surfactants. More specifically, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan trioleate; Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as oleate and polyoxyethylene sorbitan tristearate, trade names of EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Tochem Products Co., Ltd.)), trade names of MEGAFAC (registered trademark) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation), Fluorad F Examples of suitable surfactants include, but are not limited to, fluorine-based surfactants such as C430 and FC431 (manufactured by 3M Japan Ltd.), Asahiguard (registered trademark) AG710 (manufactured by AGC Corporation), and Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants can be used singly or in combination of two or more.

[0181] When the composition for forming a silicon-containing underlayer film of the present invention contains a surfactant, the content thereof is usually 0.0001 to 5 mass %, preferably 0.001 to 4 mass %, and more preferably 0.01 to 3 mass %, relative to the mass of the polysiloxane (A).

[0182] <Rheology Modifier> The rheology modifier is added primarily to improve the fluidity of the silicon-containing underlayer film-forming composition and to enhance the film thickness uniformity of the formed film, particularly during the baking process. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, di-i-butyl phthalate, dihexyl phthalate, and butyl i-decyl phthalate; adipic acid derivatives such as di-n-butyl adipate, di-i-butyl adipate, di-i-octyl adipate, and octyldecyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate. When these rheology modifiers are used, the amount added is typically less than 30% by mass based on the total solids content of the silicon-containing underlayer film-forming composition.

[0183] <Adhesion Aid> The adhesion aid is added mainly for the purpose of improving the adhesion between a film (neutral film, brush film, etc.) provided on a substrate or an upper layer and a film (underlayer film) formed from the silicon-containing underlayer film-forming composition. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; γ-chloropropyltrimethoxysilane; Examples of such adhesion promoters include other silanes such as γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine, and urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea. When such adhesion promoters are used, the amount added is usually less than 5% by mass, and preferably less than 2% by mass, based on the total solids content of the composition for forming a silicon-containing underlayer film.

[0184] <pH Adjuster> In addition to the acids having one or more carboxylic acid groups, such as the organic acids listed above as the <Stabilizer>, bisphenol S or a bisphenol S derivative can be added as a pH adjuster. When a pH adjuster is used, the amount added can be 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass per 100 parts by mass of the polysiloxane [A].

[0185] Specific examples of bisphenol S and bisphenol S derivatives include, but are not limited to, compounds represented by the following formulae (C-1) to (C-23).

[0186] <Metal Oxide> Examples of metal oxides that can be added to the silicon-containing underlayer film-forming composition of the present invention include, but are not limited to, oxides of one or a combination of two or more of metals such as tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten), and semimetals such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0187] [Method for manufacturing a substrate having a self-assembled pattern] The present invention also relates to a method for forming a self-assembled pattern using the above-mentioned silicon-containing underlayer film-forming composition, and particularly to a method for manufacturing a substrate having a self-assembled pattern by directed self-assembly (DSA). In this 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 invention.

[0188] An example of a method for producing a substrate having a self-assembled pattern includes the steps of: forming an underlayer film on a substrate using the silicon-containing underlayer film-forming composition of the present invention; and forming a self-assembled film above the underlayer film to form a self-assembled pattern.

[0189] Another example of the method for producing a substrate having a self-assembled pattern includes the steps of: forming an underlayer film on a substrate using the silicon-containing underlayer film-forming composition of the present invention; forming a neutral film on the underlayer film; and forming a self-assembled film on the neutral film to form a self-assembled pattern.

[0190] Another example of the method for manufacturing a substrate having a self-assembled pattern includes the steps of: forming an underlayer film on a substrate using the silicon-containing underlayer film-forming composition of the present invention; forming a neutral film on a portion of the underlayer film; forming a brush film on the underlayer film where the neutral film is not formed, and forming a template film for the self-assembled pattern formed from the neutral film and the brush film; and forming a self-assembled film on the template film for the self-assembled pattern, thereby obtaining a self-assembled pattern.

[0191] Another example of the method for manufacturing a substrate having a self-assembled pattern includes the steps of: forming an organic underlayer film on a substrate; forming an underlayer film on the organic underlayer film using the silicon-containing underlayer film-forming composition of the present invention; forming a neutral film on a portion of the underlayer film; forming a brush film on the underlayer film where the neutral film is not formed, and forming a template film for the self-assembled pattern formed from the neutral film and the brush film; and forming a self-assembled film on the template film for the self-assembled pattern, thereby obtaining a self-assembled pattern.

[0192] Another example of a method for manufacturing a substrate having a self-assembled pattern includes the steps of: forming an organic underlayer film on a substrate; forming an underlayer film on the organic underlayer film using the silicon-containing underlayer film-forming composition of the present invention; forming a neutral film on the underlayer film; forming a resist film on the neutral film; exposing and developing the resist film to obtain a resist pattern; etching the neutral film using the resist pattern as a mask; etching or stripping the resist pattern to obtain a patterned neutral film on the underlayer film; forming a brush film on the underlayer film and the patterned neutral film on the underlayer film; etching or stripping the brush film on the patterned neutral film to expose the neutral film and form a template film for the self-assembled pattern composed of the neutral film and the brush film; and forming a self-assembled film on the template film for the self-assembled pattern to obtain a self-assembled pattern.

[0193] The method for producing a substrate having a self-assembled pattern includes the steps of forming an underlayer film on a substrate using the silicon-containing underlayer film-forming composition of the present invention, and forming a self-assembled film as a layer above the underlayer film, thereby forming a self-assembled pattern (a pattern structure forming a self-assembled film, i.e., also referred to as a microphase-separated structure).

[0194] In a preferred embodiment, a neutralization treatment is performed on the layer on which the self-assembled film is to be formed (e.g., on the underlayer film), followed by the formation of a self-assembled film and a self-assembled pattern. In this technical field, neutralization refers to a treatment that modifies the surface of a substrate or the like on which the self-assembled film is to be formed so that it has affinity with all of the polymers that make up the block copolymer of the self-assembled film. Neutralization treatment can prevent only a phase consisting of a specific polymer from coming into contact with the surface of the substrate or the like due to phase separation. This neutralization treatment is important for forming cylindrical structures, dot structures, gyroid structures, and the like that are freely oriented on the substrate surface through phase separation. Specifically, the neutralization treatment can be performed by forming a thin film (neutral film) containing a primer that has affinity with all of the polymers that make up the block copolymer on the surface of the substrate or the like on which the self-assembled film is to be formed.

[0195] When forming a self-assembled pattern, a change in surface energy (hydrophilicity / hydrophobicity) is utilized to pattern the block copolymer into a cylindrical shape, i.e., when the above-mentioned neutral film is used, it is preferable that the water contact angle value of the polymer in the neutral film be a value between the water contact angle values ​​of each polymer chain that constitutes the block copolymer in the self-assembled film.

[0196] In the present invention, before the self-assembled film is formed, a neutral film capable of storing pattern information can be formed by electron beam lithography or laser irradiation. Furthermore, prior to the formation of the self-assembled film, lithography using a resist may be performed, or lithography can be performed without using a resist. When the block copolymer itself has the ability to form a pattern by self-assembly, a resist may not necessarily be required to utilize this effect.

[0197] In the present invention, for example, a silicon-containing underlayer film is formed on a substrate from the silicon-containing underlayer film-forming composition of the present invention, a neutral film is formed thereon, and a self-assembled film is formed thereon, thereby forming a pattern using the self-assembled film. The self-assembled film can be applied along a predetermined pattern guide, and this pattern guide can be formed using photolithography techniques. The self-assembled film self-assembled along the pattern guide has some parts that are preferentially removed by a developer, etching gas, etc., and some parts that are not removed, depending on the type of unit structure in the polymer chains that make up the self-assembled film. The parts that are to be removed can be selectively removed to reduce the pattern width (shrink) or form sidewalls.

[0198] Furthermore, when the neutral film is patterned, a brush material can be applied to eliminate the step between the patterned neutral film and the exposed underlayer (silicon-containing underlayer film) after pattern removal and to control hydrophilicity and hydrophobicity. The brush material is provided so that a self-assembled pattern does not appear in unintended areas. That is, by embedding the brush material in the exposed underlayer (silicon-containing underlayer film) after pattern removal, a template film for a self-assembled pattern composed of the patterned neutral film and the brush film can be formed.

[0199] The method for producing a substrate having a self-assembled pattern using the silicon-containing underlayer film, neutral film, and brush film can be embodied in the following manner: That is, the method can include the steps of forming an underlayer film on a substrate using a silicon-containing underlayer film-forming composition, forming a neutral film on a portion of the underlayer film, forming a brush film on the underlayer film on which the neutral film is not formed, and forming a template film for the self-assembled pattern formed from the neutral film and the brush film, and forming a self-assembled film on the template film for the self-assembled pattern to obtain a self-assembled pattern.

[0200] Furthermore, an organic underlayer film can be formed under the underlayer film (silicon-containing underlayer film). Also, a resist pattern can be used to form a neutral film on a portion of the underlayer film, i.e., to form a patterned neutral film. Such an embodiment can include the steps of: forming an organic underlayer film on a substrate; forming an underlayer film on the organic underlayer film using a silicon-containing underlayer film-forming composition; forming a neutral film on the underlayer film; forming a resist film on the neutral film; exposing and developing the resist film to obtain a resist pattern; etching the neutral film using the resist pattern as a mask; etching or stripping the resist pattern to obtain a patterned neutral film on the underlayer film; forming a brush film on the underlayer film and the patterned neutral film on the underlayer film; etching or stripping the brush film on the patterned neutral film to expose the neutral film and form a template film for a self-assembled pattern composed of the neutral film and the brush film; and forming a self-assembled film on the template film for the self-assembled pattern to obtain a self-assembled pattern.

[0201] An example of the method for manufacturing a substrate having a self-assembled pattern (self-assembled pattern formation method) of the present invention will be described below with reference to the drawings. FIGS. 1A to 1J are diagrams illustrating an example of the method for manufacturing a substrate having a self-assembled pattern (self-assembled pattern formation method) of the present invention. An underlayer film 2 is formed on a substrate 1 using a silicon-containing underlayer film-forming composition of the present invention ( FIG. 1A ). Next, a neutral film 3 is formed on the underlayer film 2 ( FIG. 1B ). Next, a resist film 4 is formed on the neutral film 3 ( FIG. 1C ). Next, the resist film 4 is irradiated with light or an electron beam, and then the resist film 4 is developed to obtain a resist pattern (patterned resist film 4) ( FIG. 1D ). 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 ( FIG. 1E ). Next, the resist pattern (patterned resist film 4) is removed ( FIG. 1F ). Next, a brush film 5 is formed on the underlayer film 2 and the patterned neutral film 3 ( FIG. 1G ). Next, a portion of the brush film 5 is removed, forming the brush film 5 in the gaps in the pattern of the patterned neutral film 3 (FIG. 1H). This forms a template film 11 for the self-assembly pattern, consisting of the neutral film 3 and the brush film 5. Next, a self-assembled film 6 is formed on the template film 11 for the self-assembly pattern. The self-assembled film 6 is, for example, a film of a block copolymer having an A block and a B block. By phase-separating the self-assembled film 6, a microphase-separated structure having domains 6a of the A block and domains 6b of the B block is obtained (FIG. 1I). By selectively removing a portion of the microphase-separated self-assembled film 6 (for example, domains 6b of the B block), a pattern corresponding to the morphology of the microphase-separated domains is obtained (FIG. 1J).

[0202] <Formation of Underlayer Film (Silicon-Containing Underlayer Film)> First, the silicon-containing underlayer film-forming composition of the present invention is applied to a substrate used in the manufacture of precision integrated circuit devices (e.g., 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 alkali-free glass, low-alkali glass, and crystallized glass), a glass substrate formed with an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film, a plastic (polyimide, PET, etc.) substrate, a low-dielectric constant material (low-k material)-coated substrate, a flexible substrate, etc.) by a suitable application method such as a spinner or coater, and then baked using a heating means such as a hot plate to harden the composition and form an underlayer film. Baking conditions are appropriately selected from a baking temperature of 40°C to 400°C or 80°C to 250°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 150° C. to 250° C. and the baking time is 0.5 minutes to 2 minutes. The thickness of the underlayer film formed here is, for example, 10 nm to 1,000 nm, or 20 nm to 500 nm, or 50 nm to 300 nm, or 100 nm to 200 nm, or 10 to 150 nm.

[0203] <Formation of Organic Underlayer Film> In the present invention, an organic underlayer film may be formed on the substrate, and then the underlayer film may be formed thereon. The organic underlayer film used here is not particularly limited, and any organic underlayer film commonly used in lithography processes may be selected and used. The organic underlayer film is formed by applying the organic underlayer film-forming composition described below to the substrate by the appropriate application method described above, and then baking and curing the applied composition. The thickness of the organic underlayer film formed on the substrate can be adjusted as needed, but may be, for example, 0.01 to 30 μm.

[0204] <Organic Underlayer Film-Forming Composition (SOC Composition)> The organic underlayer film-forming composition may contain an organic underlayer film-forming compound (SOC compound) and a solvent, and may further contain various additives, such as a crosslinker, an acid or acid generator (thermal acid generator, photoacid generator), a rheology modifier, an adhesion aid, and a surfactant, as necessary. Examples of the organic underlayer film-forming compound (SOC compound) include, but are not limited to, the compounds and polymers described below. The solvent is not particularly limited as long as it can dissolve or disperse the organic underlayer film-forming compound (SOC compound) and other components described below. For example, the solvents listed above as the solvent [C] can be used appropriately. The solids content of the organic underlayer film-forming composition may be, for example, 0.1 to 70% by mass, or 0.1 to 60% by mass. Here, the solids content refers to the total components of the organic underlayer film-forming composition excluding the solvent component. The proportion of the organic underlayer film-forming compound in the solid content can be, for example, 1 to 100% by mass, 1 to 99.9% by mass, or 50 to 99.9% by mass.

[0205] <<Organic Underlayer Film-Forming Compound (SOC Compound)>> Examples of compounds that form the organic underlayer film include, but are not limited to, organic underlayer film-forming compound 1 (SOC1 compound) to organic underlayer film-forming compound 28 (SOC28 compound) shown below.

[0206] <<Organic Underlayer Film-Forming Compound 1>> As the organic underlayer film-forming compound 1 (SOC1 compound), for example, the compounds listed in WO 2010 / 147155 (Japanese Patent No. 5641253) and WO 2012 / 077640 (Japanese Patent No. 5867732) can be used. The entire disclosures of WO 2010 / 147155 (Japanese Patent No. 5641253) and WO 2012 / 077640 are incorporated herein by reference. Specific examples include polymers containing a unit structure represented by the following formula (SOC1-1). Note that, unless otherwise specified, the symbols and definitions of the groups in formula (SOC1-1) defined below are limited to the description in formula (SOC1-1), i.e., <<Organic Underlayer Film-Forming Compound 1>>.

[0207] [In formula (SOC1-1), R １ and R ２ are each selected from the group consisting of a hydrogen atom, a halogen atom, a nitro group, an amino group, a hydroxy 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 combinations thereof, and the alkyl group, the alkenyl group, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; R ３ is selected from the group consisting of 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 combinations thereof, and the alkyl group, the alkenyl group, or the aryl group may contain an ether bond, a ketone bond, or an ester bond; R ４ represents a hydrogen atom, or an aryl or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxy group; R ５ represents 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 may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxy group, and R ４ and R ５ may form a ring together with the carbon atom to which they are attached, and n1 and n2 are each an integer of 1 to 3.

[0208] <<Organic Underlayer Film-Forming Compound 2>> As the organic underlayer film-forming compound 2 (SOC2 compound), for example, compounds listed in WO 2022 / 030468, WO 2022 / 030469, and WO 2013 / 047516 (Patent No. 6066092) can be used. The entire disclosures of WO 2022 / 030468, WO 2022 / 030469, and WO 2013 / 047516 (Patent No. 6066092) are incorporated herein by reference. Specifically, for example, a polymer containing a unit structure represented by the following formula (SOC2-1) and / or a unit structure represented by the formula (SOC2-2) can be mentioned. Unless otherwise specified, the symbols and definitions of the groups in formulas (SOC2-1) and (SOC2-2) defined below are limited only to the descriptions in formulas (SOC2-1) and (SOC2-2), i.e., <<Organic Underlayer Film-Forming Compound 2>>.

[0209] [In the formula, Ar １ , and Ar ２ represents a benzene ring or a naphthalene ring, and 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 may contain a nitrogen atom, R １ , and R ２ are Ar １ , and Ar ２ is a group that substitutes a hydrogen atom on the ring of the formula (I), and is selected from the group consisting of a halogen atom, a nitro group, an amino group, a cyano group, a hydroxy 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 combinations thereof, and the alkyl group, the alkenyl group, the alkenyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; R ３ , and R ８are each selected from the group consisting of 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 combinations thereof, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond, and the aryl group may be substituted with an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group; R ４ , and R ６ are each selected from the group consisting of 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 are optionally 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 carboxy group, or a hydroxy group, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; R ５ , and R ７ are each selected from the group consisting of 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 are optionally substituted with a halogen atom, a nitro group, an amino group, a cyano group, a hydroxy 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, or an aryl group having 6 to 40 carbon atoms, and the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may contain an ether bond, a ketone bond, or an ester bond; and R ４ and R ５ and R ６ and R ７may each form a ring together with the carbon atom to which they are attached, n1 and n2 are each an integer of 0 to 3, n3 is 1 or more, and Ar ３ n4 is an integer equal to or smaller than the number of substituents that can be substituted by R ８ is Ar ３ It bonds to the nitrogen atom contained in

[0210] <<Organic Underlayer Film-Forming Compound 3>> The compounds listed in WO 2017 / 154921 can be used as organic underlayer film-forming compound 3 (SOC3 compound). The entire disclosure of WO 2017 / 154921 is incorporated herein by reference. Specific examples include compounds containing partial structure (I) and partial structure (II) shown below. Partial structure (I) is at least one partial structure selected from the group consisting of partial structures represented by formulas (SOC3-1-1) to (SOC3-1-5) below, or a partial structure consisting of a combination of a partial structure represented by formula (SOC3-1-6) and a partial structure represented by formula (SOC3-1-7) or formula (SOC3-1-8), and partial structure (II) can be a partial structure represented by formula (SOC3-2-1) or formula (SOC3-2-2) below. Unless otherwise specified, the symbols and definitions of groups in formulas (SOC3-1-1) to (SOC3-1-8) and formulas (SOC3-2-1) to (SOC3-2-2) defined below are limited only to the descriptions in these formulas, i.e., <<Organic Underlayer Film-Forming Compound 3>>.

[0211] [In the formula, R １ , R １ａ , R ３ , R ５ , R ５ａ , and R ６ａ each represents 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 group consisting of a combination thereof; R ２ , R ２ａ , R ４ , and R ６each represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, an unsaturated hydrocarbon group having 2 to 10 carbon atoms, an oxygen atom, a carbonyl group, an amide group, an amino group, or a group consisting of a combination thereof; R ２ , R ２ａ , R ４ , R ６ represents a monovalent group, R １ , R １ａ , R ３ , R ５ａ , and R ６ａ represents a divalent group, R ５ represents a trivalent group, and R ７ , R ８ , R ９ , R １０ and R １１ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, n represents the number of repeating units from 1 to 10, and dotted lines represent chemical bonds with adjacent atoms.]

[0212] <<Organic Underlayer Film-Forming Compound 4>> As the organic underlayer film-forming compound 4 (SOC4 compound), for example, the compounds listed in WO 2018 / 186310 can be used. The entire disclosure of WO 2018 / 186310 is incorporated herein by reference. Specific examples include polymers having a unit structure represented by the following formula (SOC4-1). Note that, unless otherwise specified, the symbols and definitions of groups in formulas (SOC4-1) and (SOC4-2) defined below are limited to the descriptions in formulas (SOC4-1) and (SOC4-2), i.e., <<Organic Underlayer Film-Forming Compound 4>>.

[0213] [In formula (SOC4-1), A １ , A ２ and A ３ each independently represents an aromatic ring having 6 to 100 carbon atoms which may contain a heteroatom, or a hydrocarbon group containing an aromatic ring having 6 to 100 carbon atoms which may contain a heteroatom; B １ , B ２ and B ３ are each independently represented by the formula (SOC4-2):

[0214] (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, alkenylene group, alkynylene group and arylene group may be optionally substituted with one or more cyano groups and / or one 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 consisting of a combination thereof, R ａ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and 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 １ , A ２ , or A ３ ) and X represents a carbonyl group, a sulfonyl group, or a bond with -CR ２ ２ - group (R ２ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) or —C(CF ３ ) ２ represents a - group, n1 is an integer satisfying 1≦n1≦4, n2 is an integer satisfying 0≦n2≦4, and n3 is an integer satisfying 0≦n3≦4, and n1+n2+n3=an integer of 1 to 12.]

[0215] Examples of organic underlayer film-forming compound 4 include polymers containing a unit structure represented by formula (SOC4-3) below in addition to the unit structure represented by formula (SOC4-1) above. Note that, unless otherwise specified, the symbols and definitions of groups in formula (SOC4-3) defined below are limited to the descriptions in formula (SOC4-3), i.e., <<Organic underlayer film-forming compound 4>>.

[0216] [In formula (SOC4-3), A ４ and A ５each represents an aromatic ring having 6 to 48 carbon atoms which may contain a heteroatom, or a hydrocarbon group containing an aromatic ring having 6 to 48 carbon atoms which may contain a heteroatom; B ４ and B ５ is B in the above formula (SOC4-1) １ , B ２ and B ３ represents a group similar to the above, n4 is an integer satisfying 1≦n4≦4, n5 is an integer satisfying 0≦n5≦4, and n4+n5=an integer of 1 to 8.]

[0217] <<Organic Underlayer Film-Forming Compound 5>> As the organic underlayer film-forming compound 5 (SOC5 compound), a polymer including a unit structure formed from a reaction product of a fused heterocyclic compound and a bicyclocyclic compound, such as the compounds listed in WO 2013 / 005797 (JP Patent No. 6041104), can be used. The entire disclosure of WO 2013 / 005797 (JP Patent No. 6041104) is incorporated herein by reference. Specifically, examples of the polymer include a unit structure represented by the following formula (SOC5-1), a unit structure represented by the formula (SOC5-2), a unit structure represented by the formula (SOC5-3), or a combination thereof. Unless otherwise specified, the symbols and definitions of the groups in formulas (SOC5-1) to (SOC5-3) defined below are limited only to the descriptions in formulas (SOC1-1) to (SOC5-3), i.e., <<Organic Underlayer Film-Forming Compound 5>>.

[0218] [In the formula, R １ ~R １４ are substituents of hydrogen atoms, each independently representing a halogen atom, a nitro group, an amino group, or a hydroxy group, or an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms which may be substituted by such a group; Ar is an aromatic ring group having 6 to 40 carbon atoms; n １ , n ２ , n ５ , n ６ , n ９ , n １０ , n １３ , n １４ and n １５ are each an integer from 0 to 3, and n ３ , n４ , n ７ , n ８ , n １１ and n １２ are each an integer from 0 to 4.

[0219] <<Organic Underlayer Film-Forming Compound 6>> As the organic underlayer film-forming compound 6 (SOC6 compound), for example, the compounds listed in WO 2021 / 172295 can be used. The entire disclosure of WO 2021 / 172295 is incorporated herein by reference. Specifically, for example, a methoxymethyl group and a ROCH group other than a methoxymethyl group can be used. ２ Examples of suitable polymers include polymers (SOC6 polymers) that contain a plurality of identical or different structural units each having a - group (where R is a monovalent organic group, a hydrogen atom, or a mixture thereof, and the definition of R is limited to SOC6 compounds unless otherwise specified), and a linking group that links the plurality of structural units. In the SOC6 polymer, the monovalent organic group R is preferably a saturated or unsaturated, linear or branched C alkyl group that may be substituted with a phenyl group, a naphthyl group, or an anthracenyl group and may be interrupted by an oxygen atom or a carbonyl group. ２ -C ２０ Aliphatic hydrocarbon group, C ３ -C ２０ The term "mixed" refers to multiple ROCH groups present within a single structural unit. ２ - groups may be different, and the ROCH - groups in each of the two or more structural units may be different. ２ This also means that the - groups may be different. Typical examples of the saturated aliphatic hydrocarbon group include a linear or branched alkyl group having 2 to 20 carbon atoms, and a cyclic alkyl group having, for example, 3 to 20 carbon atoms. Typical examples of the unsaturated aliphatic hydrocarbon group include an alkenyl group having 2 to 20 carbon atoms. The saturated aliphatic hydrocarbon group, unsaturated aliphatic hydrocarbon group, and cyclic alkyl group may be interrupted once or twice or more times by an oxygen atom and / or a carbonyl group. Particularly preferably, R is -CH ２ CH ２ CH ２ CH３ group, and —CH(CH ３ ) CH ２ OCH ３ It is the base.

[0220] <<Organic Underlayer Film-Forming Compound 7>> As organic underlayer film-forming compound 7 (SOC7 compound), for example, the compounds listed in WO 2020 / 184380 can be used. The entire disclosure of WO 2020 / 184380 is incorporated herein by reference. Specific examples include copolymers having a repeating structural unit represented by the following formula (SOC7-1) and / or a repeating unit represented by formula (SOC7-2). Note that, unless otherwise specified, the symbols and definitions of groups in formulas (SOC7-1), (SOC7-2), and (SOC7-3) defined below are limited to the descriptions in formulas (SOC7-1), (SOC7-2), and (SOC7-3), respectively, i.e., <<Organic Underlayer Film-Forming Compound 7>>. [In formula (SOC7-1) and formula (SOC7-2), R １ represents a functional group represented by formula (SOC7-3), in which Q １ and Q ２ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, * represents the bond end to the oxygen atom, and 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.]

[0221] Group X in the above formula (SOC7-2) １ represents, for example, a linear, branched or cyclic divalent hydrocarbon group having 2 to 20 carbon atoms, a linear, branched or cyclic divalent organic group having 2 to 20 carbon atoms and having at least one sulfur atom or oxygen atom, or a divalent organic group containing at least one aromatic ring having 6 to 20 carbon atoms or a heterocyclic ring having 3 to 12 carbon atoms, and the heterocyclic ring has at least one sulfur atom or oxygen atom.

[0222] <<Organic Underlayer Film-Forming Compound 8>> As the organic underlayer film-forming compound 8 (SOC8 compound), compounds listed in WO 2014 / 024836 (Japanese Patent No. 6191831) can be used. The entire disclosure of WO 2014 / 024836 (Japanese Patent No. 6191831) is incorporated herein by reference. Specific examples include polymers having any one or two or more of the repeating structural units represented by the following formulae (SOC8-1a), (SOC8-1b), and (SOC8-1c): Unless otherwise specified, the symbols and definitions of the groups in formulae (SOC8-1a), (SOC8-1b), (SOC8-1c), and (SOC8-2) defined below are limited only to the descriptions in formulae (SOC8-1a), (SOC8-1b), (SOC8-1c), and (SOC8-2), i.e., <<Organic Underlayer Film-Forming Compound 8>>.

[0223] [Wherein, two R １ each 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; 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 R each independently represents an aromatic hydrocarbon group which may have a substituent; ４ each independently represents a hydrogen atom, a phenyl group, or a naphthyl group, and R bonded to the same carbon atom ３ and R ４ When each R represents a phenyl group, they may be bonded to each other to form a fluorene ring, and in formula (SOC8-1b), two R ３ and two R ４ The atoms or groups represented by may be different from each other, two k's each independently represent 0 or 1, m represents an integer of 3 to 500, and n, n １ and n ２ represents an integer of 2 to 500, p represents an integer of 3 to 500, X represents a single bond or a heteroatom, and two Qs each independently represent a group represented by the following formula (SOC8-2):

[0224] (Wherein, two R １ , two R ２ , two R ３ , two R ４ , two k, n １ , n ２ and X are the same as those in formula (SOC8-1b), and two Q １ each independently represents a structural unit represented by the formula (SOC8-2).

[0225] <<Organic Underlayer Film-Forming Compound 9>> As organic underlayer film-forming compound 9 (SOC9 compound), for example, the compounds listed in WO 2012 / 050064 (Japanese Patent No. 5920588) can be used. The entire disclosure of WO 2012 / 050064 (Japanese Patent No. 5920588) is incorporated herein by reference. Specific examples include polymers containing a unit structure represented by the following formula (SOC9-1), a unit structure represented by the formula (SOC9-2), or a combination of a unit structure represented by the formula (SOC9-1) and a unit structure represented by the formula (SOC9-2). Note that, unless otherwise specified, the symbols and definitions of the groups in formulas (SOC9-1) and (SOC9-2) defined below are limited to the descriptions in formulas (SOC9-1) and (SOC9-2), i.e., <<Organic Underlayer Film-Forming Compound 9>>.

[0226] [In formula (SOC9-1), Ar １ represents an organic group containing an arylene group or a heterocyclic group having 6 to 50 carbon atoms.] [In formula (SOC9-2), Ar ２ , Ar ３ , and Ar ４ represents an organic group containing an arylene group or a heterocyclic group having 6 to 50 carbon atoms, and T represents a carbonyl group or a sulfonyl group.

[0227] The unit structure represented by formula (SOC9-1) represents a unit structure having a polyether structure, and the unit structure represented by formula (SOC9-2) represents a unit structure having a polyether ether ketone structure or a polyether ether sulfone structure. １ ~Ar ４ The arylene group or heterocyclic group in the organic group represented by the formula (I) can be used singly or in combination of two or more. The arylene group and the heterocyclic group are, for example, divalent to tetravalent.

[0228] <<Organic Underlayer Film-Forming Compound 10>> As the organic underlayer film-forming compound 10 (SOC10 compound), compounds listed in WO 2022 / 107759 can be used. All of the matters described in WO 2022 / 107759 are incorporated herein by reference. Specifically, for example, ROCH ２ Examples of such a polymer include a polymer (SOC10 polymer) that contains a repeating structural unit in which an aromatic compound A having an - group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof, and unless otherwise specified, the definition of R is limited only to the SOC10 compound) and an aromatic compound B different from A and having 120 or less carbon atoms are alternately bonded via a linking group -O-, and 1 to 6 Bs are bonded to one A.

[0229] The SOC10 polymer is, for example, a polymer containing a repeating structural unit represented by the following formula (SOC10-1): Note that, unless otherwise specified, the symbols and definitions of groups in formula (SOC10-1) defined below are limited to the descriptions in formula (SOC10-1), i.e., <<Organic Underlayer Film-Forming Compound 10>>. [In formula (SOC10-1), A １ ROCH ２ represents an organic group derived from an aromatic compound A having a - group (R is a monovalent organic group, a hydrogen atom, or a mixture thereof); １ is A １ represents an organic group derived from an aromatic compound B having 120 or less carbon atoms, which is different from the above.]

[0230] B in the above formula (SOC10-1) １may be a group represented by the following formula (SOC10-2): Unless otherwise specified, the symbols and definitions of the groups in formula (SOC10-2) are limited to those in formula (SOC10-2), i.e., <<Organic Underlayer Film-Forming Compound 10>>. [In formula (SOOC10-2), C １ , and C ２ each independently represents an aromatic ring having 6 to 48 carbon atoms which may contain a heteroatom, or a hydrocarbon group containing an aromatic ring having 6 to 48 carbon atoms which may contain a heteroatom; Y represents a single bond, a carbonyl group, a sulfonyl group, -CR １ ２ - group, or -(CF ３ ) C (CF ３ )-group, R １ is an oxygen atom, a carbonyl group, a nitrogen atom, an alkyl group having 1 to 10 carbon atoms which may be interrupted by a carbon-carbon double bond or a carbon-carbon triple bond, or which may have a carbon-carbon double bond or a carbon-carbon triple bond attached to a terminal, a hydroxy group, a hydrogen atom, a halogen, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or -NR ２ ２ represents R ２ represents a linear or cyclic alkyl group having 1 to 10 carbon atoms, which may be interrupted by a carbon-carbon double bond or a carbon-carbon triple bond, and which may have a carbon-carbon double bond or a carbon-carbon triple bond attached to its terminal, i is 0 or 1, and the dotted line represents a bond to an oxygen atom.

[0231] <<Organic Underlayer Film-Forming Compound 11>> As the organic underlayer film-forming compound 11 (SOC11 compound), for example, the compounds listed in WO 2013 / 146670 (Japanese Patent Publication No. 6094767) can be used. The entire disclosure of WO 2013 / 146670 (Japanese Patent Publication No. 6094767) is incorporated herein by reference. Specific examples include polymers containing a unit structure represented by the following formula (SOC11-1). Note that, unless otherwise specified, the symbols and definitions of the groups in formula (SOC11-1) defined below are limited to the description in formula (SOC11-1), i.e., <<Organic Underlayer Film-Forming Compound 11>>. [In formula (SOC11-1), R １ , R ２ , and R ３ are substituents for hydrogen atoms in the ring, and each independently represents a halogen atom, a nitro group, an amino group, a hydroxy 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 may contain an ether bond, a ketone bond, or an ester bond. ４ R 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 may contain an ether bond, a ketone bond, or an ester bond. ５ is a hydrogen atom, or 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, an aryl group having 6 to 40 carbon atoms which may be substituted with a hydroxy group, or a heterocyclic group; R ６ is a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may 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 hydroxy group, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group, or R ５ and R ６ may form a ring together with the carbon atoms to which they are attached. Ring A and ring B each represent a benzene ring, a naphthalene ring, or an anthracene ring. n1, n2, and n3 each represent an integer of 0 or more up to the maximum number that can be substituted on the ring.]

[0232] <<Organic Underlayer Film-Forming Compound 12>> As the organic underlayer film-forming compound 12 (SOC12 compound), for example, the compounds listed in International Publication No. 2014 / 030579 (Japanese Patent No. 6124025) can be used. For example, the entire disclosure of International Publication No. 2014 / 030579 (Japanese Patent No. 6124025) is incorporated herein by reference. Specifically, a phenol novolak resin can be mentioned, which is obtained by reacting a compound having at least three phenol groups, each of which is bonded to a tertiary carbon atom, or each of which is bonded to a quaternary carbon atom to which a methyl group is bonded, with an aromatic aldehyde or aromatic ketone in the presence of an acidic catalyst. More specifically, the phenol novolac resin may be a resin containing a unit structure of the following formula (SOC12-1), a unit structure of the formula (SOC12-2), a unit structure of the formula (SOC12-3), a unit structure of the formula (SOC12-4), or a combination of these unit structures. Unless otherwise specified, the symbols and definitions of groups in the following formulas (SOC12-1) to (SOC12-4) and (SOC12-5) are limited to the descriptions in formulas (SOC12-1) to (SOC12-5), i.e., <<Organic Underlayer Film-Forming Compound 12>>.

[0233] [In formulas (SOC12-1), (SOC12-2), (SOC12-3), and (SOC12-4), A is an organic group having at least three phenol groups bonded to a tertiary carbon atom, and B １ , B ２ , B ３ and B ４ are the formulas (SOC12-5): [In formula (SOC12-5), C １ represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a nitro group, an amino group or a hydroxy group, C ２ represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, which may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxy group, or an aryl group or heterocyclic group having 6 to 40 carbon atoms, and C １ and C２ may form a ring together with the carbon atom to which they are attached.

[0234] <<Organic Underlayer Film-Forming Compound 13>> As the organic underlayer film-forming compound 13 (SOC13 compound), for example, the compounds listed in WO 2006 / 132088 can be used. The entire disclosure of WO 2006 / 132088 is incorporated herein by reference. Specific examples include polymers containing any of the unit structures represented by the following formulae (SOC13-1) to (SOC13-5). Note that, unless otherwise specified, the symbols and definitions of the groups in formulae (SOC13-1) to (SOC13-5) defined below are limited to the descriptions in formulae (SOC13-1) to (SOC13-5), i.e., <<Organic Underlayer Film-Forming Compound 13>>. [In each of the above formulas, A represents an organic group having an aromatic group, and Ar １ represents a substituted or unsubstituted aromatic group, Ar ２ represents an aromatic ring that 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; R １ represents a hydroxyl group, an alkyl group, an alkoxy group, a halogen atom, a thiol group, an amino group, or an amide group; m1 represents the number of A substituted on the naphthalene ring and represents an integer of 1 to 6; m2 represents the number of R substituted on the naphthalene ring; １ and represents an integer of 0 to 5; the sum of m1 and m2 is an integer of 1 to 6, and when the sum is other than 6, the remainder represents a hydrogen atom; n represents 2 to 7,000 repeating units; X represents a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, a divalent hydrocarbon group having 2 to 10 carbon atoms and an ether bond, or a carbonyl group; and Z represents a linking group represented by -O- or -OC(=O)-.]

[0235] <<Organic Underlayer Film-Forming Compound 14>> The compounds listed in WO 2016 / 072316 can be used as organic underlayer film-forming compound 14 (SOC14 compound). The entire disclosure of WO 2016 / 072316 is incorporated herein by reference. Specific examples include polymers containing a unit structure represented by the following formula (SOC14-1). Note that, unless otherwise specified, the symbols and definitions of groups in formula (SOC14-1) defined below are limited to the description in formula (SOC14-1), i.e., <<Organic Underlayer Film-Forming Compound 14>>. [In formula (SOC14-1), R １ ~R ４ each independently represents a hydrogen atom or a methyl group. １ represents a divalent organic group containing at least one arylene group which may be substituted with an alkyl group, an amino group, or a hydroxyl group.

[0236] X in formula (SOC14-1) １ can be, for example, an organic group represented by the following formula (SOC14-2) (the dotted line represents a bond). Note that, unless otherwise specified, the symbols and definitions of the groups in formulas (SOC14-2) and (SOC14-3) defined below are limited only to the descriptions in formulas (SOC14-2) and (SOC14-3), i.e., <<Organic Underlayer Film-Forming Compound 14>>. [In formula (SOC14-2), A １ represents a phenylene group or a naphthylene group. ２ is a phenylene group, a naphthylene group, or a group of the formula (SOC14-3): (In formula (SOC14-3), A ３ and A ４ each independently represents a phenylene group or a naphthylene group. A dotted line represents a bond. ) represents an organic group. A dotted line represents a bond.]

[0237] Specific examples of each group in the above formulas (SOC14-1) to (SOC14-3) are as follows. The arylene group is preferably an arylene group derived from an aryl group having 6 to 40 carbon atoms. Examples of the arylene group include a phenylene group, a biphenylene group, a terphenylene group, a fluorenylene group, a naphthylene group, an anthrylene group, a pyrenylene group, and a carbazolylene group. Examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms. Examples of the amino group include a primary amino group, a secondary amino group, and a tertiary amino group, with a secondary amino group being preferred.

[0238] <<Organic Underlayer Film-Forming Compound 15>> As organic underlayer film-forming compound 15 (SOC15 compound), a novolak resin obtained by reacting an aromatic compound with an aldehyde having a formyl group bonded to a secondary or tertiary carbon atom of an alkyl group having 2 to 26 carbon atoms, such as the compounds described in WO 2017 / 069063, can be used. The entire disclosure of WO 2017 / 069063 is incorporated herein by reference. Specific examples include polymers containing a unit structure represented by the following formula (SOC15-1), and polymers containing a more specific unit structure represented by the following formula (SOC15-2). Note that, unless otherwise specified, the symbols and definitions of the groups in formulas (SOC15-1) and (SOC15-2) defined below are limited to the descriptions in formulas (SOC15-1) and (SOC15-2), i.e., <<Organic Underlayer Film-Forming Compound 15>>. [In formula (SOC15-1), A represents a divalent group derived from an aromatic compound having 6 to 40 carbon atoms, and b １ represents an alkyl group having 1 to 16 carbon atoms, and b ２ represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. [In formula (SOC15-2), a １ and a ２ represents an optionally substituted benzene ring or naphthalene ring, and R １represents a secondary amino group or a tertiary amino group, a divalent hydrocarbon group having 1 to 10 carbon atoms which may be substituted, an arylene group, or a divalent group to which any of these groups are optionally bonded. ３ represents an alkyl group having 1 to 16 carbon atoms, and b ４ represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.

[0239] <<Organic Underlayer Film-Forming Compound 16>> As the organic underlayer film-forming compound 16 (SOC16 compound), for example, the compounds listed in WO 2017 / 094780 can be used. The entire disclosure of WO 2017 / 094780 is incorporated herein by reference. Specific examples include polymers containing a unit structure represented by the following formula (SOC16-1), particularly polymers in which the group A in formula (SOC16-1) is a divalent group derived from a compound represented by formula (SOC16-2). Note that, unless otherwise specified, the symbols and definitions of the groups in formulas (SOC16-1) and (SOC16-2) defined below are limited to the descriptions in formulas (SOC16-1) and (SOC16-2), i.e., <<Organic Underlayer Film-Forming Compound 16>>. [In formula (SOC16-1), A is a divalent group having at least two amino groups, and the group is a group derived from a compound having a fused ring structure and an aromatic group substituting a hydrogen atom on the fused ring; B １ , B ２ each independently represents a hydrogen atom, an alkyl group, a benzene ring group, a fused ring group, or a combination thereof, or B １ and B ２ may form a ring together with the carbon atoms to which they are attached. [In 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.

[0240] <<Organic Underlayer Film-Forming Compound 17>> As organic underlayer film-forming compound 17 (SOC17 compound), for example, compounds described in JP 2005-128509 A (Japanese Patent No. 4355943 A) can be used. The entire disclosure of JP 2005-128509 A (Japanese Patent No. 4355943 A) is incorporated herein by reference. Specific examples include novolak resins having a fluorene or tetrahydrospiroindene structure, which have repeating units represented by the following formula (SOC17-1a) or formula (SOC17-1b). Note that, unless otherwise specified, the symbols and definitions of groups in formulas (SOC17-1a) and (SOC17-1b) defined below are limited to the descriptions in formulas (SOC17-1a) and (SOC17-1b), i.e., <<Organic Underlayer Film-Forming Compound 17>>. [In formula (SOC17-1a), (SOC17-1b), R １ , R ２ , R ６ , R ７ are 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 are 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 are 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 and q are integers of 1 to 3. R １０ ~R １３ are independently a hydrogen atom, a halogen atom, a hydroxy 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.

[0241] <<Organic Underlayer Film-Forming Compound 18>> As the organic underlayer film-forming compound 18 (SOC18 compound), for example, the compounds described in JP 2006-259249 A (Japanese Patent No. 4539845 A) can be used. The entire disclosure of JP 2006-259249 A (Japanese Patent No. 4539845 A) is incorporated herein by reference. Specific examples include a compound containing a bisphenol group represented by the following formula (SOC18-1), and a resin having a repeating unit obtained by novolakizing a compound having a bisphenol group represented by the following formula (SOC18-2). Note that, unless otherwise specified, the symbols and definitions of the groups in formulas (SOC18-1) and (SOC18-2) defined below are limited to the description in formulas (SOC18-1) and (SOC18-2), i.e., <<Organic Underlayer Film-Forming Compound 18>>. [In formula (SOC18-1), (SOC18-2), R １ , R ２ 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, or alkenyl groups having 2 to 10 carbon atoms. ３ , R ４ represents 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; Y represents a divalent aliphatic or alicyclic hydrocarbon group having 4 to 30 carbon atoms; The ring represented by may be a bridged ring, and may have a heteroatom interposed therebetween. 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.

[0242] <<Organic Underlayer Film-Forming Compound 19>> As organic underlayer film-forming compound 19 (SOC19 compound), for example, the compounds described in JP 2006-259482 A (Japanese Patent No. 4466854 A) can be used. The entire disclosure of JP 2006-259482 A (Japanese Patent No. 4466854 A) is incorporated herein by reference. Specific examples include a compound containing multiple bisphenol groups represented by the following formula (SOC19-1), and a resin having a repeating unit obtained by novolakizing a compound having bisphenol groups represented by the following formula (SOC19-2). Unless otherwise specified, the symbols and definitions of the groups in formulas (SOC19-1) and (SOC19-2) defined below are limited only to the descriptions in formulas (SOC19-1) and (SOC19-2), i.e., <<Organic Underlayer Film-Forming Compound 19>>. [In formula (SOC19-1), (SOC19-2), R １ 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, or alkenyl groups having 2 to 10 carbon atoms. ２ are the same or different hydrogen atoms, or linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, linear, branched or cyclic alkenyl groups having 2 to 6 carbon atoms, aryl groups having 6 to 10 carbon atoms, acetal groups having 2 to 6 carbon atoms, acyl groups having 2 to 6 carbon atoms, or glycidyl groups, and n is an integer of 2 to 4. ３ 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. represents a 2n-valent hydrocarbon group having 4 to 30 carbon atoms in total, which may contain one or more of an alicyclic hydrocarbon group, a bridged cyclic hydrocarbon group, an aromatic hydrocarbon group, and a condensed polycyclic hydrocarbon group, and A represents A represents a tetravalent hydrocarbon group bonded to There are n pieces in may be interrupted by a heteroatom.

[0243] <<Organic Underlayer Film-Forming Compound 20>> As the organic underlayer film-forming compound 20 (SOC20 compound), for example, the compounds described in JP 2007-199653 A (Japanese Patent No. 4659678 A) can be used. The entire disclosure of JP 2007-199653 A (Japanese Patent No. 4659678 A) is incorporated herein by reference. Specific examples include a compound having a bisnaphthol group represented by the following formula (SOC20-1), and a novolak resin obtained by converting a compound having a bisnaphthol group represented by the following formula (SOC20-2). Note that, unless otherwise specified, the symbols and definitions of the groups in formulas (SOC20-1) and (SOC20-2) defined below are limited to the description in formulas (SOC20-1) and (SOC20-2), i.e., <<Organic Underlayer Film-Forming Compound 20>>. [In the above formulas (SOC20-1) and (SOC20-2), R １ and R ２ are independently 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, or alkenyl groups having 2 to 10 carbon atoms, and R ３ is a single bond or an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, which may 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 a hydrogen atom or a glycidyl group, and R ６ represents a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, and n represents an integer of 1 to 4.

[0244] <<Organic Underlayer Film-Forming Compound 21>> As the organic underlayer film-forming compound 21 (SOC21 compound), for example, the compounds listed in JP 2010-170013 A (Japanese Patent No. 5118073 A) can be used. The entire disclosure of JP 2010-170013 A (Japanese Patent No. 5118073 A) is incorporated herein by reference. Specific examples include a compound having a bisnaphthol group represented by the following formula (SOC21-1), and a novolak resin obtained by converting a compound having a bisnaphthol group represented by the following formula (SOC21-2): Unless otherwise specified, the symbols and definitions of the groups in formulas (SOC21-1) and (SOC21-2) defined below are limited only to the descriptions in formulas (SOC21-1) and (SOC21-2), i.e., <<Organic Underlayer Film-Forming Compound 21>>. [In formula (SOC21-1), 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, or alkenyl groups having 2 to 10 carbon atoms; R ５ ~R ８ are each a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, an acyl group, or a glycidyl group, and R ９ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogen atom, an amino group, an alkylmethylamino group having 1 to 4 carbon atoms, a diarylamino group having 6 to 10 carbon atoms, a cyano group or a nitro group; R １０ , R １１ is a linear or branched alkylene group 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.

[0245] <<Organic Underlayer Film-Forming Compound 22>> As the organic underlayer film-forming compound 22 (SOC22 compound), for example, the compounds listed in JP 2010-122656 A (Japanese Patent No. 5336306 A) can be used. The entire disclosure of JP 2010-122656 A (Japanese Patent No. 5336306 A) is incorporated herein by reference. Specific examples include a compound having a bisnaphthol group represented by the following formula (SOC22-1), and a novolak resin obtained by converting a compound having a bisnaphthol group represented by the following formula (SOC22-2): Unless otherwise specified, the symbols and definitions of the groups in formulas (SOC22-1) and (SOC22-2) defined below are limited only to the descriptions in formulas (SOC22-1) and (SOC22-2), i.e., <<Organic Underlayer Film-Forming Compound 22>>. [In formula (SOC22-1), R １ , R ２ are the same or different hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, and alkenyl groups having 2 to 20 carbon atoms. ３ , R ４ are each a hydrogen atom or a glycidyl group, and R ５ is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms; R ６ , R ７ is a benzene ring or a naphthalene ring. p and q are each 1 or 2. n is 0<n≦1. In formula (SOC22-2), R １ ~R ７ , p, and q are as described above. ８ , R ９ is a hydrogen atom, a hydroxy 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 hydroxy 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. １０ , R １１ is a benzene ring, a naphthalene ring, R１３ , R １４ is a hydrogen atom, a hydroxyl group, or a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, and R １３ and R １４ may be bonded to form a ring. １２ , R １５ is a linear or branched alkylene group having 1 to 10 carbon atoms; s is 1 or 2; 0<n<1.0, 0≦m<1.0, 0≦r<1.0, 0<m+r<1.0.

[0246] <<Organic Underlayer Film-Forming Compound 23>> As the organic underlayer film-forming compound 23 (SOC23 compound), for example, the compounds described in JP 2016-018051 A (Japanese Patent No. 6196190 A) can be used. The entire disclosure of JP 2016-018051 A (Japanese Patent No. 6196190 A) is incorporated herein by reference. Specific examples include resins obtained by novolakizing a compound having a bisnaphthol group represented by the following formula (SOC23-1). Note that, unless otherwise specified, the symbols and definitions of the groups in formula (SOC23-1) defined below are limited to the description in formula (SOC23-1), i.e., <<Organic Underlayer Film-Forming Compound 23>>. [In formula (SOC23-1), R １ , R ２ are each independently a hydrogen atom, a linear, branched, 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. ３ , R ４ are each independently a hydrogen atom or a glycidyl group. ５ is a linear or branched alkylene group having 1 to 10 carbon atoms. ６ , R ７ are each independently a benzene ring or a naphthalene ring, and a hydrogen atom in the benzene ring or naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. p and q are each independently 1 or 2.]

[0247] <<Organic Underlayer Film-Forming Compound 24>> As the organic underlayer film-forming compound 24 (SOC24 compound), for example, the compounds described in JP 2009-014816 A (Japanese Patent No. 4877101 A) can be used. The entire disclosure of JP 2009-014816 A (Japanese Patent No. 4877101 A) is incorporated herein by reference. Specific examples include resins having a group represented by the following formula (SOC24-1) and an aromatic hydrocarbon group, and more specifically, resins having a structural unit represented by the following formula (SOC24-2). Note that, unless otherwise specified, the symbols and definitions of the groups in formulas (SOC24-1) and (SOC24-2) defined below are limited to the description in formulas (SOC24-1) and (SOC24-2), i.e., <<Organic Underlayer Film-Forming Compound 24>>. [In formula (SOC24-1), n ​​represents 0 or 1. R １ represents an optionally substituted methylene group, an optionally substituted alkylene group having 2 to 20 carbon atoms, or an optionally substituted arylene group having 6 to 20 carbon atoms. ２ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. [In formula (SOC24-2), n represents 0 or 1. R １ represents an optionally substituted methylene group, an optionally substituted alkylene group having 2 to 20 carbon atoms, or an optionally substituted arylene group having 6 to 20 carbon atoms. ２ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. ３ ~R ７ represents a hydroxy group, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group having 1 to 6 carbon atoms, an optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted glycidyl ether group having 2 to 6 carbon atoms. ９represents 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.]

[0248] <<Organic Underlayer Film-Forming Compound 25>> As the organic underlayer film-forming compound 25 (SOC25 compound), for example, the compounds described in JP 2019-041059 A (Japanese Patent No. 6726142 A) can be used. The entire disclosure of JP 2019-041059 A (Japanese Patent No. 6726142 A) is incorporated herein by reference. Specific examples include polymers having a repeating unit represented by the following formula (SOC25-1). Note that, unless otherwise specified, the symbols and definitions of the groups in formulas (SOC25-1) and (SOC25-2) defined below are limited only to the description in formulas (SOC25-1) and (SOC25-2), i.e., <<Organic Underlayer Film-Forming Compound 25>>. [In formula (SOC25-1), AR1, AR2, and AR3 are benzene rings, naphthalene rings, or anthracene rings which may have a substituent, and carbon atoms on the aromatic rings of AR1 and AR2, or AR2 and AR3, may be bonded to each other directly or via a linking group to form a bridged structure. R １ , R ２ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R １ and R ２ When is an organic group, R １ and R ２ may be bonded intramolecularly to form a cyclic organic group, and Y is a group represented by the following formula (SOC25-2): [In formula (SOC25-2), R ３ is a single bond or a divalent organic group having 1 to 20 carbon atoms, and R ４ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and the dashed line represents a bond.

[0249] <<Organic Underlayer Film-Forming Compound 26>> As the organic underlayer film-forming compound 26 (SOC26 compound), for example, the compounds described in JP 2019-044022 A (Japanese Patent No. 6940335 A) can be used. The entire disclosure of JP 2019-044022 A (Japanese Patent No. 6940335 A) is incorporated herein by reference. Specific examples include polymers having a repeating unit represented by the following formula (SOC26-1). Note that, unless otherwise specified, the symbols and definitions of groups in formulas (SOC26-1), (SOC26-2), and (SOC26-3) defined below are limited to the description in formulas (SOC26-1), (SOC26-2), and (SOC26-3), i.e., <<Organic Underlayer Film-Forming Compound 26>>. [In formula (SOC26-1), AR1 and AR2 each represent a benzene ring or a naphthalene ring which may have a substituent, and R １ , R ２ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R １ and R ２ When is an organic group, R １ and R ２ may form a cyclic organic group by bonding intramolecularly. n is 0 or 1, and when n = 0, AR1 and AR2 do not form a bridged structure between the aromatic rings of AR1 and AR2 via Z, and when n = 1, AR1 and AR2 form a bridged structure between the aromatic rings of AR1 and AR2 via Z, and Z is either a single bond or a group represented by the following formula (SOC26-2). Y is a group represented by the following formula (SOC26-3). [In formula (SOC26-3), R ３ is a single bond or a divalent organic group having 1 to 20 carbon atoms, and R ４ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and the dashed line represents a bond.

[0250] <<Organic Underlayer Film-Forming Compound 27>> As organic underlayer film-forming compound 27 (SOC27 compound), for example, the compounds described in JP 2021-015222 A can be used. The entire disclosure of JP 2021-015222 A is incorporated herein by reference. Specifically, for example, a polymer having a partial structure represented by the following formula (SOC27-1A) as a repeating unit can be mentioned, and more specifically, a polymer having a partial structure represented by the following formula (SOC27-1B) as a repeating unit can be mentioned. Note that, unless otherwise specified, the symbols and definitions of the groups in formulas (SOC27-1A) and (SOC27-1B) defined below are limited to the descriptions in formulas (SOC27-1A) and (SOC27-1B), i.e., <<Organic Underlayer Film-Forming Compound 27>>. [In the above formulas (SOC27-1A) and (SOC27-1B), AR1 and AR2 are benzene rings or naphthalene rings which may have a substituent, R is a hydrogen atom or a monovalent organic group having an unsaturated bond and 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 and one or more aromatic rings.]

[0251] <<Organic Underlayer Film-Forming Compound 28>> As the organic underlayer film-forming compound 28 (SOC28 compound), for example, the compounds described in JP 2016-216367 A (Japanese Patent No. 6372887 A) can be used. The entire disclosure of JP 2016-216367 A (Japanese Patent No. 6372887 A) is incorporated herein by reference. Specific examples include compounds represented by the following formula (SOC28-1). Note that, unless otherwise specified, the symbols and definitions of groups in formulas (SOC28-1), (SOC28-2), and (SOC28-3) defined below are limited to the descriptions in formulas (SOC28-1), (SOC28-2), and (SOC28-3), i.e., <<Organic Underlayer Film-Forming Compound 28>>. [In formula SOC28-1, n1 and n2 each independently represent 0 or 1, and W is either a single bond or a structure represented by the following formula (SOC28-2): R １represents any of the structures represented by the following general formula (SOC28-3), and m1 and m2 each independently represent an integer of 0 to 7, provided that m1+m2 is 1 or more and 14 or less. [In formula (SOC28-2), l represents an integer of 0 to 3, and R ａ ~R ｆ each independently represents a hydrogen atom or an optionally fluorine-substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a phenylethyl group; R ａ and R ｂ may be bonded to form a cyclic compound. [In formula (SOC28-3), * represents a bonding site to the aromatic ring, and Q １ represents a linear or 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, anthracenyl group, or pyrenyl group. １ represents a linear, branched, saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, Q １ A methylene group constituting the formula (I) may be substituted with an oxygen atom or a carbonyl group.

[0252] <<Crosslinking Agent>> The organic underlayer film-forming composition may contain a crosslinking agent. Examples of such crosslinking agents include melamine-based compounds, substituted urea-based compounds, and polymer-based compounds thereof. Preferred crosslinking agents include those having at least two crosslink-forming substituents such as hydroxymethyl groups or alkoxymethyl groups. Specific examples include compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguwanamine, butoxymethylated benzoguwanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, and methoxymethylated thiourea. Condensates of these compounds may also be used. Furthermore, crosslinking agents with high heat resistance may be used. Preferred crosslinking agents with high heat resistance include compounds containing a crosslink-forming substituent with an aromatic ring (e.g., a benzene ring or a naphthalene ring) in the molecule. These compounds include compounds having a partial structure represented by the following formula (CLA1) and polymers or oligomers having a repeating unit represented by the following formula (CLA2).

[0253] In formula (CLA1), R ＣＬＡ１ and R ＣＬＡ２ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and n ｃｌａ１ is an integer from 1 to 4, and n ｃｌａ２ is 1 to (5-n ｃｌａ１ ), and (n ｃｌａ１ +n ｃｌａ２ ) represents an integer of 2 to 5. In formula (CLA2), R ＣＬＡ３ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ＣＬＡ４ is an alkyl group having 1 to 10 carbon atoms, and n ｃｌａ３ is an integer from 1 to 4, and n ｃｌａ４ is 0 to (4-n ｃｌａ３ ), and (n ｃｌａ３ +n ｃｌａ４) represents an integer of 1 to 4. The oligomer and polymer can be used when the number of repeating structural units is in the range of 2 to 100, or 2 to 50. Examples of these alkyl groups and aryl groups include the alkyl groups and aryl groups listed in <<Organic Underlayer Film-Forming Compound 1 (SOC Compound 1)>>.

[0254] Examples of compounds, polymers and oligomers represented by formula (CLA1) and formula (CLA2) are shown below.

[0255]

[0256]

[0257] The above compounds are available as products of Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the above crosslinking agents, the compound of formula (CLA-21) is available from Asahi Organic Chemicals Co., Ltd. under the trade name TM-BIP-A.

[0258] The amount of crosslinking agent added to the organic underlayer film-forming composition varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 to 80 mass %, preferably 0.01 to 50 mass %, and more preferably 0.05 to 40 mass %, based on the total solids content. These crosslinking agents may undergo a crosslinking reaction by self-condensation, but when crosslinkable substituents are present in the above organic underlayer film-forming compounds 1 to 28 (SOC1 compounds to SOC28 compounds), they can undergo a crosslinking reaction with those crosslinkable substituents.

[0259] <<Acid or Acid Generator>> The organic underlayer film-forming composition may contain an acid or acid generator as a catalyst for accelerating the crosslinking reaction, i.e., an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, an ammonium salt of trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, pyridinium paraphenolsulfonate, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, or naphthalenecarboxylic acid, and / or a thermal acid generator such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, or another organic sulfonate alkyl ester. The amount of these compounds to be added is 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and preferably 0.01 to 3% by mass, based on the total solids content of the organic underlayer film-forming composition.

[0260] The acid generator may be a photoacid generator in addition to the thermal acid generators described above. Examples of the photoacid generator contained in the organic underlayer film-forming composition include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound. Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride. Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide. Examples of disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane. One type of photoacid generator may be used alone, or two or more types may be used in combination.

[0261] When a photoacid generator is used, the proportion thereof is 0.01 to 5 parts by mass, or 0.1 to 3 parts by mass, or 0.5 to 1 part by mass, per 100 parts by mass of the solid content of the organic underlayer film-forming composition.

[0262] <<Other Additives>> In addition to the above components, the organic underlayer film-forming composition may further contain, as needed, a rheology modifier, an adhesion aid, a surfactant, etc. These can be added to the organic underlayer film-forming composition in the amounts and in the form of the various compounds, etc., listed above as components that can be added to the silicon-containing underlayer film-forming composition.

[0263] <Formation of Neutral Film> The neutral film can be formed by applying the neutral film-forming composition described below to the underlayer film (silicon-containing underlayer film) using the appropriate application method described above, followed by baking. Baking conditions are appropriately selected from a baking temperature of 80°C to 300°C or 80°C to 250°C and a baking time of 0.3 to 60 minutes. Preferably, the baking temperature is 150°C to 250°C and the baking time is 0.5 to 2 minutes. The thickness of the neutral film formed here is, for example, 10 to 1,000 nm, or 20 to 500 nm, or 10 to 300 nm, or 5 to 100 nm.

[0264] <Neutral Film-Forming Composition> The neutral film (NL film) used in the present invention can be a material that has been used as an underlayer film to facilitate the arrangement of a self-assembled film into a desired pattern. For example, a polymer containing a unit structure derived from an aromatic vinyl compound (neutral film-forming polymer 1) or a polymer having a unit structure containing an aliphatic polycyclic structure derived from an aliphatic polycyclic compound in its main chain (neutral film-forming polymer 2) can be used, but is not limited to these. The composition for forming the neutral film (NL film) (referred to as the neutral film-forming composition) can contain the neutral film-forming polymer and the solvent described below. In this case, the solids content of the neutral film-forming composition can be, for example, 0.01 to 20% by mass, 0.01 to 15% by mass, or 0.1 to 15% by mass. Here, the solids content is the remaining proportion of the neutral film-forming composition excluding the solvent and water. The proportion of the above polymers (neutral film-forming polymer 1, neutral film-forming polymer 2) in the solid content is usually 50 to 100 mass%, in one embodiment 60 to 95 mass%, and in another embodiment 70 to 90 mass%.

[0265] <<Neutral Film-Forming Polymer 1: Polymer Containing an Aromatic Vinyl Compound>> The neutral film-forming composition used in the present invention can include, for example, a polymer (neutral film-forming polymer 1) having 20 mol % or more of unit structures derived from an aromatic vinyl compound per total unit structure of the polymer, and having 1 mol % or more, or 20 mol % to 100 mol %, or 50 mol % to 100 mol % of unit structures derived from a polycyclic aromatic vinyl compound per total unit structure derived from the aromatic vinyl compound. The aromatic vinyl compound preferably includes vinylnaphthalene, acenaphthylene, or vinylcarbazole, each of which may be substituted, and the polycyclic aromatic vinyl compound is preferably vinylnaphthalene, acenaphthylene, or vinylcarbazole. The polymer used in the neutral film-forming composition essentially contains a unit structure derived from a polycyclic aromatic vinyl compound, and aromatic vinyl compounds are a generic concept of polycyclic aromatic vinyl compounds.

[0266] Examples of the polycyclic aromatic vinyl compound include vinylnaphthalene, vinylanthracene, acenaphthylene, and vinylcarbazole. Other examples of aromatic vinyl compounds include styrene. The aromatic vinyl compound preferably includes an optionally substituted styrene and an optionally substituted vinylnaphthalene, acenaphthylene, or vinylcarbazole. In this case, the polycyclic aromatic vinyl compound can be vinylnaphthalene, acenaphthylene, or vinylcarbazole. The aromatic vinyl compound preferably includes an optionally substituted styrene and an optionally substituted vinylnaphthalene, acenaphthylene, or vinylcarbazole. In this case, the polycyclic aromatic vinyl compound can be an optionally substituted vinylnaphthalene, acenaphthylene, or vinylcarbazole. When the aromatic vinyl compound consists solely of a polycyclic aromatic vinyl compound, the aromatic vinyl compound can be an optionally substituted vinylnaphthalene, acenaphthylene, or vinylcarbazole. In this case, it is preferable to use a polymer containing 60 to 95 mol % of unit structures derived from the aromatic vinyl compound relative to the total unit structures of the polymer. The aromatic vinyl compound and the polycyclic aromatic vinyl compound can be copolymerized to form a polymer.

[0267] In the aromatic vinyl compounds and polycyclic aromatic vinyl compounds, examples of the substituent on the aromatic ring include an alkyl group, a hydroxy group, a carboxyl group, a halogen group (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), etc. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, an n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a ... 1,1-dimethyl-n-pentyl group, a Examples of the alkyl group include a methyl group, a 4-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,2-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 2,3-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 2-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1,2,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, and a 1-ethyl-2-methyl-n-propyl group.Furthermore, a cyclic alkyl group can also be used as the alkyl group. Examples of cyclic alkyl groups having 1 to 10 carbon atoms 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-ethyl ...2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclobutyl, Examples of such groups include 1-n-propylcyclobutyl 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-i-propylcyclopropyl group, 2-i-propylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, and 2-ethyl-3-methylcyclopropyl group.

[0268] The polymer may further have a unit structure having a crosslinking group as a copolymerization component. When the polymer has the unit structure having the crosslinking group, the polymer may have the unit structure having the crosslinking group in a proportion of 1 to 80 mol %, preferably 5 to 40 mol %, per total unit structure of the polymer. The crosslinking group may be a hydroxy group, an epoxy group, a protected hydroxy group, or a protected carboxyl group.

[0269] Examples of monomers having a hydroxy group include hydroxyalkyl (meth)acrylates, vinyl-containing hydroxy groups derived from vinyl alcohol, and phenolic hydroxy groups such as hydroxystyrene. Examples of the alkyl group include the above-mentioned alkyl groups, such as methyl, ethyl, propyl, isopropyl, and butyl. In this specification, (meth)acrylate refers to both methacrylate and acrylate.

[0270] Examples of the monomer having an epoxy group include vinyl group-containing epoxy groups derived from epoxy (meth)acrylate, glycidyl (meth)acrylate, and the like.

[0271] Examples of monomers having a protected hydroxy group include a monomer (4-tert-butoxystyrene) in which the hydroxy group of hydroxystyrene is protected with a tertiary butoxy (tert-butoxy) group. Other examples include a monomer in which the hydroxy group is protected by reacting a phenolic hydroxy group, such as hydroxystyrene, with a vinyl ether compound, and a monomer in which the hydroxy group is protected by reacting an alcoholic hydroxy group, such as hydroxyethyl methacrylate, with a vinyl ether compound. Examples of such vinyl ether compounds include aliphatic vinyl ether compounds having an alkyl chain having 1 to 10 carbon atoms and a vinyl ether group, such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether, as well as cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 2,3-dihydro-4H-pyran.

[0272] Examples of the monomer having a protected carboxyl group include monomers in which the carboxyl group of (meth)acrylic acid or vinylbenzoic acid is protected by reacting the carboxyl group with a vinyl ether compound. Examples of the vinyl ether compound used here include the above-mentioned vinyl ether compounds.

[0273] A polymer obtained by copolymerizing a vinyl compound in addition to the unit structure derived from the aromatic vinyl compound, the unit structure derived from the polycyclic aromatic vinyl compound, and the unit structure having the cross-linking group can be used as the neutral film-forming polymer 1. When the neutral film-forming polymer 1 has a unit structure derived from the vinyl compound, the polymer may have 1 to 80 mol %, preferably 5 to 40 mol %, of the unit structure derived from the vinyl compound relative to the total unit structures of the polymer. Examples of these vinyl compounds include methyl (meth)acrylate, ethyl (meth)acrylate, normal hexyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, anthrylmethyl (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, butyric acid methyl acrylate, methyl meth ... Examples of the vinyl ether include 2-ethyl(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, vinylacetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, and 2-methoxyethyl vinyl ether.

[0274] The weight-average molecular weight of the neutral film-forming polymer 1 used in the neutral film-forming composition can be in the range of 1,000 to 200,000, or 1,000 to 100,000, or 1,000 to 50,000. The weight-average molecular weight can be measured by GPC, and the GPC measurement conditions can be, for example, a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade names Shodex KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, an eluent (elution solvent) of tetrahydrofuran, a flow rate (flow rate) of 1.0 ml / min, and a standard sample of polystyrene (manufactured by Showa Denko K.K.).

[0275] <<Neutral film-forming polymer 2: polymer having a unit structure containing an aliphatic polycyclic structure of an aliphatic polycyclic compound in its main chain>> The neutral film-forming composition used in the present invention can contain, for example, a polymer (neutral film-forming polymer 2) having a unit structure containing an aliphatic polycyclic structure derived from an aliphatic polycyclic compound in its main chain.

[0276] The neutral film-forming polymer 2 can be a polymer having a unit structure containing an aliphatic polycyclic structure derived from an aliphatic polycyclic compound in the main chain of the polymer chain, and a unit structure containing an aromatic ring structure derived from an aromatic ring-containing compound in the main chain of the polymer chain. The polymer can also be a polymer having a unit structure containing an aliphatic polycyclic structure derived from an aliphatic polycyclic compound in the main chain of the polymer chain, and a unit structure containing a vinyl group-containing compound in the main chain of the polymer chain. Examples of vinyl group-containing compounds include alkenes such as ethylene and propylene, and acrylates and methacrylates such as methyl acrylate and methyl methacrylate.

[0277] The polymer has, for example, a structure represented by the following formula (11). In formula (11), Q is a single bond, a divalent group having a polymer chain that is a structure derived from a vinyl group-containing compound, or a divalent group having a polymer chain that is an aromatic ring-containing structure derived from an aromatic ring-containing compound, and T is a divalent group having a polymer chain that is an aliphatic polycyclic structure derived from an aliphatic polycyclic compound. In formula (11), when Q is a divalent group having a polymer chain that is an aromatic ring-containing structure derived from an aromatic ring-containing compound and T is a divalent group having a polymer chain that is an aliphatic polycyclic structure derived from an aliphatic polycyclic compound, the polymer corresponds to a novolak resin.

[0278] In the above formula (11), the group T is a divalent group having an aliphatic polycyclic structure derived from an aliphatic polycyclic compound as a polymer chain. This aliphatic polycyclic compound preferably has at least two double bonds in the ring, and can be a diene compound having two to six rings. Examples of these diene compounds include bicyclo compounds, tricyclo compounds, tetracyclo compounds, pentacyclo compounds, and hexacyclo compounds. Examples of the aliphatic polycyclic compound include 2,5-norbornadiene, 3a,4,7,7a-tetrahydroindene, 1,3a,4,6a-tetrahydropentalene, and dicyclopentadiene, and 2,5-norbornadiene and dicyclopentadiene are preferred. The aliphatic polycyclic compound can have any substituent, and examples of the substituent include an alkyl group, a phenyl group, a hydroxy group, a carboxyl group, a cyano group, a nitro group, and a halogen atom.

[0279] In formula (11), when Q is a divalent group having an aromatic ring-containing structure derived from an aromatic ring-containing compound as a polymer chain, the aromatic ring-containing compound may be a monocyclic compound (also called a carbocyclic compound) or a heterocyclic compound. The monocyclic compound may be an optionally substituted benzene or an optionally substituted naphthalene, and the heterocyclic compound may be an optionally substituted carbazole or an optionally substituted phenothiazine. The aromatic ring-containing compound may be a compound having a hydroxy group or an amino group as an electron-donating organic group. Examples of aromatic ring-containing compounds include phenol, cresol, 4-phenylphenol, 1-naphthol, catechol, resorcinol, hydroquinone, 4,4'-biphenol, 2,2'-biphenol, 2,2-bis(hydroxyphenyl)propane, 1,5-dihydroxynaphthalene, pyrogallol, phloroglucinol, aniline, carbazole, phenyl-1-naphthylamine, triphenylamine, 2-phenylindole, and phenothiazine, and preferred are phenol, carbazole, and phenothiazine.

[0280] In formula (11), Q is a divalent group having an aromatic ring-containing structure derived from an aromatic ring-containing compound as a polymer chain, and T is a divalent group having an aliphatic polycyclic structure derived from an aliphatic polycyclic compound as a polymer chain. A novolak resin is obtained by the condensation reaction of an aromatic ring-containing compound with an aliphatic polycyclic compound. In this condensation reaction, 0.1 to 10 equivalents of an aliphatic polycyclic compound having a diene structure can be used per equivalent of phenyl groups contained in the aromatic ring-containing compound and participating in the reaction. Examples of acid catalysts used in the condensation reaction include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and p-toluenesulfonic acid monohydrate; and carboxylic acids such as formic acid and oxalic acid. The amount of acid catalyst used varies depending on the type of acid used. Typically, the amount of acid is 0.001 to 10,000 parts by mass, preferably 0.01 to 1,000 parts by mass, and more preferably 0.1 to 100 parts by mass, per 100 parts by mass of the aromatic ring-containing compound and the diene-containing aliphatic polycyclic compound combined. The condensation reaction can be carried out without a solvent, but is typically carried out using a solvent. Any solvent that does not inhibit the reaction can be used. Examples include toluene, 1,4-dioxane, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and butyrocellosolve. Furthermore, if the acid catalyst used is liquid, such as formic acid, it can also function as a solvent. The reaction temperature during condensation is typically 40°C to 200°C. The reaction time varies depending on the reaction temperature, but is typically about 30 minutes to 50 hours. The weight-average molecular weight Mw of the novolak resin obtained in this manner is typically 500 to 1,000,000, or 600 to 200,000.

[0281] Examples of the novolak resin include resins having structural units represented by the following formulas (11-1) to (11-19).

[0282]

[0283] The novolac resin may have an epoxy group. Examples of the novolac resin having an epoxy group include epoxyphenol-dicyclopentadiene resin, epoxycresol-dicyclopentadiene resin, epoxyphenol-norbornadiene resin, epoxynaphthol-dicyclopentadiene resin, and epoxydihydroxynaphthalene-dicyclopentadiene resin. In particular, epoxyphenol-dicyclopentadiene resin is known as a commercially available product (dicyclopentadiene epoxy resin, product name: EPICLON HP-7200H, manufactured by DIC Corporation).

[0284] Examples of the novolac resin having an epoxy group include resins having structural units represented by the following formulas (12-1) to (12-5).

[0285]

[0286] Furthermore, the novolac resin having the epoxy group can be added with an organic compound Z that reacts with the epoxy group. Examples of such organic compound Z include carboxylic acids, phenols, amines, and imide compounds. Examples of the organic compound Z include benzoic acid, 4-toluic 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-anthracenecarboxylic acid, n-butanoic acid, n-hexanoic acid, n-octanoic acid, pivalic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, adamantanecarboxylic 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, and diallylisocyanuric acid. Particularly preferred are 4-tert-butylbenzoic acid, 4-phenylbenzoic acid, 1-naphthoic acid, 9-anthracenecarboxylic acid, n-butanoic acid, n-hexanoic acid, n-octanoic acid, pivalic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, cinnamic acid, 1-naphthol, and 4-phenylphenol.

[0287] In the reaction between the novolac resin containing epoxy groups and the organic compound Z capable of being added to the epoxy groups, the organic compound Z can be used in a ratio of 0.1 to 1 equivalent per equivalent of epoxy groups contained in the novolac resin containing epoxy groups. Two or more organic compounds Z can also be used in combination. The catalyst used to activate the epoxy groups in the addition reaction is, for example, a quaternary phosphonium salt such as ethyltriphenylphosphonium bromide or a quaternary ammonium salt such as benzyltriethylammonium chloride, typically in an amount of 0.001 to 1 equivalent per equivalent of epoxy groups contained in the novolac resin. The addition reaction can be carried out without a solvent, but is typically carried out using a solvent. Any solvent that does not inhibit the reaction can be used. For example, alcohols such as propylene glycol monomethyl ether, esters such as propylene glycol monomethyl ether acetate and ethyl lactate, and ketones such as cyclohexanone have high solubility in novolac resins and are more preferably used. The reaction temperature during the addition reaction is typically 40°C to 200°C. The reaction time is generally about 30 minutes to 50 hours, depending on the reaction temperature. The weight average molecular weight Mw of the novolak resin obtained in the above manner is generally 500 to 1,000,000, or 600 to 200,000.

[0288] Examples of the novolak resin, which is an adduct of the novolak resin having an epoxy group and the organic compound Z, include resins having structural units represented by the following formulas (13-1) to (13-12).

[0289]

[0290] In addition to the neutral film-forming polymer 1 or neutral film-forming polymer 2, the neutral film-forming composition may contain other polymers within a range that does not impair the effects of the present invention. When other polymers are contained, the proportion of the neutral film-forming polymer 1 or neutral film-forming polymer 2 relative to the mass of all polymers in the neutral film-forming composition may be 0.1 to 100% by mass, preferably 5 to 100% by mass, and more preferably 10 to 100% by mass, although this varies depending on the coating solvent used, the baking conditions of the neutral film-forming composition, the baking conditions of the self-assembled film formed on the upper layer, the base substrate used, etc.

[0291] <<Crosslinking Agent Component>> The neutral film-forming composition may contain a crosslinking agent component. Examples of the crosslinking agent include melamine-based compounds, substituted urea-based compounds, and polymer compounds thereof. A crosslinking agent having at least two crosslink-forming substituents such as hydroxymethyl groups or alkoxymethyl groups is preferred, specifically a compound such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguwanamine, butoxymethylated benzoguwanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Condensates of these compounds may also be used. Furthermore, the crosslinking agent may be any of the crosslinking agents listed in the description of the organic underlayer film-forming composition. The amount of crosslinking agent added to the neutral film-forming composition varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 to 80 mass %, preferably 0.01 to 50 mass %, and more preferably 0.05 to 40 mass %, of the total solids content. These crosslinking agents may cause a crosslinking reaction by self-condensation, but when crosslinkable substituents are present in the above polymers (neutral film-forming polymer 1, neutral film-forming polymer 2), they can cause a crosslinking reaction with those crosslinkable substituents.

[0292] <<Acid or Acid Generator>> The neutral film-forming composition may contain an acid or acid generator as a catalyst for accelerating the crosslinking 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, or naphthalenecarboxylic acid, and / or a thermal acid generator such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, or other organic sulfonic acid alkyl esters. The amount of these compounds to be added is 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and preferably 0.01 to 3% by mass, based on the total solids content of the neutral film-forming composition.

[0293] The acid generator may be a photoacid generator in addition to the thermal acid generator. The photoacid generator generates acid when the resist is exposed to light. This allows the acidity of the neutral film to be adjusted. This is one way to match the acidity of the neutral film to that of the overlying self-assembled monolayer. Furthermore, adjusting the acidity of the neutral film allows the pattern shape of the overlying self-assembled monolayer to be adjusted.

[0294] Examples of the photoacid generator contained in the neutral film-forming composition include an onium salt compound, a sulfonimide compound, and a disulfonyldiazomethane compound. Examples of the onium salt compound include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-normal butanesulfonate, diphenyliodonium perfluoro-normal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-normal butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride. Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide. Examples of disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane. A single photoacid generator may be used, or two or more types may be used in combination. When a photoacid generator is used, 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, per 100 parts by weight of the solids content of the neutral film-forming composition.

[0295] <<Other Additives>> In addition to the above components, the neutral film-forming composition may further contain, as needed, a rheology modifier, an adhesion aid, a surfactant, etc. These can be added to the neutral film-forming composition in the same amounts as the various compounds, etc. listed above as components that can be added to the silicon-containing underlayer film-forming composition.

[0296] <Patterning of Neutral Film> In one embodiment for inducing a microphase-separated structure in a desired pattern, a template film for a self-assembled pattern can be formed from a neutral film and a brush film (described later). In this case, pattern formation using a photoresist can be utilized to form the desired pattern in the neutral film.

[0297] To form a pattern using a photoresist, first, a layer of photoresist material (resist film) is formed on the neutral film. The resist film can be formed by a well-known method, i.e., by applying a coating-type resist material (e.g., a photoresist film-forming composition) on the neutral film and baking it. Baking conditions can be, for example, a baking temperature of 70 to 150°C and a baking time of 0.5 to 5 minutes. The film thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.

[0298] The photoresist material used in the resist film is not particularly limited as long as it is sensitive to the light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.), and both negative and positive photoresist materials can be used. Examples include a positive photoresist material composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester, a chemically amplified photoresist material composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate and a photoacid generator, a chemically amplified photoresist material composed of a low molecular weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist material, an alkali-soluble binder, and a photoacid generator, and a chemically amplified photoresist material composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate, a low molecular weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist material, and a photoacid generator. Specific examples of commercially available products include, but are not limited to, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., AR2772JN (trade name) manufactured by JSR Corporation, and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. Other examples include fluorine-containing polymer photoresist materials such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0299] Furthermore, instead of a photoresist film, the resist film can be a resist film for electron beam lithography (also referred to as an electron beam resist film) or a resist film for EUV lithography (also referred to as an EUV resist film). The electron beam resist material can be either a negative-type material or a positive-type material. Specific examples include a chemically amplified resist material comprising an acid generator and a binder having a group that decomposes in the presence of an acid to change the alkaline dissolution rate; a chemically amplified resist material comprising an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that decomposes in the presence of an acid to change the alkaline dissolution rate of the resist material; a chemically amplified resist material comprising an acid generator, a binder having a group that decomposes in the presence of an acid to change the alkaline dissolution rate, and a low-molecular-weight compound that decomposes in the presence of an acid to change the alkaline dissolution rate of the resist material; a non-chemically amplified resist material comprising a binder having a group that decomposes in the presence of an electron beam to change the alkaline dissolution rate; and a non-chemically amplified resist material comprising a binder having a moiety that is cleaved by an electron beam to change the alkaline dissolution rate. When these electron beam resist materials are used, a resist film pattern can be formed in the same manner as when a photoresist material is used with an electron beam as the irradiation source. Furthermore, a methacrylate resin-based resist material can be used as the EUV resist material.

[0300] Next, the formed resist film is exposed through a predetermined mask (reticle). For exposure, 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 can be used. After exposure, a 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.

[0301] Next, development is carried out using a developer (e.g., an alkaline developer). As a result, when a positive photoresist film is used, for example, the exposed portions of the photoresist film are removed, forming a photoresist film pattern. Examples of the developer (alkaline developer) include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers. Development conditions are appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0302] An organic solvent can also be used as the developer, and development is carried out with the developer (solvent) after exposure. As a result, when a negative photoresist film is used, for example, the photoresist film in the unexposed areas is removed, forming a photoresist film pattern.Examples of the developer (organic solvent) include 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 butyl 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, carbonate Examples of the developer include ethyl, 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, etc. Furthermore, a surfactant or the like can also be added to these developers.The conditions for development are suitably selected from the temperature range of 5° C. to 50° C. and the time range of 10 seconds to 600 seconds.

[0303] Next, the neutral film is etched using the pattern of the resist film as a protective film, and the neutral film is patterned. The neutral film is removed (patterned) using an oxygen-based gas (oxygen gas, oxygen / nitrogen (N ２ This is because the silicon-containing underlayer film, which contains a large amount of silicon atoms and is provided below the neutral film, is difficult to remove by dry etching using an oxygen-based gas.

[0304] The resist film (pattern) is then removed by etching or stripping to obtain a patterned neutral film. The resist film can be removed by plasma or ozone etching, or an existing resist stripper can be used depending on the type of photoresist.

[0305] <Formation of a Template Film for Self-Assembled Patterning Composed of a Neutral Film and a Brush Film> To form the template film for the self-assembled pattern, first, a brush film-forming material (brush layer-forming composition) is applied to the underlayer film (exposed portion) and the patterned neutral film on the underlayer film obtained in the above process by the appropriate application method described above, so as to cover the patterned neutral film on the silicon-containing underlayer film. The resulting material is then baked to form a brush film over the entire substrate. The baking conditions are appropriately selected from a baking temperature of 80°C to 300°C or 80°C to 250°C and a baking time of 0.3 to 60 minutes. Preferably, the baking temperature is 80°C to 100°C and the baking time is 0.5 to 2 minutes. The thickness of the film formed here need only be thick enough to cover the patterned neutral film.

[0306] The brush film is a film that is provided so as not to cause self-organized patterns to appear in unintended places, and in order to achieve such a function, the film is required to have the property of sufficiently adhering to the silicon-containing underlayer film, while not adhering to the neutral film.

[0307] <<Brush Layer-Forming Composition>> The brush layer-forming composition contains, for example, a brush polymer and a solvent. The brush layer-forming composition is, for example, a composition containing polymer chains capable of directly bonding to the substrate surface. A film or layer formed by polymer chains arranged in a brush-like pattern on a substrate is sometimes called a brush layer. The brush layer-forming composition is, for example, a composition for forming an underlayer film for forming an underlayer film of a layer containing a block copolymer. Furthermore, a film formed from the brush layer-forming composition serves, for example, as a guide that controls the position of the polymer phase formed by self-assembly. For example, a film formed from the brush layer-forming composition has a concave-convex structure and serves as the sidewall of a recess in a physical guide (grapho-epitaxy) for forming a microphase-separated pattern in the recess. Furthermore, for example, a film formed from the brush layer-forming composition is, for example, a chemical guide (chemical-epitaxy) that is formed under a self-assembling material and controls the position of the microphase-separated pattern based on the difference in surface energy.

[0308] <<<Brush Polymer>>> The brush polymer is not particularly limited as long as it is a brush polymer used in forming the underlayer film.

[0309] An example of a brush polymer is a polymer having a neutral wetting bottom surface, as described in JP-A-2011-515537. Examples of such a polymer include a random copolymer as described in claim 15 of JP-A-2011-515537 and a grafted blend of multiple homopolymers as described in claim 16. The contents of JP-A-2011-515537 are incorporated herein by reference to the same extent as if expressly set forth in its entirety.

[0310] Another example of the brush polymer is the random copolymer described in JP-T-2011-518652. One example of the random copolymer described in JP-T-2011-518652 is the photocrosslinkable random PS-r-PMMA described in paragraph

[0028] . The contents of JP-T-2011-518652 are incorporated herein by reference to the same extent as if set forth in their entirety.

[0311] Another example of a brush polymer is a resin in which 20 mol % to 80 mol % of the total structural units are derived from aromatic ring-containing monomers. Such a resin is, for example, the resin component contained in the primer described in WO 2012 / 036121. The contents of WO 2012 / 036121 are incorporated herein by reference in their entirety.

[0312] Another example of the brush polymer is the random copolymer described in claim 1 of JP 2013-166934 A. The contents of JP 2013-166934 A are incorporated herein by reference in their entirety to the same extent as if set forth explicitly herein.

[0313] Another example of the brush polymer is a polymer having 0.2 mol% or more of a polycyclic aromatic vinyl compound unit structure per total unit structure. Examples of such polymers include the polymers contained in the underlayer film-forming composition described in International Publication No. 2014 / 097993. The contents of International Publication No. 2014 / 097993 are incorporated herein by reference in their entirety.

[0314] Another example of a brush polymer is the polymer contained in the brush backfill composition described in JP 2015-130496 A (e.g., poly(alkyl acrylate) having functional groups capable of reacting with semiconductor substrates), the contents of which are incorporated herein by reference in their entirety to the same extent as if set forth herein.

[0315] Another example of the brush polymer is the addition polymer described in claim 1 of JP 2016-148024 A. The contents of JP 2016-148024 A are incorporated herein by reference in their entirety to the same extent as if set forth explicitly herein.

[0316] Another example of the brush polymer is the polymer contained in the pinning material described in claim 1 of JP-T-2016-528713. Such a polymer is, for example, the polymer described in claim 3 of JP-T-2016-528713. The contents of JP-T-2016-528713 are incorporated herein by reference in their entirety to the same extent as if set forth explicitly herein.

[0317] Another example of a brush polymer is an acid-sensitive copolymer comprising an acid-decomposable group, an attachment group, and a functional group, as described in claim 1 of JP 2018-139007 A. The contents of JP 2018-139007 A are incorporated herein by reference in their entirety to the same extent as if set forth herein.

[0318] Another example of the brush polymer is the hydrophobic polymer brush precursor described in claim 1 of JP-T-2018-503241, the contents of which are incorporated herein by reference in their entirety to the same extent as if set forth herein.

[0319] The brush polymer preferably has a functional group capable of bonding to a substrate. Examples of functional groups capable of bonding to a substrate include a hydroxy group, an amino group, and a sulfonic acid group. The brush polymer may have the functional group capable of bonding to a substrate at the end of the polymer chain, or at a location other than the end of the polymer chain. There are no particular limitations on the method for introducing the functional group capable of bonding to a substrate into the end of the polymer chain. For example, in the case of an addition polymerization type polymer, a method may be used in which a compound having a functional group capable of bonding to a substrate is used as a polymerization initiator or chain transfer agent.

[0320] The brush polymer is preferably an addition polymerization type polymer obtained, for example, by polymerizing one or more radically polymerizable monomers.

[0321] The radical polymerizable monomer is not particularly limited, and examples thereof include (meth)acrylic compounds, aromatic group-containing vinyl compounds, etc. Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid esters, etc. Examples of the (meth)acrylic acid esters include 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, and tert-butyl (meth)acrylate. Examples of aromatic group-containing vinyl compounds include 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, and vinylpyridine.

[0322] <<<<<Polymer (P)>>>> The brush polymer is preferably a polymer (P) containing the following structural units (A) and (B), in that a microphase-separated structure of the block copolymer can be induced perpendicular to the substrate. 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 the substrate. Structural unit (B): a structural unit derived from an aromatic group-containing vinyl compound.

[0323] The molar ratio of the structural unit (A) to all structural units in the polymer (P) is more than 0% and not more than 5%. When the molar ratio of the structural unit (A) to all structural units in the polymer (P) is more than 0% and not more than 5%, a film can be formed in which a microphase-separated structure of the block copolymer is induced perpendicular to the substrate. When the molar ratio of the structural unit (A) to all structural units in the polymer (P) exceeds 5%, the arrangement of the microphase-separated structure of the block copolymer becomes disordered, and it is not possible to induce a microphase-separated structure of the block copolymer perpendicular to the substrate.

[0324] The polymer (P) is not particularly limited as long as it contains the structural units (A) and (B), but is preferably an addition polymer obtained by polymerizing a compound having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, and a (meth)acryloyl group.

[0325] The polymer (P) is, for example, a random copolymer.

[0326] The polymer (P) may contain structural units other than the structural units (A) and (B).

[0327] The structural unit (A) is a structural unit derived from a (meth)acrylic compound. The (meth)acrylic compound has a (meth)acryloyl group. The (meth)acrylic compound has a functional group capable of bonding to a substrate. The (meth)acryloyl group is a notation that indicates an acryloyl group and a methacryloyl group. The acryloyl group is a CH ２ =CH-CO-, and a methacryloyl group is a group represented by CH ２ =C(CH ３ )-CO-.

[0328] The functional group capable of bonding to a substrate is not particularly limited, and examples thereof include a hydroxy group, an amino group, and a sulfonic acid group. The number of functional groups capable of bonding to a substrate in the structural unit (A) may be one or two or more, but is preferably one. The number of (meth)acryloyl groups in the (meth)acrylic compound may be one or two or more, but is preferably one.

[0329] The structural unit (A) is a structural unit different from the structural unit (B), and therefore the structural unit (B) does not have an aromatic ring.

[0330] The structural unit (A) in the polymer (P) may be of one type or of two or more types.

[0331] The structural unit (A) preferably contains a structural unit (A-1) represented by the following formula (1). (In formula (1), X represents —O— or —NH—. Y represents a hydroxy group, an amino group, or a sulfonic acid group. R １ represents an alkylene group having 1 to 10 carbon atoms which may be substituted with a halogen atom. ２ represents a hydrogen atom or a methyl group.

[0332] The amino group is preferably a primary amino group or a secondary amino group. A primary amino group is a monovalent functional group (—NH ２ A secondary amino group refers to a monovalent functional group (-NHR (wherein R represents an organic group) formed by removing a hydrogen atom from a primary amine. R represents, for example, an alkyl group having 1 to 6 carbon atoms.

[0333] The alkylene group having 1 to 10 carbon atoms and optionally substituted with a halogen atom may be linear, branched, or cyclic. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The number of halogen atoms in the alkylene group having 1 to 10 carbon atoms and optionally substituted with a halogen atom may be one or two or more.

[0334] The alkylene group having 1 to 10 carbon atoms may be a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, a 1,3-propylene group (a trimethylene group), a 1-methylethylene group (a 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, and a 1,10-decylene group.

[0335] The molar ratio of the structural unit (A) to all 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, and particularly preferably 0.5% or more and 4.0% or less.

[0336] Examples of the (meth)acrylic compound include compounds represented by the following formula (1-1). (In formula (1-1), X represents —O— or —NH—. Y represents a hydroxy group, an amino group, or a sulfonic acid group. R １ represents an alkylene group having 1 to 10 carbon atoms which may be substituted with a halogen atom. ２ represents a hydrogen atom or a methyl group.

[0337] Examples of the (meth)acrylic compound include hydroxy group-containing (meth)acrylates, amino group-containing (meth)acrylates, sulfonic acid group-containing (meth)acrylates, hydroxy group-containing (meth)acrylamides, and sulfonic acid group-containing (meth)acrylamides.

[0338] Examples of hydroxy group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate.

[0339] Examples of amino group-containing (meth)acrylates include primary amino group-containing (meth)acrylates and secondary amino group-containing (meth)acrylates. Examples of primary amino group-containing (meth)acrylates include aminomethyl (meth)acrylate and aminoethyl (meth)acrylate. Examples of secondary amino group-containing (meth)acrylates include t-butylaminoethyl (meth)acrylate and t-butylaminopropyl (meth)acrylate.

[0340] Examples of sulfonic acid group-containing (meth)acrylates include 2-sulfoethyl (meth)acrylate and 3-sulfopropyl (meth)acrylate.

[0341] Examples of hydroxy group-containing (meth)acrylamides include N-(hydroxymethyl)(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, and N-(4-hydroxybutyl)(meth)acrylamide.

[0342] The structural unit (B) is a structural unit derived from an aromatic group-containing vinyl compound. The aromatic ring contained in the aromatic group-containing vinyl compound may be an aromatic hydrocarbon ring or an aromatic heterocycle, but an aromatic hydrocarbon ring is preferred. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring. The aromatic group-containing vinyl compound does not have, for example, a functional group capable of bonding to a substrate. The aromatic group-containing vinyl compound does not have, for example, a hydroxy group, an amino group, or a sulfonic acid group.

[0343] The structural unit (B) does not have, for example, a functional group capable of bonding to a substrate, such as a hydroxy group, an amino group, or a sulfonic acid group.

[0344] The structural unit (B) in the polymer (P) may be of one type or of two or more types.

[0345] The structural unit (B) preferably contains a structural unit (B-1) represented by the following formula (2): The structural unit (B) preferably contains a structural unit (B-2) represented by the following formula (3): (In formula (2), n Ys each independently represent 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.) (In formula (3), R ３ ~R ５ each independently represents a hydrogen atom or a tert-butyl group. ３ ~R ５ One or two of represents a tert-butyl group.

[0346] Examples of the halogen atom for Y in formula (2) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group for Y in formula (2) is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkoxy group for Y in formula (2) is preferably an alkoxy group having 1 to 15 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, even more preferably an alkoxy group having 1 to 6 carbon atoms, and particularly preferably an alkoxy group having 1 to 3 carbon atoms. The alkyl group in the alkoxy group may be linear, branched, or cyclic. The alkoxycarbonyl group for Y in formula (2) is preferably an alkoxycarbonyl group having 2 to 15 carbon atoms, more preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, even more preferably an alkoxycarbonyl group having 2 to 6 carbon atoms, and particularly preferably an alkoxycarbonyl group having 2 to 3 carbon atoms. The alkyl group in the alkoxycarbonyl group may be linear, branched, or cyclic. Examples of the thioalkyl group for Y in formula (2) include groups in which -O- of the above alkoxy group is replaced with -S-.

[0347] The molar ratio of the structural unit (B) to all structural units in the polymer (P) is not particularly limited, but 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%.

[0348] The molar ratio of the structural unit (A) to the structural unit (B) in the polymer (P) (structural unit (A):structural unit (B)) is not particularly limited, but is preferably 1:200 to 1:10, and more preferably 1:150 to 1:20.

[0349] When the polymer (P) contains the structural unit (B-1) represented by formula (2), the molar ratio of the structural unit (A) to the 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.

[0350] When the polymer (P) contains the structural unit (B-2) represented by formula (3), the molar ratio of the structural unit (A) to the structural unit (B-2) in the polymer (P) (structural unit (A):structural unit (B-2)) is not particularly limited, but is preferably 1:100 to 1:5, and more preferably 1:75 to 1:10.

[0351] When 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, but 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.

[0352] Examples of the aromatic group-containing vinyl compound include a compound represented by the following formula (2-1) and a compound represented by the following formula (3-1). (In formula (2-1), n ​​Ys each independently represent 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.) (In formula (3-1), R ３ ~R ５ each independently represents a hydrogen atom or a tert-butyl group. ３ ~R ５ One or two of represents a tert-butyl group.

[0353] The weight average molecular weight of the brush polymer measured by gel permeation chromatography (GPC) is not particularly limited, but is, for example, 1,000 to 50,000, and preferably 2,000 to 20,000, in terms of polystyrene.

[0354] <<<<<Method for Producing Brush Polymers>>>> The method for producing a brush polymer is not particularly limited. For example, when the brush 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 preferred, and in this case, for example, polymerization can be carried out by adding the desired monomer to a solvent to which a polymerization initiator has been added. For example, when the brush polymer is an addition polymerization type random copolymer, it can be produced by copolymerizing various monomers to an appropriate molar ratio by a conventional method, such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization. Examples of such polymerization include radical polymerization. The brush polymer can also be produced by a polymerization method other than radical polymerization. For example, it can be produced by ionic (anionic or cationic) addition polymerization, polycondensation, or polyaddition reaction.

[0355] The polymer (P) can be produced, 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 an aromatic group-containing vinyl compound.

[0356] [Polymerization Initiator] As the polymerization initiator, an organic peroxide or a diazo compound can be used.

[0357] Examples of organic peroxides include diacyl peroxides, peroxydicarbonates, peroxyesters, and peroxysulfonates. Examples of diacyl peroxides include diacetyl peroxide, diisobutyl peroxide, didecanoyl peroxide, benzoyl peroxide, and succinic acid peroxide. Examples of peroxydicarbonates include diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diallyl peroxydicarbonate. Examples of peroxyesters include tert-butyl peroxyisobutyrate, tert-butyl neodecanoate, and cumene peroxyneodecanate. Examples of peroxysulfonates include acetylcyclohexylsulfonyl peroxide.

[0358] Examples of diazo compounds include 2,2'-azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(4-methoxy-2,4-dimethoxyvaleronitrile), and 2,2'-azobis(2-cyclopropylpropionitrile).

[0359] When it is desired to complete the polymerization in a short time, it is preferable to use a polymerization initiator having a decomposition half-life of 10 hours or less at 80° C. As such a polymerization initiator, benzoyl peroxide and 2,2′-azobisisobutyronitrile are preferred, and 2,2′-azobisisobutyronitrile is more preferred.

[0360] The amount of the polymerization initiator used is, for example, 0.0001 to 0.2 equivalents, and preferably 0.0005 to 0.1 equivalents, based on the total amount of the monomers used.

[0361] [Solvent] The solvent used in the polymerization is not particularly limited as long as it is inert to the polymerization reaction and compatible with the resulting brush polymer. Examples of the solvent include aromatic hydrocarbons, alicyclic hydrocarbons, aliphatic hydrocarbons, ketones, ethers, esters, amides, sulfoxides, alcohols, and polyhydric alcohol derivatives. Examples of aromatic hydrocarbons include benzene, toluene, and xylene. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aliphatic hydrocarbons include n-hexane and n-octane. Examples of ketones include acetone, methyl ethyl ketone, and cyclohexanone. Examples of ethers include tetrahydrofuran and dioxane. Examples of esters include ethyl acetate and butyl acetate. Examples of amides include N,N-dimethylformamide and N,N-dimethylacetamide. Examples of sulfoxides include dimethyl sulfoxide. Examples of alcohols include methanol and ethanol. Examples of polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc. These may be used alone or in combination of two or more.

[0362] The polymerization temperature is not particularly limited as long as it is within a temperature range in which side reactions such as transfer reactions and termination reactions do not occur and the monomer is consumed to complete the polymerization, but it is preferably carried out within a temperature range of -100°C or higher and the boiling point of the solvent or lower. The concentration of the monomer relative to the solvent is not particularly limited, but is usually 1 to 40% by mass, preferably 10 to 30% by weight. The polymerization reaction time can be appropriately selected, but is usually within a range of 2 to 50 hours.

[0363] <<<Solvent>>> The solvent contained in the brush layer-forming composition is not particularly limited as long as it dissolves the brush polymer. Examples of the solvent include 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, γ-butyrolactone, N-methyl-2-pyrrolidone, methyl 2-hydroxyisobutyrate, and ethyl 3-ethoxypropionate. These can be used alone or in combination of two or more.

[0364] The content of the solvent in the brush layer-forming composition is not particularly limited, but is, for example, 90% by mass or more and 99.9% by mass or less.

[0365] <<<Other Components>>> The brush layer-forming composition preferably does not contain a crosslinking agent. For example, by reacting the brush polymer with the substrate, the film obtained from the brush layer-forming composition becomes a film that is insoluble in the solvent contained in the self-assembled film-forming composition containing the block copolymer. Therefore, the brush layer-forming composition does not need to contain a crosslinking agent. In the present invention, "not containing a crosslinking agent" may also include the inclusion of a small amount of crosslinking agent to the extent that it does not fully function as a crosslinking agent. In an embodiment 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, relative to the brush polymer.

[0366] Examples of the crosslinking agent include nitrogen-containing compounds having 2 to 4 nitrogen atoms substituted with methylol groups or alkoxymethyl groups.

[0367] Examples of crosslinking agents include hexamethoxymethylmelamine, tetramethoxymethylglycoluril, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0368] The brush layer-forming composition may contain a surfactant. The surfactant is an additive for improving the coatability to the substrate. Known surfactants such as nonionic surfactants and fluorine-based surfactants can be used as the surfactant. The content of the surfactant in the brush layer-forming composition is, for example, 0.1% by mass to 5% by mass relative to the brush polymer.

[0369] In the brush layer-forming composition, if the components excluding the solvent are defined as the solid content, the solid content includes the brush polymer and additives added as needed. The concentration of the solid content in the brush layer-forming composition is not particularly limited, but is, for example, 0.1% by mass to 15% by mass, and preferably 0.1% by mass to 10% by mass.

[0370] The brush film-forming material can be a polymer material known in the art as a brush material, such as hydroxyl-terminated polystyrene polymer (PS, manufactured by POLYMER SOURCE INC.).

[0371] After forming a brush film on the entire surface (on the patterned neutral film and on the exposed underlayer film), the brush film on the patterned neutral film is etched or stripped to expose the neutral film, forming a template film for self-assembly patterns composed of the neutral film and the brush film. The brush film can be removed using, for example, a mixed solution of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (e.g., OK73 Thinner, manufactured by Tokyo Ohka Kogyo Co., Ltd.).

[0372] <Formation of Self-Assembled Film and Formation of Self-Assembled Pattern> A self-assembled film can be formed by applying the self-assembled film-forming composition described below to the neutral film, preferably the template film obtained in the above step, by the appropriate application method described above, followed by baking. The baking temperature is appropriately selected from, for example, 80 to 140°C and the baking time is 0.3 to 60 minutes. Preferably, the baking temperature is 80 to 120°C and the baking time is about 0.5 to 2 minutes. The thickness of the self-assembled film is, for example, 30 to 10,000 nm, or 20 to 2,000 nm, or about 10 to 200 nm.

[0373] The self-assembled film thus formed is then subjected to a treatment that results in rearrangement of the block copolymer material, such as ultrasonic treatment, solvent treatment, or thermal annealing, to generate a microphase-separated structure and obtain a self-assembled pattern. In many applications, it may be possible to achieve phase separation of the block copolymer layer simply by heating or so-called thermal annealing. Thermal annealing can be performed in the atmosphere or in an inert gas under normal, reduced, or increased pressure conditions. The conditions for thermal annealing are not particularly limited, but can be, for example, 180°C to 300°C, 190°C to 280°C, or 260°C in the atmosphere. The treatment time is not particularly limited, but is typically 1 to 30 minutes, for example, 3 to 10 minutes.

[0374] [Self-Assembled Film and Self-Assembled Film-Forming Composition] A self-assembled film is, for example, a film containing a block copolymer.

[0375] The thickness of the self-assembled film is not particularly limited, but is preferably 10 nm to 100 nm, more preferably 30 nm to 80 nm, and particularly preferably 40 nm to 60 nm.

[0376] <<Self-Assembled Film-Forming Composition>> The self-assembled film-forming composition contains, for example, a block copolymer. The self-assembled film-forming composition usually contains a solvent.

[0377] The self-assembled film-forming composition may have a solids content of 0.1 to 10% by mass, or 0.1 to 5% by mass, or 0.1 to 3% by mass. The solids content is the percentage remaining after removing the solvent from the film-forming composition. The proportion of the block copolymer in the solids content may be 30 to 100% by mass, or 50 to 100% by mass, or 50 to 90% by mass, or 50 to 80% by mass. The number of types of blocks present in the block copolymer may be two or three or more. The number of blocks present in the block copolymer may be two or three or more.

[0378] <<<Block Copolymers>>> Block polymers include combinations such as AB, ABAB, ABA, and ABC. Methods for synthesizing block copolymers include living radical polymerization and living cationic polymerization, in which the polymerization process consists only of an initiation reaction and a propagation reaction, and does not involve side reactions that deactivate the growing ends. The growing ends can maintain their propagation activity during the polymerization reaction. By preventing chain transfer, a polymer (PA) of uniform length can be obtained. By adding a different monomer (mb), the growing end of this polymer (PA) can be used to polymerize the monomer (mb) and form a block copolymer (AB).

[0379] For example, when there are two types of blocks, PA and PB, the molar ratio of the polymer chain (PA) to the polymer chain (PB) can be 1:9 to 9:1, preferably 3:7 to 7:3. The volume ratio of the block copolymer is, for example, 30:70 to 70:30. The homopolymer PA or PB is a polymer of a polymerizable compound having at least one radically polymerizable reactive group (vinyl group or vinyl group-containing organic group).

[0380] The weight average molecular weight Mw of the block copolymer is preferably 1,000 to 100,000, or 5,000 to 100,000. A molecular weight Mw of 1,000 or more provides excellent coatability onto the base substrate, while a molecular weight Mw of 100,000 or less provides excellent solubility in solvents. The polydispersity index (Mw / Mn) of the block copolymer is preferably 1.00 to 1.50, and more preferably 1.00 to 1.20.

[0381] Known block copolymers can be used in the present invention. Specific examples of block copolymers include a combination of a silicon-containing polymer chain and a silicon-free polymer chain, which is preferable because it can increase the difference in dry etching rate. Examples of silicon-containing polymer chains include silylated polystyrene derivatives. Examples of silylated polystyrene derivatives include polysilanes (e.g., polydihexylsilane), polysiloxanes (e.g., polydimethylsiloxane), poly(trimethylsilylstyrene), and poly(pentamethyldisilylstyrene). In particular, the silylated polystyrene derivatives are preferably poly(4-trimethylsilylstyrene) and poly(4-pentamethyldisilylstyrene), which have a substituent at the 4-position.

[0382] A preferred example of the block copolymer is a block copolymer obtained by combining a silicon-containing polymer having a structural unit of styrene, which may be substituted with an organic group, or a silicon-containing polymer having a structural unit derived from lactide, with a silicon-containing polymer having a structural unit of styrene substituted with a silicon-containing group. Among these, a combination of a silylated polystyrene derivative and a polystyrene derivative, or a combination of a silylated polystyrene derivative and polylactide is preferred. Among these, a combination of a silylated polystyrene derivative having a substituent at the 4-position and a polystyrene derivative having a substituent at the 4-position, or a combination of a silylated polystyrene derivative having a substituent at the 4-position and polylactide is preferred. More preferred examples of the block copolymer include a combination of poly(trimethylsilylstyrene) and polymethoxystyrene, a combination of polystyrene and poly(trimethylsilylstyrene), and a combination of poly(trimethylsilylstyrene) and poly(D,L-lactide). More preferred specific examples of the block copolymer include a combination of poly(4-trimethylsilylstyrene) and poly(4-methoxystyrene), a combination of polystyrene and poly(4-trimethylsilylstyrene), and a combination of poly(4-trimethylsilylstyrene) and poly(D,L-lactide). Most preferred specific examples of the block copolymer include a poly(4-methoxystyrene) / poly(4-trimethylsilylstyrene) block copolymer and a polystyrene / poly(4-trimethylsilylstyrene) block copolymer. The entire disclosure of WO2018 / 135456 is incorporated herein by reference.

[0383] The block copolymer may be a block copolymer obtained by bonding a non-silicon-containing polymer with a silicon-containing polymer having a structural unit of styrene substituted with a silicon-containing group, and the non-silicon-containing polymer may be a block copolymer containing a unit structure represented by the following formula (1-1c) or formula (1-2c): (In formula (1-1c) or formula (1-2c), R １ and R ２each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms; R ３ ~R ５ each independently represents a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cyano group, an amino group, an amido group, or a carbonyl group.

[0384] The silicon-containing group may contain one silicon atom. The silicon-containing polymer may contain a unit structure represented by the following formula (2c): (In formula (2c), R ６ ~R ８ each independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0385] Furthermore, the block copolymer may be one described in JP-T-2019-507815 A, including the following [BCP11] to [BCP14]. The entire disclosure of JP-T-2019-507815 A is incorporated herein by reference. [BCP11]: A block copolymer containing 5-vinylbenzo[d][1,3]dioxole. [BCP12]: The block copolymer described in [BCP11], wherein the block copolymer further contains a silicon-containing block. [BCP13]: The block copolymer described in [BCP12], wherein the block copolymer further contains pentamethyldisilylstyrene. [BCP14]: The block copolymer described in [BCP13], wherein the block copolymer is poly(5-vinylbenzo[d][1,3]dioxole)-b-poly(pentamethyldisilylstyrene).

[0386] The synthesis of the above-described poly(5-vinylbenzo[d][1,3]dioxole-block-4-pentamethyldisilylstyrene) is shown in Scheme 1 below. (Scheme 1) Me represents a methyl group.

[0387] Preferably, the silicon-containing polymer or silicon-containing block is poly(4-trimethylsilylstyrene) derived from 4-trimethylsilylstyrene. Preferably, the silicon-containing polymer or silicon-containing block is poly(pentamethyldisilylstyrene) derived from pentamethyldisilylstyrene. The aryl group having 6 to 40 carbon atoms refers to a monovalent group of a monocyclic or polycyclic aromatic hydrocarbon having 6 to 40 carbon atoms, and specific examples include a phenyl group, a naphthyl group, and an anthryl group. The entire disclosure of WO2020 / 017494 is incorporated herein by reference.

[0388] Also, a block copolymer made of a combination of the following monomers may be used: styrene, methyl methacrylate, dimethylsiloxane, propylene oxide, ethylene oxide, vinylpyridine, vinylnaphthalene, D,L-lactide, methoxystyrene, methylenedioxystyrene, trimethylsilylstyrene, and pentamethyldisilylstyrene.

[0389] Useful block copolymers contain at least two blocks and may be diblock, triblock, tetrablock, etc. copolymers with distinct blocks, each of which may be a homopolymer or a random or alternating copolymer.

[0390] Typical block copolymers include polystyrene-b-polyvinylpyridine, polystyrene-b-polybutadiene, polystyrene-b-polyisoprene, polystyrene-b-polymethylmethacrylate, polystyrene-b-polyalkenyl aromatic, polyisoprene-b-polyethylene oxide, polystyrene-b-poly(ethylene-propylene), polyethylene oxide-b-polycaprolactone, polybutadiene-b-polyethylene oxide, polystyrene-b-poly(t-butyl (meth)acrylate), polymethylmethacrylate-b-poly(t-butyl methacrylate), polyethylene oxide-b-polypropylene oxide, polystyrene-b-polytetrafluoroethylene Examples of block copolymers include hydrofuran, polystyrene-b-polyisoprene-b-polyethylene oxide, poly(styrene-b-dimethylsiloxane), poly(methyl methacrylate-b-dimethylsiloxane), poly(methyl (meth)acrylate-r-styrene)-b-polymethyl methacrylate, poly(methyl (meth)acrylate-r-styrene)-b-polystyrene, poly(p-hydroxystyrene-r-styrene)-b-polymethyl methacrylate, poly(p-hydroxystyrene-r-styrene)-b-polyethylene oxide, polyisoprene-b-polystyrene-b-polyferrocenylsilane, or a combination comprising at least one of the foregoing block copolymers.

[0391] Further examples include block copolymers formed from a combination of the organic polymers and / or metal-containing polymers described below.

[0392] Typical organic polymers include poly(9,9-bis(6'-N,N,N-trimethylammonium)-hexyl)-fluorenephenylene) (PEP), poly(4-vinylpyridine) (4PVP), hydroxypropyl methylcellulose (HPMC), polyethylene glycol (PEG), poly(ethylene oxide)-poly(propylene oxide) diblock or multiblock copolymers, polyvinyl alcohol (PVA), poly(ethylene-vinyl alcohol) (PEVA), polyacrylic acid (PAA), polylactic acid (PLA), poly(ethyloxazoline), poly(alkyl acrylate), poly(acrylic acid), poly(ethylene-vinyl alcohol ... Examples of suitable polyvinyl alcohols include, but are not limited to, polyvinyl amides, poly(N-alkylacrylamides), poly(N,N-dialkylacrylamides), polypropylene glycol (PPG), polypropylene oxide (PPO), partially or fully hydrogenated poly(vinyl alcohol), dextran, polystyrene (PS), polyethylene (PE), polypropylene (PP), polyisoprene (PI), polychloroprene (CR), polyvinyl ether (PVE), polyvinyl acetate (PVA), polyvinyl chloride (PVC), polyurethane (PU), polyacrylates, polymethacrylates, oligosaccharides, or polysaccharides.

[0393] Metal-containing polymers include, but are not limited to, silicon-containing polymers such as polydimethylsiloxane (PDMS), polyhedral silsesquioxane (POSS), or poly(trimethylsilylstyrene) (PTMSS) or polymers containing silicon and iron such as poly(ferrocenyldimethylsilane) (PFS).

[0394] Exemplary block copolymers include, but are not limited to, diblock copolymers such as polystyrene-b-polydimethylsiloxane (PS-PDMS), poly(2-vinylpropylene)-b-polydimethylsiloxane (P2VP-PDMS), polystyrene-b-poly(ferrocenyldimethylsilane) (PS-PFS), or polystyrene-b-polyDL-lactic acid (PS-PLA) or triblock copolymers such as polystyrene-b-poly(ferrocenyldimethylsilane)-b-poly(2-vinylpyridine) (PS-PFS-P2VP), polyisoprene-b-polystyrene-b-poly(ferrocenyldimethylsilane) (PI-PS-PFS), or polystyrene-b-poly(ferrocenyldimethylsilane)-b-polystyrene (PS-PTMSS-PS). In one embodiment, the PS-PTMSS-PS block copolymer comprises a poly(trimethylsilylstyrene) polymer block composed of two chains of PTMSS connected by a linker containing four styrene units. Modified versions of block copolymers, such as those disclosed in U.S. Patent Application Publication No. 2012 / 0046415, are also contemplated.

[0395] Other block copolymers include, for example, a block copolymer in which a polymer having styrene or a derivative thereof as a constituent unit is bonded to a polymer having a (meth)acrylic acid ester as a constituent unit, a block copolymer in which a polymer having styrene or a derivative thereof as a constituent unit is bonded to a polymer having siloxane or a derivative thereof as a constituent unit, and a block copolymer in which a polymer having alkylene oxide as a constituent unit is bonded to a polymer having a (meth)acrylic acid ester as a constituent unit. Note that "(meth)acrylic acid ester" refers to either or both of an acrylic acid ester having a hydrogen atom bonded to the α-position and a methacrylic acid ester having a methyl group bonded to the α-position.

[0396] Examples of (meth)acrylic acid esters include those in which a substituent such as an alkyl group or a hydroxyalkyl group is bonded to a carbon atom of (meth)acrylic acid. Examples of the alkyl group used as the substituent include linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms. Specific examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, anthracene (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethane (meth)acrylate, and propyltrimethoxysilane (meth)acrylate.

[0397] Examples of styrene derivatives include 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, and vinylpyridine.

[0398] Examples of siloxane derivatives include dimethylsiloxane, diethylsiloxane, diphenylsiloxane, methylphenylsiloxane, etc. Examples of alkylene oxides include ethylene oxide, propylene oxide, isopropylene oxide, butylene oxide, etc.

[0399] Examples of the block copolymer include polystyrene / poly(methyl methacrylate) block copolymer, styrene-polyethyl methacrylate block copolymer, styrene-(poly-t-butyl methacrylate) block copolymer, styrene-polymethacrylic acid block copolymer, styrene-polymethyl acrylate block copolymer, styrene-polyethyl acrylate block copolymer, styrene-(poly-t-butyl acrylate) block copolymer, styrene-polyacrylic acid block copolymer, etc. The entire disclosure of WO2022 / 039187 is incorporated herein by reference.

[0400] <<<Solvent>>> Examples of solvents that can be used in the self-assembled film-forming composition include the following organic solvents: Aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane Aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, and trimethylbenzene Methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, Monoalcohol solvents such as sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; Polya...

Claims

1. A composition for forming a silicon-containing underlayer film for forming a self-assembled pattern, comprising: [A] a polysiloxane; [B] a strongly acidic additive in an amount of 0 to less than 2 parts by mass per 100 parts by mass of the polysiloxane; and [C] a solvent, wherein the polysiloxane contains a structural unit derived from a hydrolyzable silane (A) represented by the following formula (A-1): (In formula (A-1), a represents an integer of 1 to 3. b represents an integer of 0 to 2. a+b represents an integer of 1 to 3. R １ represents an organic group having a ring structure other than an aromatic hydrocarbon ring. ２ represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or 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. X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. R １ , R ２ and when X is plural, R １ , R ２ and X may be the same or different.

2. The composition for forming a silicon-containing underlayer film according to claim 1, wherein the strongly acidic additive is a strongly acidic additive having a first acid dissociation constant in water of 1 or less.

3. The composition for forming a silicon-containing underlayer film according to claim 1, wherein the strongly acidic additive is a photoacid generator.

4. The above R １ The composition for forming a silicon-containing underlayer film according to claim 1 , wherein the ring structure in the formula (I) contains a heteroatom.

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

6. A method for manufacturing a substrate having a self-assembled pattern, comprising: a step of forming an underlayer film on a substrate using a silicon-containing underlayer film forming composition according to any one of claims 1 to 5; and a step of forming a self-assembled film above the underlayer film to form a self-assembled pattern.

7. A method for manufacturing a substrate having a self-assembled pattern, comprising the steps of: forming an underlayer film on a substrate using a silicon-containing underlayer film forming composition described in any one of claims 1 to 5; forming a neutral film on the underlayer film; and forming a self-assembled film on the neutral film to form a self-assembled pattern.

8. A method for manufacturing a substrate having a self-assembled pattern, comprising: forming an underlayer film on a substrate using a silicon-containing underlayer film forming composition described in any one of claims 1 to 5; forming a neutral film on a portion of the underlayer film; forming a brush film on the underlayer film on which the neutral film is not formed, and forming a template film for the self-assembled pattern formed from the neutral film and the brush film; and forming a self-assembled film on the template film for the self-assembled pattern, to obtain a self-assembled pattern.

9. A method for manufacturing a substrate having a self-assembled pattern, comprising the steps of: forming an organic underlayer film on a substrate; forming an underlayer film on the organic underlayer film using a silicon-containing underlayer film forming composition described in any one of claims 1 to 5; forming a neutral film on a portion of the underlayer film; forming a brush film on the underlayer film on which the neutral film is not formed, and forming a template film for a self-assembled pattern formed from the neutral film and the brush film; and forming a self-assembled film on the template film for the self-assembled pattern, thereby obtaining a self-assembled pattern.

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

11. A method for producing a substrate having the self-assembled pattern according to claim 6, which is used for forming a self-assembled pattern by directed self-assembly (DSA).

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

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