Method for manufacturing laminated body and method for manufacturing semiconductor element

Abstract

A method for manufacturing a laminate having a surface modification layer and a semiconductor substrate, comprising: a first step of applying a surface modifier containing an organic compound (A) having a hydroxyl group protected with a deprotectable protecting group and a solvent (B) on a semiconductor substrate, and then performing firing to obtain a surface modification layer precursor; and a second step of thinning the surface modification layer precursor by contacting the surface modification layer precursor with a thinning liquid (X) to obtain a surface modification layer having a film thickness of 5 nm or less.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a multilayer, and suitably to a method for manufacturing a multilayer on which a resist pattern is formed. Furthermore, this invention relates to a method for manufacturing a semiconductor device. Background Technology

[0002] Photolithography, which uses resist compositions, has been a standard technique in semiconductor device manufacturing for a long time. In recent years, with the increasing integration of semiconductor devices, there has been a demand for finer patterns, such as wiring. As patterns become finer, shorter wavelengths of light, such as far-ultraviolet light, vacuum ultraviolet light, electron beams (EB), and X-rays, are being used as light sources. In particular, recently, short-wavelength light, such as KrF excimer lasers (wavelength 248nm) and ArF excimer lasers (wavelength 193nm), has been used to form resist patterns.

[0003] Along with this, the diffuse reflection of active light from the semiconductor substrate and the effects of standing waves have become major problems. Therefore, in order to solve this problem, methods of setting a bottom anti-reflective coating (BARC) between the photoresist and the semiconductor substrate have been extensively studied. As such an anti-reflective coating, considering its ease of use, organic anti-reflective coatings formed from compositions containing polymers with light-absorbing groups (chromophores) have been extensively studied (for example, Patent Document 1).

[0004] On the other hand, while EUV (ultraviolet light, wavelength 13.5nm) and electron beams used in further microfabrication techniques do not cause reflection from the semiconductor substrate, the problem arises from the collapse of the resist pattern accompanying the pattern miniaturization. Therefore, research was conducted on a resist underlayer film with high adhesion to the resist.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Publication No. 2008-501985 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] In conventional photoresist underlayers, etching defects such as side etching during the etching process are prone to occur. Therefore, if the substrate surface can be modified by a surface modification layer that is thinner than conventional underlayers, etching defects such as side etching can be expected to be eliminated, the adhesion of the photoresist will be improved, and the photoresist resolution in advanced lithography processes will be improved.

[0010] However, it is not easy to form a thin surface modification layer uniformly.

[0011] The present invention was made in view of such circumstances, and its object is to provide a method for manufacturing a stack capable of forming a thin surface-modified layer, a method for manufacturing a semiconductor device using the manufacturing method, and a stack having a thin surface-modified layer.

[0012] Methods for solving problems

[0013] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above-mentioned problems could be solved, and completed the present invention with the following main points.

[0014] That is, the present invention includes the following solutions.

[0015] [1] A method for manufacturing a stack having a surface modification layer and a semiconductor substrate, comprising the following steps: The first step involves coating a surface modifier containing an organic compound (A) having hydroxyl groups that can be deprotected by a protecting group and a solvent (B) onto a semiconductor substrate, followed by firing to obtain a surface-modified layer precursor; and The second step involves contacting the aforementioned surface-modified layer precursor with a thinning solution (X) to thin the surface-modified layer precursor, thereby obtaining a surface-modified layer with a film thickness of 5 nm or less.

[0016] [2] According to the method for manufacturing the laminate described in [1], the organic compound (A) is any one of the following: a vinyl polymer having hydroxyl groups (A1), a polymer having a unit structure shown in formula (Y) (A2), a resin (A3), a polymer having a unit structure shown in formula (Z1) (A4), and a compound (A5) having two or more of the following structures (M). The resin (A3) described above is a resin with a composite unit structure, which has: a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms. The resin (A3) described above is obtained by a reaction in which a covalent bond is formed between the carbon atom of the aromatic ring constituting the unit structure (A) and the carbon atom in the unit structure (B).

[0017]

[0018] (In formula (Y), T represents a divalent group with an aliphatic ring.)

[0019] Q represents a divalent organic group with a hydroxyl group, indicating that T is combined with R. 11 Connected divalent organic groups.

[0020] R 11 (This indicates a base with a 1 valence.)

[0021] (In formula (Z1), A independently represents a hydrogen atom, a methyl atom, or an ethyl atom, and Q...) 1 and Q 2 (These represent divalent bases independently.)

[0022] (In structure (M), R) 101 This indicates a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or an alkoxyalkyl group with 2 to 6 carbon atoms. * indicates a bonding bond.

[0023] [3] According to the method of manufacturing the laminate as described in [1] or [2], the solvent (B) comprises at least one selected from carboxylic acids having hydroxyl groups, straight-chain or cyclic alkyl ketones, cyclic lactones, monoalkylene glycol monoalkyl ethers, monocarboxylic acid esters of monoalkylene glycol monoalkyl ethers, and alkoxycarboxylic acid esters of monoalkylene glycol monoalkyl ethers.

[0024] [4] In the method for manufacturing the laminate according to any one of [1] to [3], the thinning liquid (X) comprises at least one of an organic solvent and water.

[0025] [5] In the method for manufacturing the laminate according to any one of [1] to [4], the surface modifier further comprises at least one compound (C) selected from acids, their salts and acid-producing agents.

[0026] [6] In the manufacturing method of the stacked body according to any one of [1] to [5], the semiconductor substrate is an inorganic or organic substrate, or a substrate having a film of inorganic or organic material.

[0027] [7] According to the manufacturing method of the laminate described in [6], the inorganic material is selected from at least one of metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides and metal carbonitrides.

[0028] [8] According to the manufacturing method of the stacked body described in [6], the organic material is selected from at least one of amorphous carbon, graphite, fullerene, carbon nanotubes, diamond, diamond-like carbon, polyimide, and organic films that have been partially doped or replaced with boron, oxygen, nitrogen, phosphorus, silicon, sulfur or halogen.

[0029] [9] The method for manufacturing a laminate according to any one of [1] to [8] further comprises a resist underlayer film.

[0030]

[10] In the manufacturing method of the laminate according to any one of [1] to [9], the second step is to obtain a surface modified layer with a film thickness of 5 nm or less by spin-coating the surface modified layer precursor with the thinning liquid (X).

[0031]

[11] The method for manufacturing the stack according to any one of [1] to

[10] is used for EUV or electron beam lithography.

[0032]

[12] A method for manufacturing a semiconductor device, comprising the following steps: The step of forming a resist film on a laminate obtained by the manufacturing method of any one of [1] to

[11] ; and The process of exposing and developing the above-mentioned resist film to obtain a resist pattern.

[0033]

[13] A stack having a semiconductor substrate and a surface-modified layer with a thickness of less than 5 nm formed using an organic compound (A) containing hydroxyl groups that can be deprotected by a protective group and a solvent (B).

[0034]

[14] The stack according to

[13] is used for EUV or electron beam lithography.

[0035]

[15] A surface modifier is a surface modifier containing an organic compound (A) having hydroxyl groups that can be protected by a deprotecting group and a solvent (B). It is used in the manufacturing method of the laminate as described in any one of [1] to

[11] .

[0036] The effects of the invention

[0037] According to the present invention, a method for manufacturing a stack capable of forming a thin surface-modified layer, a method for manufacturing a semiconductor device using the method, and a stack having a thin surface-modified layer can be provided. Detailed Implementation

[0038] (Manufacturing method of laminated bodies and laminated bodies)

[0039] The method for manufacturing the laminate of the present invention includes a first step and a second step. The method for manufacturing the laminate of the present invention may further include other steps.

[0040] The first step involves coating a surface modifier containing an organic compound (A) with hydroxyl groups that can be deprotected by a protective group and a solvent (B) onto a semiconductor substrate, followed by firing to obtain a surface modified layer precursor.

[0041] The second step is to thin the surface modification layer precursor by contacting it with a thinning solution (X) to obtain a surface modification layer with a film thickness of less than 5 nm.

[0042] An organic film is obtained by coating an organic compound (A) containing hydroxyl groups that can be deprotected by a protecting group and a solvent (B) with a surface modifier, followed by firing. However, it is not easy to obtain a thin film (e.g., a film thickness of less than 5 nm) without film defects such as pinholes and uneven coating by this process alone. It is necessary to carefully control the coating conditions, firing conditions, etc.

[0043] Therefore, the inventors conducted an in-depth study on a method for manufacturing a laminate capable of forming a thin surface-modified layer, and found that, as a first step, a layer (a precursor of the surface-modified layer) with a film thickness that is thicker than the target film thickness is formed, and as a second step, the layer is thinned by contacting it with a thinning solution (X), thereby enabling the formation of a thin surface-modified layer, thus completing the present invention.

[0044] When the surface-modified layer precursor obtained from the surface modifier is brought into contact with the thinning solution (X), the surface-modified layer precursor is not completely removed from the substrate, and remains as a thin surface-modified layer on the substrate. The inventors believe that this is related to the interaction between the hydroxyl groups of the organic compound (A), which can be protected by deprotected protecting groups, and the substrate.

[0045] The laminate obtained by the manufacturing method of the present invention has a surface modification layer and a semiconductor substrate.

[0046] The laminate obtained by the manufacturing method of the present invention is suitable for use in EUV (extreme ultraviolet light, wavelength 13.5 nm) or electron beam lithography.

[0047] The laminate obtained by the manufacturing method of the present invention may further have other layers or films. Examples of other layers include, for example, a photoresist underlayer. There are no particular limitations on the photoresist underlayer, as long as it is used in the photolithography process. For example, the photoresist underlayer may be a silicon-containing photoresist underlayer or an organic underlayer. Examples of organic underlayers include, for example, organic underlayers with high carbon content. Organic underlayers with high carbon content are obtained, for example, from compositions containing broadly defined phenolic varnish resins. Examples of such compositions include, for example, the compositions for forming photoresist underlayers described in International Publication No. 2010 / 147155, International Publication No. 2012 / 077640, International Publication No. 2013 / 005797, and International Publication No. 2017 / 094780.

[0048] The photoresist underlayer is, for example, the underlayer of the surface modification layer. The photoresist underlayer is disposed, for example, between the semiconductor substrate and the surface modification layer.

[0049] Furthermore, in this invention, there is no clear distinction between film and layer.

[0050] The thickness of the surface-modified layer is less than 5 nm, preferably less than 3 nm. There is no particular limitation on the lower limit of the thickness of the surface-modified layer; the thickness of the surface-modified layer can be greater than 0.1 nm or greater than 0.2 nm.

[0051] In this invention, the film thickness is measured as follows.

[0052] The film thickness was measured using an elliptic film thickness measuring device RE-3100 (manufactured by SCREEN).

[0053] <Step 1>

[0054] The first step is to obtain the precursor for the surface-modified layer.

[0055] In the first step, after the surface modifier is coated on the semiconductor substrate, it is fired to obtain the surface modified layer precursor.

[0056] There are no particular restrictions on the semiconductor substrate used in the first process, for example, as long as it is a substrate used in the manufacture of precision integrated circuit components.

[0057] Examples of semiconductor substrates include inorganic substrates, organic substrates, substrates with inorganic films, and substrates with organic films.

[0058] Examples of inorganic substances include arsenic, metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and metal carbonitrides. They can be used individually or in combination of two or more.

[0059] Examples of metals include silicon, germanium, titanium, tungsten, hafnium, zirconium, chromium, copper, aluminum, indium, gallium, palladium, iron, tantalum, iridium, molybdenum, or alloys thereof.

[0060] Examples of metal oxides include SiO2 and TiO2.

[0061] Examples of metal nitrides include SiN, TiN, and TaN.

[0062] Examples of metal carbides include SiC and TiC.

[0063] Examples of metal oxynitrides include SiON and TiON.

[0064] Examples of metal oxycarbides include SiOC and TiOC.

[0065] Examples of metal carbonitrides include SiCN and TiCN.

[0066] Examples of organic compounds include amorphous carbon, graphite, fullerenes, carbon nanotubes, diamond, diamond-like carbon, and polyimide. They can be used individually or in combination of two or more. These organic compounds can be partially doped or replaced with boron, oxygen, nitrogen, phosphorus, silicon, sulfur, or halogens.

[0067] Examples of semiconductor substrates include, for example, silicon wafers coated with silicon oxide, silicon nitride, or silicon oxynitride films; silicon nitride substrates; quartz substrates; glass substrates (including alkali-free glass, low-alkali glass, and crystal glass); glass substrates with ITO (indium tin oxide) or IZO (indium zinc oxide) films; plastic substrates (polyimide, PET, etc.); substrates coated with low-k materials; and flexible substrates.

[0068] There are no particular limitations on the method of applying surface modifiers to semiconductor substrates; for example, it can be carried out by appropriate coating methods such as spin coaters or coating machines.

[0069] The firing process after the surface modifier is applied to the semiconductor substrate can be carried out using heating methods such as a hot plate.

[0070] The firing conditions are appropriately selected from a firing temperature of 40℃~400℃ or 80℃~250℃ and a firing time of 0.3 minutes~60 minutes. Preferably, the firing temperature is 120℃~250℃ and the firing time is 0.5 minutes~2 minutes.

[0071] A layered surface-modified layer precursor is obtained by evaporating the solvent in the surface modifier through firing. Furthermore, depending on the situation, a crosslinking reaction occurs through firing to obtain a crosslinked layer. The crosslinking includes partial crosslinking.

[0072] The thickness of the precursor film for the surface-modified layer formed here is, for example, 1 nm to 1,000 nm, or 1 nm to 500 nm, or 1 nm to 300 nm, or 1 nm to 200 nm or 1 to 150 nm.

[0073] <<Surface Modifiers>>

[0074] The surface modifier contains an organic compound (A) having hydroxyl groups that can be protected by a deprotecting group and a solvent (B). The surface modifier may further contain other components.

[0075] The surface modifier used in the manufacturing method of the laminate of the present invention is also the subject of the present invention.

[0076] <<<Organic Compound (A)>>>

[0077] As an organic compound (A), there are no particular restrictions as long as it has a hydroxyl group that can be deprotected by a protecting group, and it can be appropriately selected according to the purpose.

[0078] Organic compound (A) can be a low-molecular-weight compound or a high-molecular-weight compound. Organic compound can be a resin or a polymer.

[0079] As a protecting group for hydroxyl groups, there are no particular limitations as long as deprotection is possible. Examples include alkyl groups with 1 to 4 carbon atoms and alkoxyalkyl groups with 2 to 6 total carbon atoms.

[0080] The hydroxyl group protected by a protecting group that can be deprotected is, for example, the hydroxyl group in a hydroxymethyl group that is bonded to a nitrogen atom or a carbon atom that forms an aromatic hydrocarbon ring.

[0081] Protecting groups capable of deprotection can be deprotected, for example, by heat. Protecting groups capable of deprotection can also be deprotected in the presence of a catalyst.

[0082] When the organic compound (A) is a resin or polymer, specific examples include polyesters, polystyrene, polyimide, acrylic polymers, methacrylic polymers, polyvinyl ether, phenolic varnish, naphthol varnish, polyether, polyamide, polycarbonate, and other addition and condensation polymers.

[0083] There are no particular limitations on the weight-average molecular weight of the organic compound (A), for example, it can be 300 to 1,000,000. From the viewpoint of suppressing precipitation from surface modifiers, it is preferable to have a weight-average molecular weight of 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of combining storage stability and coating properties, it is preferable to have a weight-average molecular weight of 300 or more.

[0084] Here is an example of an organic compound (A).

[0085] <<<<Polymer (A1)>>>>

[0086] As an example of an organic compound (A), polymer (A1) is a vinyl polymer having hydroxyl groups. A vinyl polymer is a polymer formed by the polymerization of polymerically unsaturated bonds of compounds having groups having polymerically unsaturated bonds. Polymer (A1) can be a homopolymer or a copolymer.

[0087] Examples of groups having polymerizable unsaturated bonds include (meth)acryloyl, (meth)acrylamido, vinyl, vinylaryl (e.g., styryl), vinyloxy, allyl, maleimide, etc.

[0088] The polymer (A1) has, for example, the unit structure shown by the following formula (X1).

[0089]

[0090] (In equation (X1), R) 1 Indicates an alkyl group having 1 to 10 hydrogen or carbon atoms. L 1 This represents an ester bond, which can be a phenylene or amide bond with substituents. L 2 This indicates a monovalent group containing a hydroxyl group.

[0091] As an example of the unit structure shown in equation (X1), examples include the unit structure shown in equation (X1-1) to the unit structure shown in equation (X1-3).

[0092]

[0093] (In equations (X1-1) to (X1-3), R) 1 Indicates an alkyl group having 1 to 10 hydrogen or carbon atoms. L 2 This indicates a monovalent group containing a hydroxyl group. R 2 Each substituent can be represented independently. m represents an integer from 0 to 4.

[0094] As R 1Alkyl groups having 1 to 10 carbon atoms include, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, 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, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl 1,2-Dimethyl-cyclopropyl, 2,3-Dimethyl-cyclopropyl, 1-Ethyl-cyclopropyl, 2-Ethyl-cyclopropyl, n-Hexyl, 1-Methyl-n-pentyl, 2-Methyl-n-pentyl, 3-Methyl-n-pentyl, 4-Methyl-n-pentyl, 1,1-Dimethyl-n-butyl, 1,2-Dimethyl-n-butyl, 1,3-Dimethyl-n-butyl, 2,2-Dimethyl-n-butyl, 2,3-Dimethyl-n-butyl, 3,3-Dimethyl-n-butyl, 1-Ethyl-n-butyl, 2-Ethyl-n-butyl, 1,1,2-Trimethyl -n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl Cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, n-heptyl, cycloheptyl, norbornyl, n-octyl, cyclooctyl, n-nonyl, isobornyl, tricyclononyl, n-decyl, adamantyl, tricyclodecyl, etc. Among these, methyl is preferred.

[0095] As R 2 Examples of substituents in this context include halogen atoms, hydroxyl groups, alkyl groups with 1 to 3 carbon atoms, and alkoxy groups with 1 to 3 carbon atoms.

[0096] L 2 It can have one or more hydroxyl groups.

[0097] As L 2 Examples include hydroxyl groups and monovalent groups with 1 to 20 carbon atoms that have hydroxyl groups.

[0098] The constituent atoms of a monovalent group having 1 to 20 carbon atoms and containing a hydroxyl group can be only carbon atoms and hydrogen atoms, excluding the hydroxyl group.

[0099] Monovalent groups with 1 to 20 carbon atoms that contain a hydroxyl group may or may not have heteroatoms. Examples of heteroatoms include oxygen, nitrogen, and sulfur atoms.

[0100] A monovalent group with 1 to 20 carbon atoms containing a hydroxyl group may or may not have a halogen atom.

[0101] A monovalent group with 1 to 20 carbon atoms containing a hydroxyl group may or may not have an aromatic ring. Examples of aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles. Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings.

[0102] Examples of monomers used for the unit structure shown in formula (X1-1) include the following compounds.

[0103]

[0104] Examples of monomers used for the unit structure shown in formula (X1-2) include the following compounds.

[0105]

[0106] (Me represents methyl.)

[0107] Examples of monomers used for the unit structure shown in formula (X1-3) include the following compounds.

[0108]

[0109] The polymer (A1) may have unit structures other than those shown in formula (X1).

[0110] Examples of monomers that derive such unit structures include, but are not limited to, acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, acrylonitrile, etc.

[0111] Specific examples of acrylate compounds include methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthracene methyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 3-acryloyloxypropyltriethoxysilane, glycidyl acrylate, etc., but are not limited to these.

[0112] Specific examples of methacrylate compounds include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, bromophenyl methacrylate, etc., but are not limited to these.

[0113] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthraylacrylamide.

[0114] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthraylmethacrylamide.

[0115] Specific examples of vinyl compounds include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinylacetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc., but are not limited to these.

[0116] Specific examples of styrene compounds include styrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetylstyrene, etc., but are not limited to these.

[0117] Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide, but are not limited to these.

[0118] <<<<Polymer (A2)>>>>

[0119] Polymer (A2), as an example of organic compound (A), is a polymer having the unit structure shown in the following formula (Y).

[0120]

[0121] (In formula (Y), T represents a divalent group with an aliphatic ring.)

[0122] Q represents a divalent organic group with a hydroxyl group, indicating that T is combined with R. 11 Connected divalent organic groups.

[0123] R 11 (This indicates a base with a 1 valence.)

[0124] R 11 -Q group is a substituent for aliphatic rings.

[0125] Aliphatic rings are, for example, rings in which 4 to 10 carbon atoms are linked in a ring-like manner, preferably rings in which 6 carbon atoms are linked in a ring-like manner.

[0126] Aliphatic rings except R 11 Other substituents besides the -Q group can also be present. Examples of such substituents include alkyl groups with 1 to 10 carbon atoms, aryl groups with 6 to 20 carbon atoms, halogen atoms, nitro groups, and amino groups.

[0127] The polymer (A2) is preferably a polymer having the unit structure shown in the following formula (Y1).

[0128]

[0129] (In equation (Y1), R) 11 R represents a base with a valence of 1. 12 Represents a hydrogen atom or a methyl group. R 13 (This indicates a hydrogen atom or a methyl group.)

[0130] As R 11 There are no particular limitations; examples include organic groups with 1 to 20 carbon atoms.

[0131] The polymer (A2) is obtained, for example, by reacting a polymer having the unit structure shown in formula (Y-1) with a compound shown in formula (Y-2).

[0132]

[0133] (In equation (Y-1), R) 12 Represents a hydrogen atom or a methyl group. R 13 It represents a hydrogen atom or a methyl group.

[0134] In equation (Y-2), R 11 (This indicates a base with a 1 valence.)

[0135] The above reaction is carried out, for example, in the presence of a catalyst. A catalyst, for example, is tetrabutyl bromide. ethyltriphenylbromide That kind of season Salts, such as quaternary ammonium salts like benzyltriethylammonium chloride. The amount of catalyst used can be selected from 0.1% to 10% by mass relative to the total mass of the reactants used in the reaction. The optimal conditions for the reaction, for example, can be selected from the range of 80 to 160°C and 2 to 50 hours.

[0136] R in equations (Y1) and (Y-2) 11 There are no particular restrictions as long as it is a monovalent group. Examples of monovalent groups include monovalent groups with 1 to 20 carbon atoms. Preferably, an aromatic group is an example of a monovalent group. Examples of aromatic groups include monocyclic aromatic hydrocarbon groups and fused-ring aromatic hydrocarbon groups.

[0137] Examples of polymers having the unit structure shown in formula (Y-1) include, for example, 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (manufactured by Daiser Chemical Industry Co., Ltd., trade name: EHPE3150), 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol and 3,4-epoxycyclohexenylmethyl-3,'4'-epoxycyclohexenecarboxylate (manufactured by Daiser Chemical Industry Co., Ltd., trade name: EHPE3150CE).

[0138] The compound represented by formula (Y-2) is preferably, for example, a fused-ring aromatic carboxylic acid or a monocyclic aromatic carboxylic acid. Examples of fused-ring aromatic carboxylic acids include naphtholic acid and anthracenic acid, but 9-anthracarboxylic acid is preferred. Benzoic acid is preferred as a monocyclic aromatic carboxylic acid.

[0139] Examples of polymers (A2) include polymers having unit structures as shown in formula (Y1-1) to polymers having unit structures as shown in formula (Y1-12).

[0140]

[0141] <<<<Resin (A3)>>>>

[0142] The resin (A3), as an example of an organic compound (A), is a resin having a composite unit structure.

[0143] The composite unit structure has: a unit structure with an aromatic ring (A) and a unit structure with more than one carbon atom (B).

[0144] Resin (A3) is a resin obtained by reacting carbon atoms of the aromatic ring constituting unit structure (A) with carbon atoms in unit structure (B) to form covalent bonds.

[0145] Additionally, resin (A3) will sometimes be referred to as resin (G) below.

[0146] In this specification, resin (G) is sometimes referred to as "phenolic varnish resin".

[0147] The unit structure (A) contains a skeleton with an aromatic ring, which is a phenolic skeleton.

[0148] The unit structure (A) has, for example, at least one of the following: an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom bonded to an aromatic ring.

[0149] Unit structure (A), for example, does not have heteroatoms as atoms constituting aromatic rings and atoms bonded to aromatic rings.

[0150] Unit structure (B) is a unit structure derived from aldehyde compounds or aldehyde equivalents.

[0151] The unit structure (A) has, for example, at least one of the following: an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom bonded to an aromatic ring.

[0152] Unit structure (A), for example, does not have heteroatoms as atoms constituting aromatic rings and atoms bonded to aromatic rings.

[0153] Unit structures (B) are, for example, unit structures derived from aldehyde compounds or aldehyde equivalents.

[0154] The so-called aldehyde equivalent is an organic compound that can covalently bond with an aromatic ring. It is an organic compound having a ketone group; an acetal group; a ketal group; a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom; a hydroxyl, alkoxy, or halogroup bonded to the α-carbon atom of an alkyl aryl group; or a carbon-carbon unsaturated bond.

[0155] [I. Definition of the term]

[0156] In this specification, the definitions of key terms related to phenolic varnish resins, which are an aspect of the invention of this application, are explained below. Unless otherwise specifically stated, the definitions of the following terms apply to phenolic varnish resins.

[0157] (I-1) "Phenolic varnish resins"

[0158] The term "phenolic varnish resin" is used not only in the narrow sense of phenol / formaldehyde resin (so-called phenolic varnish type phenolic resin) and aniline / formaldehyde resin (so-called phenolic varnish type aniline resin), but also in a broader sense, encompassing resins formed by organic compounds having functional groups capable of covalently bonding with aromatic rings (e.g., aldehyde group; ketone group; acetal group; ketal group; hydroxyl or alkoxy group bonded to secondary or tertiary carbon atoms; hydroxyl, alkoxy, or halogen group bonded to the α-carbon atom (benzyl carbon atom, etc.) of alkyl aryl groups; carbon-carbon unsaturated bonds of divinylbenzene, dicyclopentadiene, etc.) with aromatic rings (preferably having heteroatoms such as oxygen, nitrogen, and sulfur atoms as constituent atoms of the aromatic ring or atoms bonded to the aromatic ring) through covalent bonding (substitution reaction, addition reaction, condensation reaction, or addition-condensation reaction, etc.).

[0159] Therefore, the so-called phenolic varnish resin in this application specification is formed by linking multiple compounds having aromatic rings together by an organic compound containing carbon atoms (sometimes referred to as "linking carbon atoms") derived from the above-mentioned functional groups to form a covalent bond between the linking carbon atoms and the aromatic rings in the compound having aromatic rings.

[0160] In this specification, the terms "unit structure (A)" and "unit structure (B)" are used as the unit structures constituting "phenolic varnish resins". Unit structure (A) is a unit structure derived from a compound having an aromatic ring. Unit structure (B) is a unit structure derived from a compound having functional groups capable of covalently bonding with the aromatic ring of unit structure (A).

[0161] (I-2) "Residues"

[0162] A "residue" is an organic group obtained by replacing a hydrogen atom bonded to a carbon atom or heteroatom (nitrogen atom, oxygen atom, sulfur atom, etc.) with a bonding bond. It can be a monovalent group or a polyvalent group. For example, if one hydrogen atom is replaced by one bonding bond, it becomes a monovalent organic group; if two hydrogen atoms are replaced by bonding bonds, it becomes a divalent organic group.

[0163] (I-3) "Aromatic rings" (aromatic groups, aryl groups, arylene groups)

[0164] The term "aromatic ring" refers to a concept encompassing aromatic hydrocarbon rings, aromatic heterocycles, and their residues [sometimes referred to as "aromatic groups," "aryl" (in the case of monovalent groups), or "anelyl" (in the case of divalent groups)]. It includes both monocyclic (aromatic monocyclic) and polycyclic (aromatic polycyclic) forms. In the case of polycyclic forms, at least one monocycle is an aromatic monocycle, and the remaining monocycle forming a fused ring with this aromatic monocycle can be a monocyclic heterocycle (heterocyclic monocycle) or a monocyclic alicyclic hydrocarbon (alicyclic monocycle).

[0165] In this specification, heteroaryl groups are included within aryl groups. Heteroarylene groups are included within arylene groups.

[0166] Examples of aromatic rings include benzene, indene, naphthalene, azulene, styrene, toluene, xylene, mesitylene, isopropylbenzene, anthracene, phenanthrene, benzo[9,10]phenanthrene, benzo[9,10]anthracene, pyrene, Fluorene, biphenyl, cardinalene, perylene, fluoranthene, benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[ghi]perylene, halobenzene, dibenzo[g,p] Aromatic hydrocarbon rings such as acenaphthylene, dihydroacenaphthene, tetraphenylene, pentaphenylene, and cyclooctatetraene, and more typically, aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and pyrene; furan, pyran, pyridine, pyrimidine, pyrazine, thiophene, pyrrole, N-alkylpyrrole, N-arylpyrrole, imidazole, pyridine, pyrimidine, pyrazine, triazine, thiazole, indole, phenylindole, bisindole fluorene, bisindole benzo[a]fluorene, bisindole dibenzo[a]fluorene, purine, quinoline, isoquinoline, chromene, thiamethoxam, phenothiazine, phenanthrene, etc. Aromatic heterocyclic compounds such as azines, xanthannes, acridine, phenazine, carbazole, and indole-carbazole, more typically furan, thiophene, pyrrole, indole, phenylindole, bisindofluorene, phenothiazine, carbazole, and indole-carbazole, but not limited to these.

[0167] Aromatic rings (such as benzene rings, naphthalene rings, etc.) can have substituents at will. Examples of such substituents include the following atoms and groups.

[0168] Halogen atoms A saturated or unsaturated straight-chain, branched, or cyclic hydrocarbon group (-R) that can be interrupted more than once by an oxygen atom in the middle of the hydrocarbon chain. a (This includes alkyl, alkenyl, and alkynyl groups (e.g., propargyl) and aryl groups, which can be interrupted more than once by an oxygen atom in the middle of the hydrocarbon chain.) -OR (where R represents the hydrocarbon group -R)a 。 ) aryloxy -NH2, -NHR, or -NR2 (the two Rs can be the same or different), where R represents the aforementioned hydrocarbon group -R. a .

[0169] hydroxyl Hydroxyalkyl carboxyl formyl group cyano Nitro Ester group (e.g., -CO2R or -OCOR, where R represents the aforementioned hydrocarbon group -R) a 。 ) Amide groups [e.g., -NHCOR, -CONHR, -NRCOR (the two Rs can be the same or different) or -CONR2 (the two Rs can be the same or different), where R represents the aforementioned hydrocarbon group -R] a 。 A sulfonyl group (e.g., -SO2R, where R represents the aforementioned hydrocarbon group -R) a Or hydroxyl group -OH. Thiol group (-SH) The group containing sulfide (-SR, where R represents the aforementioned hydrocarbon group -R) a 。 ) Organic groups containing ether bonds [R] 11 -OR 11 (R 11 Each of these groups independently represents an alkyl, phenyl, naphthyl, anthraceneyl, pyrene, or other aryl group having 1 to 6 carbon atoms, such as methyl or ethyl. (The remaining group represents the residues of an ether compound; for example, an organogroup containing an ether bond, such as methoxy, ethoxy, or phenoxy.) The "aromatic ring" further includes an organic group having one or more aromatic rings (benzene, naphthalene, anthracene, pyrene, etc.) and one or more aliphatic rings or heterocycles. Furthermore, examples of aliphatic rings include cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, cycloheptane, and cycloheptene; examples of heterocycles include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, and morpholine.

[0170] An "aromatic ring" can be an organogroup having a structure in which two or more aromatic rings are linked by a divalent linker. Examples of divalent linkers include alkylene, arylene, -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO2-. Furthermore, a divalent linker can be a divalent group from which one hydrogen atom has been removed from any of the substituents of the aforementioned aromatic rings.

[0171] (I-4) "Heterocyclic rings"

[0172] "Heterocycle" encompasses both aliphatic and aromatic heterocycles, including both monocyclic (heteromonocyclic) and polycyclic (heteropolycyclic) forms. In the case of a polycyclic form, at least one monocycle is a heteromonocyclic ring, and the remaining monocycles can be either aromatic hydrocarbon monocycles or alicyclic monocycles. For aromatic heterocycles, refer to the example in (I-3) above. Similar to the aromatic rings in (I-3) above, they can have substituents.

[0173] (I-5) "Non-aromatic ring" (aliphatic ring)

[0174] The term "non-aromatic monocyclic ring" in the context of a monocyclic ring refers to a monocyclic hydrocarbon that does not belong to the aromatic group, typically a monocyclic alicyclic compound. It can be called an aliphatic monocyclic ring (and may include aliphatic heterocyclic rings; as long as it is not an aromatic compound, it can contain unsaturated bonds). Similar to the aromatic rings described in (I-3) above, it can have substituents.

[0175] Examples of non-aromatic monocyclic rings (aliphatic rings, aliphatic monocyclic rings) include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, cyclohexene, methylcyclohexene, cycloheptane, and cycloheptene.

[0176] The term "non-aromatic polycyclic" refers to polycyclic hydrocarbons that do not belong to the aromatic group, typically alicyclic compounds. They can be called aliphatic polycyclics [and can include aliphatic heterocyclic polycyclics (at least one of the monocyclic rings constituting the polycyclic structure is an aliphatic heterocycle), and can contain unsaturated bonds as long as they are not aromatic compounds]. They include non-aromatic bicyclic, non-aromatic tricyclic, and non-aromatic tetracyclic rings.

[0177] The term "non-aromatic bicycle" in the context of a bicycle refers to a fused ring composed of two monocyclic hydrocarbons that are not aromatic, typically two alicyclic compounds. In this specification, it is sometimes also referred to as an aliphatic bicycle (which may include aliphatic heterocycles; as long as it is not an aromatic compound, it may contain unsaturated bonds). Examples of non-aromatic bicycles include dicyclopentane, dicyclooctane, and dicycloheptene.

[0178] The term "non-aromatic tricyclic ring" refers to a fused ring composed of three monocyclic hydrocarbons that are not aromatic. Typically, it consists of three alicyclic compounds (each of which can be a heterocycle, and as long as it is not an aromatic compound, it can contain unsaturated bonds). Examples of non-aromatic tricyclic rings include tricyclooctane, tricyclononane, and tricyclodecane.

[0179] The so-called "non-aromatic tetracycle" in the case of a "non-aromatic ring" is a fused ring composed of four monocyclic hydrocarbons that are not aromatic. Typically, it is a fused ring of four alicyclic compounds (each of which can be a heterocycle, and as long as it is not an aromatic compound, it can contain unsaturated bonds). Examples of non-aromatic tetracycles include hexadecylhydropyrene.

[0180] (I-6)

[0181] The term "carbon atom constituting part of the ring" refers to the carbon atoms that make up the ring in the context of a hydrocarbon ring without substituents (which can be any of the aromatic, aliphatic, or heterocyclic rings).

[0182] (I-7)

[0183] The term "hydrocarbon group" refers to a group formed by removing one or more hydrogen atoms from a hydrocarbon. Such hydrocarbons include saturated or unsaturated aliphatic hydrocarbons, saturated or unsaturated alicyclic hydrocarbons, and aromatic hydrocarbons.

[0184] (I-8)

[0185] In the chemical structural formula of the unit structure of the phenolic varnish resin shown in this application specification, bonding bonds (represented by *) are sometimes described for convenience. Unless otherwise specified, such bonding bonds can be used at any bonding position in the unit structure, and the bonding position in the unit structure is not limited at all.

[0186] -Resin(G)-

[0187] Resin (G) has a composite unit structure.

[0188] The composite unit structure has: a unit structure with an aromatic ring (A) and a unit structure with more than one carbon atom (B).

[0189] The composite unit structure of resin (G) can be represented, for example, by the following formula (AB).

[0190]

[0191] (In equation (AB), A represents the unit structure (A), and B represents the unit structure (B).)

[0192] --A-1: Unit Structure (A)--

[0193] The unit structure (A) has an aromatic ring.

[0194] The unit structure (A) has, for example, at least one of the following: an oxygen atom constituting an aromatic ring, a sulfur atom constituting an aromatic ring, an oxygen atom bonded to an aromatic ring, a nitrogen atom constituting an aromatic ring, and a nitrogen atom directly bonded to an aromatic ring.

[0195] Unit structure (A), for example, does not have heteroatoms as atoms constituting aromatic rings and atoms bonded to aromatic rings.

[0196] The number of carbon atoms in the unit structure (A) is not particularly limited, for example, it is 4 to 100, preferably 4 to 50.

[0197] Preferably, such aromatic rings have 4 to 30, more preferably 4 to 24 carbon atoms.

[0198] Preferably, such aromatic rings are one or more benzene rings, naphthalene rings, anthracene rings, pyrene rings; or fused rings of benzene rings, naphthalene rings, anthracene rings, pyrene rings and heterocycles or aliphatic rings (fluorene rings, benzo[a]fluorene rings, dibenzo[a]fluorene rings, indole rings, carbazole rings, indole[a]carbazole rings, etc.).

[0199] Aromatic rings can have substituents at will, and from the viewpoint of polymerization reactivity, these substituents can contain a necessary minimum number of heteroatoms. Furthermore, two or more aromatic rings can be linked by a linking group, which can contain a necessary minimum number of heteroatoms. Examples of heteroatoms include, for instance, oxygen, nitrogen, and sulfur atoms.

[0200] An "aromatic ring" may contain at least one heteroatom selected from N, S, and O on, within, or between rings.

[0201] Examples of heteroatoms that can be included on the ring include, for example, the nitrogen atom contained in amino groups (e.g., propargylamino) and cyano groups; the oxygen atom contained in formyl groups, hydroxyl groups, carboxyl groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups (e.g., propargyloxy groups), and aryloxy groups, which are oxygen-containing substituents; and the nitrogen and oxygen atoms contained in nitro groups, which are both oxygen-containing and nitrogen-containing substituents.

[0202] Examples of heteroatoms that can be included within a ring include, for example, the oxygen atom contained in furan and xaton, the nitrogen atom contained in carbazole and pyrrole, and the sulfur atom contained in phenothiazine.

[0203] Examples of heteroatoms that can be included in a linking group of two or more aromatic rings include nitrogen, oxygen, and sulfur atoms contained in -NH-, -NHCO-, -O-, -COO-, -CO-, -S-, -SS-, and -SO2-.

[0204] In this specification, the term "atom constituting an aromatic ring" has the same meaning as "atoms contained within the ring". The term "atoms bonded to the aromatic ring" refers to, for example, "atoms directly bonded to the ring among atoms or groups contained on the ring" and "atoms directly bonded to the ring among atoms contained between the rings".

[0205] For example, the atoms that make up the benzene ring are carbon atoms.

[0206] For example, the atoms that make up the pyrrole ring are carbon atoms and nitrogen atoms.

[0207] For example, the oxygen atom of the hydroxyl group in phenol is not an atom that forms an aromatic ring.

[0208] For example, the oxygen atom of the hydroxyl group in phenol is an atom that is bonded to the benzene ring, and is an atom that is directly bonded to the benzene ring among the groups contained on the benzene ring.

[0209] ---A-2: An example of the skeleton that constitutes the unit structure (A)---

[0210] The unit structure (A) has, for example, a skeleton with aromatic rings.

[0211] The skeleton containing aromatic rings is a phenolic skeleton.

[0212] The unit structure (A) is, for example, a residue from a skeleton having two hydrogen atoms removed.

[0213] The aromatic ring skeleton is derived, for example, from an aromatic ring compound during the synthesis of resin (G). The aromatic ring skeleton is, for example, a compound with an aromatic ring from which two hydrogen atoms have been removed.

[0214] A skeleton with an aromatic ring can have substituents.

[0215] ----A-2-3: Phenolic skeleton----

[0216] The so-called phenolic skeleton refers to a skeleton that has an aromatic ring and hydroxyl groups bonded to the aromatic ring.

[0217] There is no particular limitation on the number of hydroxyl groups that are bonded to the aromatic ring in the phenolic skeleton; it can be one or more. In many cases, it can be 2 to 10 or 2 to 8. In many cases, the hydroxyl groups can be bonded to the same aromatic ring (e.g., a benzene ring) or to different aromatic rings.

[0218] Furthermore, as will be described later, in unit structure (A), the hydrogen atoms of the hydroxyl groups bonded to the aromatic ring can be replaced with substituents.

[0219] Examples of phenolic skeletons include those shown in formula (A-4) below.

[0220]

[0221] (In the formula, n1, n2, n4, n5, n6, and n9 each independently represent integers from 1 to 4. n3a, n3b, n7a, n7b, n8a, and n8b each independently represent integers from 0 to 4. Among them, the sum of n3a and n3b ​​is 1 or more, the sum of n7a and n7b is 1 or more, and the sum of n8a and n8b is 1 or more.)

[0222] Furthermore, examples of phenolic skeletons include those shown in formula (A-5a) or formula (A-5d).

[0223]

[0224] (where Ar) 41 Each of them independently represents a residue of the aromatic ring.

[0225] X 1 This indicates an alkylene group that can be substituted by -O-, -S-, -SO2-, or a halogen atom.

[0226] X 2 Each can independently represent a single bond, -O-, -S-, -SO2-, or an alkylene group that can be substituted by a halogen atom.

[0227] Y 1 It represents a trivalent saturated hydrocarbon group.

[0228] Y 2 It represents a tetravalent saturated hydrocarbon group.

[0229] m1 and m2 each independently represent integers from 0 to 3. The sum of m1 and m2 is 1 or higher.

[0230] m3 to m5 each independently represent integers from 0 to 3. The sum of m3 to m5 is 1 or higher.

[0231] m6 to m8 each independently represent integers from 0 to 3. The sum of m6 to m8 is 1 or higher.

[0232] m9 to m12 each independently represent integers from 0 to 3. The sum of m9 to m12 is 1 or higher.

[0233] As Ar 41 The aromatic ring in the residues of the aromatic ring can be exemplified by, for example, the aromatic ring shown in the following formula (G3).

[0234]

[0235] As X 1 and X 2 Examples of the number of carbon atoms in the alkylene group that can be replaced by halogen atoms include, for example, 1 to 20. Examples of structures of the alkylene group include, for example, straight-chain, branched, and cyclic structures, as well as combinations of two or more of these. Examples of halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.

[0236] As Y 1 and Y 2 Examples of the number of carbon atoms in the saturated hydrocarbon group include, for example, 1 to 20. Examples of structures for the saturated hydrocarbon group include, for example, straight-chain, branched, and cyclic structures, as well as combinations of two or more of them.

[0237] Furthermore, examples of phenolic skeletons include those shown in formulas (A-6a), (A-6b-1), (A-6b-2), (A-6c), or (A-6d).

[0238]

[0239] (In equations (A-6a), (A-6b-1), (A-6b-2), (A-6c), and (A-6d), Ar 51 Each element independently represents a residue of the aromatic ring. n11 independently represents an integer from 1 to 4. p independently represents 0 or 1. When p is 1, the oxygen atom acts as an ether bond to form a bridging structure between aromatic rings; when p is 0, the ether bond that forms the bridging structure between aromatic rings does not exist. L represents a single bond or a divalent linker.

[0240] As Ar 51 The aromatic ring in the formula (G1) can be exemplified by, for example, the aromatic ring shown in the following formula (G1), preferably a benzene ring or a naphthalene ring.

[0241]

[0242] As for L, examples include a divalent group from which two hydrogen atoms have been removed from the following structure.

[0243]

[0244] n11, for example, can represent 1 or 2 independently.

[0245] Furthermore, examples of phenolic skeletons include those shown in formula (A-7a), formula (A-7b), or formula (A-7c).

[0246]

[0247] (In equations (A-7a), (A-7b), and (A-7c), Ar) 61 Each element independently represents a residue of the aromatic ring. n21 independently represents an integer from 1 to 4.

[0248] As Ar 61 The aromatic ring in the formula (G1) can be exemplified by, for example, the aromatic ring shown in the formula above, preferably a benzene ring or a naphthalene ring.

[0249] For example, n21 can be represented independently as 1 and 2.

[0250] Furthermore, examples of phenolic skeletons include those shown in formulas (A-8a-1), (A-8a-2), (A-8b), (A-8c), (A-8d), (A-8e), (A-8f), (A-8g-1), or (A-8g-2).

[0251]

[0252] In equations (A-8a-1), (A-8b), (A-8c), (A-8e), (A-8f), (A-8g-1), and (A-8g-2), n31 independently represents an integer from 1 to 4.

[0253] In equation (A-8a-2), n32 and n33 each independently represent integers from 0 to 4. The sum of n32 and n33 is 1 or more.

[0254] In equation (A-8d), n32 and n33 each independently represent integers from 0 to 4. The sum of n32 and n33 is 1 or more.

[0255] In equation (A-8b), X 1 It represents -O- or -NH-.

[0256] In equation (A-8d), X 2 It indicates -O- or -S-.

[0257] In equation (A-8e), X 3 It represents -S-, -CH2-, or -NH-.

[0258] In equation (A-8f), X 4 Indicates -CO- or -O-, X 5 (This indicates -CH2- or -O-.)

[0259] n31, for example, can represent 1 or 2 independently.

[0260] n32 and n33, for example, can each independently represent 0, 1, or 2.

[0261] As an example of the skeleton shown in Equation (A-4), the following skeletons can be cited.

[0262]

[0263] As an example of the skeleton shown in formula (A-5a), the following skeletons can be cited.

[0264]

[0265] As an example of the skeleton shown in equation (A-5b), the following skeletons can be cited.

[0266]

[0267] As an example of the skeleton shown in formula (A-5c), the following skeletons can be cited.

[0268]

[0269] As an example of the skeleton shown in formula (A-5d), the following skeletons can be cited.

[0270]

[0271] As an example of the skeleton shown in formula (A-6a), the following skeletons can be cited.

[0272]

[0273] Examples of skeletons that can be represented as the skeletons shown in formula (A-6b-1) or formula (A-6b-2) include the following skeletons.

[0274]

[0275] As an example of the skeleton shown in formula (A-6c), the following skeletons can be cited.

[0276]

[0277] As an example of the skeleton shown in formula (A-6d), the following skeletons can be cited.

[0278]

[0279] Examples of skeletons shown in formulas (A-7a), (A-7b), or (A-7c) include the following skeletons.

[0280]

[0281] Examples of skeletons that can be represented as the skeletons shown in formula (A-8a-1) or formula (A-8a-2) include the following skeletons.

[0282]

[0283] As an example of the skeleton shown in formula (A-8b), the following skeletons can be cited.

[0284]

[0285] As the skeleton shown in formula (A-8c), examples of the following skeletons can be cited.

[0286]

[0287] As an example of the skeleton shown in formula (A-8d), the following skeletons can be cited.

[0288]

[0289] As the skeleton shown in equation (A-8e), examples of the following skeletons can be cited.

[0290]

[0291] As the skeleton shown in equation (A-8f), examples of the following skeletons can be cited.

[0292]

[0293] Examples of skeletons that can be represented as the skeletons shown in formula (A-8g-1) or formula (A-8g-2) include the following skeletons.

[0294]

[0295] Other skeletons that can serve as phenolic skeletons include, for example, the following skeletons.

[0296]

[0297] Furthermore, the H atoms of hydroxyl groups bonded to the aromatic ring in the aforementioned skeleton with an aromatic ring and the hydrogen atoms bonded to the aromatic ring in the skeleton with an aromatic ring can be replaced with substituents.

[0298] Examples of such substituents include the substituents (S) shown in formulas (S1) to (S7) below.

[0299]

[0300] (In equations (S1) to (S7), R sa It represents a monovalent non-aromatic hydrocarbon group with 1 to 10 carbon atoms.

[0301] R sb Each can independently represent a single bond or a divalent non-aromatic hydrocarbon group with 1 to 10 carbon atoms.

[0302] R sc Each group independently represents a divalent non-aromatic hydrocarbon group with 1 to 10 carbon atoms.

[0303] R sd alkynyl Each group independently represents an alkynyl group with 2 to 4 carbon atoms.

[0304] Ar sa Each group independently represents a monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms.

[0305] Ar sb Each group independently represents a divalent aromatic hydrocarbon group with 6 to 20 carbon atoms.

[0306] X sa and X sb Each independently represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms, or X sa and X sb Together with the carbon atom bonded to the hydroxyl group, it forms a carbonyl group.

[0307] n represents an integer from 0 to 5.

[0308] * indicates a bonding bond.

[0309] <R sa >

[0310] As R sa Examples of monovalent non-aromatic hydrocarbon groups with 1 to 10 carbon atoms include alkyl groups with 1 to 10 carbon atoms and monovalent unsaturated hydrocarbon groups with 2 to 10 carbon atoms.

[0311] A monovalent unsaturated hydrocarbon group with 2 to 10 carbon atoms has one or more carbon-carbon multiple bonds. When this type of group has two or more carbon-carbon multiple bonds, these bonds can be entirely carbon-carbon double bonds, entirely carbon-carbon triple bonds, or a mixture of both. These multiple carbon-carbon multiple bonds can be conjugated or not.

[0312] <R sb and R sc >

[0313] As R sb and R sc Examples of divalent non-aromatic hydrocarbon groups with 1 to 10 carbon atoms include alkylene groups with 1 to 10 carbon atoms and divalent unsaturated hydrocarbon groups with 2 to 10 carbon atoms.

[0314] A divalent unsaturated hydrocarbon group with 2 to 10 carbon atoms has one or more carbon-carbon multiple bonds. When a divalent unsaturated hydrocarbon group with 2 to 10 carbon atoms has two or more carbon-carbon multiple bonds, these multiple bonds can be all carbon-carbon double bonds, all carbon-carbon triple bonds, or a mixture of both. The two or more carbon-carbon multiple bonds can be conjugated or not conjugated.

[0315] As R sb and R sc Examples of such groups include the following.

[0316]

[0317] (* indicates a bonding bond.)

[0318] <R sd alkynyl >

[0319] R sd alkynyl This refers to an alkynyl group having 2 to 4 carbon atoms. Examples of alkynyl groups having 2 to 4 carbon atoms include vinyl, 1-propynyl, and propynyl (2-propynyl).

[0320] <Ar sa >

[0321] Ar sa The monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms is a residue from an aromatic hydrocarbon with 6 to 20 carbon atoms by removing one hydrogen atom. Examples of aromatic hydrocarbons with 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, 2,3-dihydro-1H-phenanthrene, pyrene, fluorene, biphenyl, etc.

[0322] <Arsb >

[0323] Ar sb The divalent aromatic hydrocarbon group with 6 to 20 carbon atoms is a residue from an aromatic hydrocarbon with 6 to 20 carbon atoms by removing two hydrogen atoms. Examples of aromatic hydrocarbons with 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, and biphenyl.

[0324] <X sa and X sb >

[0325] As X sa and X sb Monovalent hydrocarbon groups with 1 to 20 carbon atoms can be exemplified by, for example, monovalent non-aromatic hydrocarbon groups with 1 to 10 carbon atoms and monovalent aromatic hydrocarbon groups with 6 to 20 carbon atoms.

[0326] Examples of monovalent non-aromatic hydrocarbon groups having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms.

[0327] A monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms is a residue from an aromatic hydrocarbon with 6 to 20 carbon atoms by removing one hydrogen atom. Examples of aromatic hydrocarbons with 6 to 20 carbon atoms include benzene, naphthalene, anthracene, phenanthrene, 2,3-dihydro-1H-phenanthrene, pyrene, fluorene, biphenyl, etc.

[0328] Examples of substituents shown in formula (S1) include the following groups.

[0329]

[0330] (* indicates a bonding bond.)

[0331] Examples of substituents shown in formula (S2) include the following groups.

[0332]

[0333] (* indicates a bonding bond.)

[0334] Examples of substituents shown in formula (S3) include the following groups.

[0335]

[0336] (* indicates a bonding bond.)

[0337] Examples of substituents shown in formula (S4) include the following groups.

[0338]

[0339] (* indicates a bonding bond.)

[0340] Examples of substituents shown in formula (S5) include the following groups.

[0341]

[0342] (* indicates a bonding bond.)

[0343] Examples of substituents shown in formula (S6) include the following groups.

[0344]

[0345] (* indicates a bonding bond.)

[0346] Examples of substituents shown in formula (S7) include the following groups.

[0347]

[0348] (* indicates a bonding bond.)

[0349] Other substituents include, for example, the following groups.

[0350]

[0351] (* indicates a bonding bond.)

[0352] As the unit structure (A), it is preferred to select at least one of the following. In addition, the positions of the two bonds shown in each unit structure described below are merely for convenience, and each can extend from any possible carbon atom, without limitation on its position.

[0353] (Examples of unit structures composed of phenolic skeletons)

[0354] --B-1: Unit Structure (B)--

[0355] The unit structure (B) has more than one carbon atom.

[0356] Unit structures (B) are, for example, unit structures derived from aldehyde compounds or aldehyde equivalents.

[0357] Unit structure (B) is one or more unit structures containing connecting carbon atoms bonded to the aromatic ring in unit structure (A) [refer to (I-1) above], for example, including the structures shown in formulas (B1), (B2) or (B3) described later. Unit structure (B) can connect two unit structures (A) by covalent bonding with unit structure (A).

[0358] ---B-2: Equation (B1)---

[0359] The unit structure (B) includes, for example, the structure shown in equation (B1) below. The unit structure (B) can be the structure shown in equation (B1) below.

[0360]

[0361] In equation (B1), R and R' each independently represent a hydrogen atom, an aromatic ring with 6 to 30 carbon atoms (which may have substituents), a heterocyclic ring with 3 to 30 carbon atoms (which may have substituents), or a straight-chain, branched, or cyclic alkyl group with 10 or fewer carbon atoms (which may have substituents). R and R' can form a ring structure together with the carbon atoms they are bonded to. * indicates a bonding bond.

[0362] Examples of substituents include hydroxyl, carboxyl, formyl, nitro, alkyl, alkoxy, aryl, aryloxy, cyano, and groups in which the H of the hydroxyl group is replaced by the aforementioned substituent (S).

[0363] Furthermore, each of the two bonding bonds in equation (B1) can be covalently bonded to each of the aromatic rings in the two unit structures (A).

[0364] In the definitions of R and R' in equation (B1), the terms "aromatic ring" and "heterocyclic ring" can be found in (I-3) and (I-4) above.

[0365] In the definitions of R and R' in formula (B1), examples of "alkyl" include, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, 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, cyclopentyl, 1-methyl-cyclobutyl, 2 1-Methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl- n-Butyl, 2-Ethyl-n-Butyl, 1,1,2-Trimethyl-n-Propyl, 1,2,2-Trimethyl-n-Propyl, 1-Ethyl-1-Methyl-n-Propyl, 1-Ethyl-2-Methyl-n-Propyl, Cyclohexyl, 1-Methyl-Cyclopentyl, 2-Methyl-Cyclopentyl, 3-Methyl-Cyclopentyl, 1-Ethyl-Cyclobutyl, 2-Ethyl-Cyclobutyl, 3-Ethyl-Cyclobutyl, 1,2-Dimethyl-Cyclobutyl, 1,3-Dimethyl-Cyclobutyl, 2,2-Dimethyl-Cyclobutyl, 2,3-Dimethyl-Cyclobutyl, 2 4-Dimethyl-cyclobutyl, 3,3-Dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl and 2-ethyl-3-methyl-cyclopropyl, n-heptyl, n-octyl, n-nonyl, n-decyl.

[0366] Preferably, R and R' are each independently phenyl, naphthyl, anthraceneyl, phenanthryl, tetraphenyl, or pyrene.

[0367] As a ring structure formed by R and R' together with the carbon atoms they are bonded to, examples include structures shown in the following formula.

[0368]

[0369] (In the formula, Ar independently represents each residue of the aromatic ring. The carbon atom represented by * in formula (B1) is the carbon atom bonded to R and R'.)

[0370] As an aromatic ring of Ar, examples include the aromatic ring shown in formula (G1).

[0371] The unit structure (B) of the structure represented by formula (B1) is derived from, for example, aldehyde compounds and ketone compounds.

[0372] Examples of aldehyde compounds include, for instance, the compound shown in the following formula (B-1a).

[0373] Examples of ketone compounds include, for instance, the compound shown in formula (B-1b) below.

[0374]

[0375] In equations (B-1a) and (B-1b), R and R' have the same meaning as R and R' in equation (B1). Among them, R excludes hydrogen atoms.

[0376] In formula (B-1b), R and R' can form a ring structure together with the carbon atoms they are bonded to.

[0377] For example, when obtaining resin (G), the carbonyl groups in formulas (B-1a) and (B-1b) are converted to *-C-* in formula (B1).

[0378] If we give specific examples of the unit structure (B) containing the structure shown in formula (B1), then it is as follows. * Basically represents the connection point with the unit structure (A). It goes without saying that it can be a structure that contains the illustrated structure as part of the whole.

[0379]

[0380] ---B-3: Equation (B2)---

[0381] The unit structure (B) includes, for example, the structure shown in equation (B2) below. The unit structure (B) can be the structure shown in equation (B2) below.

[0382]

[0383] In equation (B2), Z 0This refers to an organogroup consisting of 6 to 30 carbon atoms, including aromatic ring residues, aliphatic ring residues, or two aromatic or aliphatic rings linked by a single bond. Examples of organogroups consisting of two aromatic or aliphatic rings linked by a single bond include divalent residues such as biphenyl, cyclohexylphenyl, and dicyclohexyl.

[0384] Examples of substituents include hydroxyl, carboxyl, formyl, nitro, alkyl, alkoxy, aryl, aryloxy, cyano, and groups in which the H of the hydroxyl group is replaced by the aforementioned substituent (S).

[0385] J 1 and J 2 Each can be independently represented as a directly bonded or potentially substituent-containing divalent organogroup. Preferably, this divalent organogroup is a straight-chain or branched alkylene group with 1 to 6 carbon atoms, which can be substituted by a hydroxyl group, an aryl group (phenyl, substituted phenyl, etc.), or a halogen group (e.g., fluorine). Examples of straight-chain alkylene groups include, for example, methylene, ethylene, propylene, butylene, pentylene, and hexylene.

[0386] The unit structure (B) containing the structure shown in formula (B2) originates, for example, from compounds having a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom, compounds having a hydroxyl, alkoxy, or halogroup bonded to an α-carbon atom (such as a benzyl carbon atom) of an alkyl aryl group, or compounds having two carbon-carbon double bonds. These compounds are aldehyde equivalents.

[0387] Examples of compounds having a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom include, for example, compounds represented by the following formula (B-2a).

[0388] Examples of compounds having a hydroxyl, alkoxy, or halogroup bonded to the α-carbon atom (benzyl carbon atom, etc.) of an alkyl aryl group include, for example, the compound shown in formula (B-2b).

[0389] Examples of compounds having two carbon-carbon double bonds include, for example, compounds represented by formula (B-2c) or formula (B-2d).

[0390]

[0391] (In equations (B-2a), (B-2b), and (B-2b), J 1 J 2 and Z 0 J in equation (B2) 1 J 2 and Z 0 They have the same meaning.

[0392] In equation (B-2a), X aand X b Each can be used independently to represent a hydroxyl or alkoxy group bonded to a secondary or tertiary carbon atom.

[0393] In equation (B-2b), Y a and Y b Each of these groups independently represents a hydroxyl, alkoxy, or halogroup bonded to the α-carbon atom of an alkyl aryl group (or the carbon atom at the benzyl position, etc.).

[0394] In equation (B-2d), n represents an integer from 0 to 4.

[0395] For example, when obtaining resin (G), X in formula (B-2a) a -J 1 Transformed into *-J in equation (B2) 1 J 2 -X b J is transformed into equation (B2) 2 -*.

[0396] For example, when obtaining resin (G), Y in formula (B-2b) a -J 1 Transformed into *-J in equation (B2) 1 J 2 -Y b J is transformed into equation (B2) 2 -*.

[0397] An example of formula (B-2a) is the following compound.

[0398]

[0399] An example of formula (B-2b) is the following compound.

[0400]

[0401] An example of formula (B-2c) is the following compound.

[0402]

[0403] If we give specific examples of unit structures that include the structure shown in equation (B2), then it is as follows. * indicates the junction with unit structure A. It goes without saying that a unit structure can be a part of a whole that includes the illustrated structure.

[0404]

[0405] ---B-4: Equation (B3)---

[0406] In equation (B3), Z is a group having a fused ring of 4 to 25 carbon atoms, which may have substituents, in the form of a monocyclic, bicyclic, tricyclic, or tetracyclic ring. Furthermore, the number of carbon atoms referred to here refers to the number of carbon atoms that constitute the ring skeleton of the fused ring of 4 to 25 carbon atoms, excluding substituents, and does not include the number of heteroatoms constituting the heterocycle in the case where the monocyclic or fused ring is a heterocycle.

[0407] The aforementioned single rings are single rings whose number of π electrons does not satisfy 4n+2 (n is an integer greater than or equal to 0) (hereinafter, sometimes referred to as "non-Hückel single rings"). At least one of the single rings constituting the aforementioned two-, three-, and four-ring structures is a single ring whose number of π electrons does not satisfy 4n+2 (n is an integer greater than or equal to 0), and the remaining single rings can be either single rings whose number of π electrons satisfies 4n+2 (n is an integer greater than or equal to 0) or single rings whose number of π electrons does not satisfy 4n+2 (n is an integer greater than or equal to 0).

[0408] The aforementioned monocyclic, bicyclic, tricyclic, or tetracyclic fused rings can further form fused rings with one or more aromatic rings to become fused rings of five or more rings. The number of carbon atoms in the fused ring of five or more rings is preferably 40 or less. Here, the number of carbon atoms refers to the number of carbon atoms that constitute the ring skeleton of the aforementioned fused ring of five or more rings, excluding substituents, and does not include the number of heteroatoms constituting the heterocycle in the case where the aforementioned fused ring of five or more rings is a heterocycle.

[0409] If X and Y are the same or different, it indicates -CR 31 R 32 -base, R 31 and R 32 They may be the same or different, representing hydrocarbon groups with 1 to 6 hydrogen or carbon atoms.

[0410] x and y represent numbers in X and Y respectively, and each independently represents 0 or 1.

[0411] In formula (B3) In the formula (B3) At least one of them is bonded to any carbon atom (referred to as "carbon atom Z") of the aforementioned non-Hückel monocycle constituting Z (in the case of x=1, y=1) or extends from carbon atom Z (in the case of x=0, y=0).

[0412] For example, in equation (B3) It combines with any carbon atom (referred to as "carbon atom 1") of the aforementioned non-Hückel monocycle constituting Z (in the case of x=1) or extends from carbon atom 1 (in the case of x=0). In formula (B3) It combines with any carbon atom (referred to as "carbon atom 2") of the aforementioned non-Hückel monocycle constituting Z (in the case of y=1) or extends from carbon atom 2 (in the case of y=0). Carbon atom 1 and carbon atom 2 can be the same or different. In different cases, they can belong to the same non-Hückel monocycle or different non-Hückel monocycles.

[0413] Furthermore, in formula (B3), the connecting carbon atoms other than carbon atom 1 and carbon atom 2 can be included arbitrarily.

[0414] Furthermore, when Z is a fused ring with three or more rings, the serration relationship between the one or two non-Hückel monocycles to which carbon atoms 1 and 2 belong in equation (B3) and the remaining monocycles in the fused ring is arbitrary. When carbon atoms 1 and 2 belong to different non-Hückel monocycles (referred to as "non-Hückel monocycle 1" and "non-Hückel monocycle 2" respectively), the serration relationship between non-Hückel monocycle 1 and non-Hückel monocycle 2 in the fused ring is also arbitrary.

[0415] The following is an example of an organic group containing the structure shown in formula (B3). The site of connection with unit structure A is not particularly limited. It goes without saying that a structure can contain the illustrated structure as part of a whole.

[0416] Additionally, examples are included where the number of bonding bonds (*) exceeds 2, but the remaining bonding bonds can be used for bonding with aromatic rings in other polymer chains, bridging, etc., and can be bonding bonds with hydrogen bonds.

[0417]

[0418] Below, in equation (B3), the following will be discussed regarding the content of equation (B3). In the formula (B3) The case in which only one of the atoms in Z is combined with any carbon atom (referred to as "carbon atom Z") of the aforementioned non-Hückel monocycle constituting Z (in the case of x=1, y=1) or extended from carbon atom Z (in the case of x=0, y=0) will be explained.

[0419] As a more specific structure of formula (B3) in this case, for example, for formula (C31) below, the unit structure (B) shown in formula (B3) can be formed by p and k1 or p and k2, which can be the bonding bonds. The remaining bonding bonds are bonded to hydrogen atoms.

[0420]

[0421] Furthermore, in the following formula (C32), the unit structure (B) shown in formula (B3) can be formed by p with k1, p with k2, or p with m among p, k1, k2, and m, which can become bonding bonds. The remaining bonding bonds are bonded to hydrogen atoms.

[0422]

[0423] If we were to give several more specific examples of equation (B3) that are equivalent to equation (31) or equation (32), the following would be provided. * indicates the connection point with the unit structure (A).

[0424] For equation (B3), the bonding bonds that connect with other unit structures (e.g., unit structure (A)) extend separately from the aromatic rings in those structures, but for the specific examples described below, such bonding bonds are omitted. It goes without saying that the unit structure can contain the illustrated structure as part of the whole.

[0425]

[0426] Furthermore, in the specific examples described above, there are examples where the polymer terminus can be formed without the bonding bonds from the aromatic ring.

[0427] <<<<Polymer (A4)>>>>

[0428] Polymer (A4), as an example of organic compound (A), is a polymer having the unit structure shown in the following formula (Z1).

[0429]

[0430] In the formula, A independently represents a hydrogen atom, a methyl atom, or an ethyl atom, and Q... 1 and Q 2 Each represents a divalent base independently.

[0431] Q 1 and Q 2 It is preferable to express equations (Z2) or (Z3) independently of each other.

[0432]

[0433] In equation (Z2), Q 3 This indicates that the alkylene group, alkenyl group, phenylene group, naphthylene group, or anthracene group, which may contain a sulfur bond or disulfide bond, has 1 to 10 carbon atoms. The aforementioned phenylene, naphthylene, and anthracene groups can be independently substituted by groups selected from alkyl, phenyl, halogen, alkoxy, nitro, cyano, hydroxyl, and alkylthio groups, which have 1 to 6 carbon atoms.

[0434] In formula (Z3), B independently represents a single bond or an alkylene group having 1 to 5 carbon atoms. In formulas (Z2) and (3), * represents a bond.

[0435] n is 0 or 1 independently of each other.

[0436] m is 0 or 1 independently of each other.

[0437] X is a group represented by formula (Z4), formula (Z5) or formula (Z6).

[0438]

[0439] In equations (Z4) and (Z5), R 1 Each of these groups independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group. The alkyl and alkenyl groups can be substituted with a halogen atom, a hydroxyl group, or a cyano group. The hydrogen atom on the aromatic ring of the benzyl group can be substituted with a hydroxyl group. The phenyl group can be substituted with a group selected from alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms. The two R groups... 1 They can combine to form rings with 3 to 6 carbon atoms. * indicates a bonding bond. *1 indicates a bonding bond with a carbon atom in formula (Z3). *2 indicates a bonding bond with a nitrogen atom in formula (Z3).

[0440] In equation (Z6), R 2 This represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group, or a phenyl group. The phenyl group can be substituted with a group selected from alkyl groups having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms. *1 represents a bonding bond with a carbon atom in formula (Z3). *2 represents a bonding bond with a nitrogen atom in formula (Z3).

[0441] For example, Q 1 and Q 2 At least one of them contains the structure shown in equation (Z3).

[0442] As an alkylene group having 1 to 10 carbon atoms, it can be linear, branched, or cyclic, and examples include methylene, ethylene, propylene, 1,5-pentane, cyclohexane, 2-methylpropylene, and 1-methylethylene. Furthermore, as an alkylene group having 1 to 10 carbon atoms containing a sulfur bond or a disulfide bond, examples include alkylene groups containing sulfur bonds or disulfide bonds as shown in the following formulas.

[0443]

[0444] (In the formula, * represents a bonding bond.)

[0445] As an alkenyl group having 2 to 10 carbon atoms, it can be any of straight-chain, branched, or cyclic. Examples include vinylene, propenylene, butenylene, pentenylene, hexenylene, heptenylene, octeneylene, and nonenylene.

[0446] As an alkyl group having 1 to 6 carbon atoms, it can be any of the following: straight-chain, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopentyl, and cyclohexyl.

[0447] As an alkoxy group having 1 to 6 carbon atoms, it can be any of the following: linear, branched, or cyclic. Examples include methoxy, ethoxy, isopropoxy, n-pentyloxy, n-hexyloxy, and cyclohexyloxy.

[0448] As an alkylthio group having 1 to 6 carbon atoms, it can be any of the following: linear, branched, or cyclic. Examples include methylthio, ethylthio, isopropylthio, n-pentylthio, and cyclohexylthio.

[0449] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0450] As 2 R 1 The rings formed by combining carbon atoms with 3 to 6 carbon atoms include cyclobutane rings, cyclopentane rings, and cyclohexane rings.

[0451] As the unit structure shown in formula (Z1), examples can be the unit structures shown in formulas (7) to (31) below, but are not limited to them. In addition, in the following formulas, Me is methyl. Furthermore, the resin (A4) can have various unit structures shown in formula (Z1). For example, the resin (A4) can have the unit structure shown in formula (7) and the unit structure shown in formula (32).

[0452]

[0453] In the above formulas, X represents the group shown in formula (Z4), formula (Z5), or formula (Z6), and R... 6 and R 7 Each element independently represents an alkylene group with 1 to 3 carbon atoms or a direct bond, where p is the number of unit structures, representing an integer from 5 to 100.

[0454] In the above formulas, X represents the group shown in formula (Z4), formula (Z5), or formula (Z6), and R... 6 and R 7 Each independently represents an alkylene group with 1 to 3 carbon atoms or a direct bond, R 8 This indicates an alkylene group with 1 to 3 carbon atoms, where m represents 0 or 1, and r is the unit cell number, representing an integer from 5 to 100.

[0455] In formula (31) above, R is an alcohol residue (an organic group of an alcohol other than a hydroxyl group), where R represents an alkyl group, an ether group, or a combination thereof. Examples of R include alkyl groups, alkoxyalkyl groups, etc. Examples of alkyl and alkoxy groups are given above.

[0456] <<<<Compound (A5)>>>>

[0457] Compound (A5), as an example of an organic compound (A), is a compound having two or more of the following structures (M).

[0458]

[0459] (In structure (M), R) 101 This indicates a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or an alkoxyalkyl group with 2 to 6 carbon atoms. * indicates a bonding bond.

[0460] Bonding bonds include, for example, bonds with nitrogen atoms or carbon atoms that form aromatic hydrocarbon rings.

[0461] R in structure (M) 101 Except in the case of hydrogen atoms, it is a protecting group that can be deprotected.

[0462] As R 101 Preferably, it contains hydrogen atoms, methyl, ethyl or groups represented by the following structures.

[0463]

[0464] (In the structure, R) 102 * Represents a hydrogen atom, methyl group, or ethyl group. * Represents a bond.

[0465] As compound (A5), melamine compounds, guanidine compounds, glycourea compounds, urea compounds, and compounds having phenolic hydroxyl groups are preferred. They can be used alone or in combination of two or more.

[0466] Examples of melamine compounds include, for example, hexamethylolmelamine, hexamethoxymethylmelamine, compounds of hexamethylolmelamine in which 1 to 6 hydroxymethyl groups are methoxymethylated, or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds of hexamethylolmelamine in which 1 to 6 hydroxymethyl groups are acyloxymethylated, or mixtures thereof.

[0467] Examples of guanidine compounds include, for example, tetrahydroxymethylguanidine, tetramethoxymethylguanidine, compounds of tetrahydroxymethylguanidine in which 1 to 4 hydroxymethyl groups are methoxymethylated, or mixtures thereof, tetramethoxyethylguanidine, tetraacyloxyguanidine, compounds of tetrahydroxymethylguanidine in which 1 to 4 hydroxymethyl groups are acyloxymethylated, or mixtures thereof.

[0468] Examples of glycourea compounds include, for example, tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, compounds of tetrahydroxymethylglycourea in which 1 to 4 hydroxymethyl groups are methoxymethylated, or mixtures thereof, compounds of tetrahydroxymethylglycourea in which 1 to 4 hydroxymethyl groups are acylmethylated, or mixtures thereof.

[0469] In addition, as a glycourea compound, it can be, for example, a glycourea derivative as shown in the following formula (1E).

[0470]

[0471] (In formula (1E), each of the four R1s independently represents a methyl or ethyl group, and each of the R2 and R3 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

[0472] Examples of glycourea derivatives represented by the above formula (1E) include compounds represented by formulas (1E-1) to (1E-6).

[0473]

[0474] The glycourea derivative shown in formula (1E) can be obtained, for example, by reacting the glycourea derivative shown in formula (2E) with at least one compound shown in formula (3d).

[0475]

[0476] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.)

[0477] (In formula (3d), R1 represents methyl or ethyl.)

[0478] Examples of glycourea derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4). Further examples of compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2).

[0479]

[0480] Examples of urea compounds include tetrahydroxymethylurea, tetramethoxymethylurea, compounds of tetrahydroxymethylurea in which 1 to 4 hydroxymethyl groups are methoxymethylated, or mixtures thereof, and tetramethoxyethylurea.

[0481] Examples of compounds having phenolic hydroxyl groups include, for example, compounds represented by formula (G-1) or formula (G-2) below.

[0482]

[0483] (In equations (G-1) and (G-2), Q) 1 It represents a single bond or an m1-valent organic group.

[0484] R 1 and R 4 They respectively represent alkyl groups having 2 to 10 carbon atoms or alkyl groups having 1 to 10 carbon atoms and having 2 to 10 carbon atoms.

[0485] R 2 and R 5 These represent hydrogen atoms or methyl groups, respectively.

[0486] R 3 and R 6 They represent alkyl groups with 1 to 10 carbon atoms or aryl groups with 6 to 40 carbon atoms, respectively.

[0487] n1 represents an integer where 1 ≤ n1 ≤ 3, n2 represents an integer where 2 ≤ n2 ≤ 5, n3 represents an integer where 0 ≤ n3 ≤ 3, and n4 represents an integer where 0 ≤ n4 ≤ 3 and 3 ≤ (n1 + n2 + n3 + n4) ≤ 6.

[0488] n5 represents an integer where 1 ≤ n5 ≤ 3, n6 represents an integer where 1 ≤ n6 ≤ 4, n7 represents an integer where 0 ≤ n7 ≤ 3, and n8 represents an integer where 0 ≤ n8 ≤ 3 and 2 ≤ (n5 + n6 + n7 + n8) ≤ 5.

[0489] m1 represents an integer from 2 to 10.

[0490] Furthermore, examples of compounds having phenolic hydroxyl groups include, for example, compounds represented by formula (G-3) or formula (G-4) below.

[0491] The compound represented by formula (G-1) or formula (G-2) can be obtained by reacting the compound represented by formula (G-3) or formula (G-4) below with an ether compound containing a hydroxyl group or an alcohol having 2 to 10 carbon atoms.

[0492]

[0493] (In equations (G-3) and (G-4), Q) 2 It represents a single bond or an m2 valence organic group.

[0494] R 8 R 9 R 11 and R 12 These represent hydrogen atoms or methyl groups, respectively.

[0495] R 7 and R 10 They represent alkyl groups with 1 to 10 carbon atoms or aryl groups with 6 to 40 carbon atoms, respectively.

[0496] n9 represents an integer where 1 ≤ n9 ≤ 3, n 10 It means 2≤n 10 Integers ≤ 5, n 11 It means 0≤n 11 Integers ≤ 3, n 12 It means 0≤n 12 Integers ≤ 3, 3 ≤ (n ≤ 9 + n) 10 +n 11 +n 12 Integers ≤ 6.

[0497] n 13 It means 1≤n 13 Integers ≤ 3, n 14 It means 1≤n 14 Integers ≤ 4, n 15 It means 0≤n 15 Integers ≤ 3, n 16 It means 0≤n 16 Integers ≤ 3, 2 ≤ (n 13 +n 14 +n15 +n 16 Integers ≤ 5.

[0498] m2 represents an integer from 2 to 10.

[0499] As Q 2 Examples of m2-valent organic groups include those with 1 to 4 carbon atoms.

[0500] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds.

[0501]

[0502] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds.

[0503]

[0504] Me represents methyl.

[0505] The above-mentioned compounds can be obtained as products manufactured by Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. For example, Asahi Organic Materials Co., Ltd.'s trade name TMOM-BP can be cited as an example of such a product.

[0506] The content of organic compound (A) in the surface modifier is not particularly limited, but is preferably 0.01% to 10% by mass, more preferably 0.05% to 5% by mass, and particularly preferably 0.1% to 3% by mass.

[0507] <<<Solvent (B)>>>

[0508] The solvent (B) contained in the surface modifier can be used without particular restriction as long as it is a solvent that can dissolve / mix the organic compound (A) and other components contained in the surface modifier as needed.

[0509] Examples of solvents include organic solvents and water.

[0510] Examples of organic solvents include alcohols, carboxylic acids having hydroxyl groups, straight-chain or cyclic alkyl ketones, cyclic lactones, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylic esters (monocarboxylic esters of alkylene glycol monoalkyl ethers and alkoxycarboxylic esters of alkylene glycol monoalkyl ethers).

[0511] Examples of alcohols include monohydric alcohol solvents and polyhydric alcohol solvents.

[0512] Examples of monohydric alcohol solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylmethanol, diacetone alcohol, cresol, etc.

[0513] Examples of polyol solvents include ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol.

[0514] Examples of carboxylic acids having a hydroxyl group include ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, etc.

[0515] Examples of linear or cyclic alkyl ketones include, for example, methyl ethyl ketone, cyclopentanone, and cyclohexanone.

[0516] Examples of cyclic lactones include, for instance, γ-butyrolactone.

[0517] Examples of alkylene glycol alkyl ethers include, for example, alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers.

[0518] Examples of monoalkylene glycol monoalkyl ethers include, for example, 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 methanol, and propylene glycol monobutyl ether.

[0519] Examples of alkylene glycol dialkyl ethers include, for example, 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, etc.

[0520] Examples of monoalkylene glycol monoalkyl ether carboxylic esters include, for example, monocarboxylic esters of monoalkylene glycol monoalkyl ethers and alkoxycarboxylic esters of monoalkylene glycol monoalkyl ethers.

[0521] Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include, for instance, alkylene glycol monoalkyl ether acetates.

[0522] Examples of alkylene glycol monoalkyl ether acetates include, for example, methyl cellosolve acetate, ethyl cellosolve acetate, 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, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate.

[0523] Examples of alkoxycarboxylic acid esters that are monoalkylene glycol ethers include, for example, 2-methoxyethyl methyl carbonate, 2-ethoxyethyl methyl carbonate, 2-ethoxyethyl ethyl carbonate, and 2-propoxyethyl methyl carbonate.

[0524] Specific examples of other solvents include toluene, xylene, ethyl ethoxylate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl pyruvate, ethyl formate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl glycolate, and ethyl glycolate. Esters, methyl 3-methoxy-2-methylpropionate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutylacetate, 3-methoxypropylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, etc.

[0525] These solvents can be used alone or in combination of two or more.

[0526] Furthermore, the surface modifier may contain water as a solvent. When water is contained as a solvent, its content relative to the total mass of the solvent contained in the surface modifier may be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less.

[0527] <<<Acids, their salts, and acid-producing agents; compounds (C)>>>

[0528] The surface modifier may contain at least one compound (C) selected from acids, their salts, and acid-producing agents. Where the organic compound (A) has only hydroxyl groups protected by deprotected protecting groups as hydroxyl groups, the surface modifier preferably contains compound (C).

[0529] Examples of acids and their salts include, for example, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid and their salts.

[0530] Both thermal acid-generating agents and photo-acid-generating agents can be used as acid-generating agents, but thermal acid-generating agents are preferred.

[0531] Examples of heat-generating acid agents include p-toluenesulfonic acid, trifluoromethanesulfonic acid, and pyridine. - p-Toluenesulfonate (pyridine) -p-Toluenesulfonic acid), pyridine Phenolsulfonic acid, pyridine - p-Hydroxybenzenesulfonic acid (p-phenolsulfonic acid pyridine) salt), pyridine - Sulfonic acid compounds and carboxylic acid compounds such as trifluoromethanesulfonic acid, salicylic acid, camphor sulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzene disulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0532] Examples of photoacid-generating agents include, Salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds, etc.

[0533] As Salt compounds, for example, diphenyliodine Hexafluorophosphate, diphenyliodine Trifluoromethanesulfonate, diphenyliodine Nonafluoro-n-butane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphor sulfonate, bis(4-tert-butylphenyl)iodine Camphor sulfonate and bis(4-tert-butylphenyl)iodine Iodine, such as trifluoromethanesulfonate Sulfonate compounds, and sulfonate compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro n-butane sulfonate, triphenylsulfonium camphor sulfonate, and triphenylsulfonium trifluoromethane sulfonate.

[0534] Examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0535] Examples of disulfonyldiazomethane compounds include, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0536] The concentration of the film-forming component in the surface modifier relative to the total mass of the composition can be, for example, 0.01–50% by mass, 0.01–30% by mass, 0.01–25% by mass, or 0.01–20.0% by mass.

[0537] The content of organic compound (A) in the membrane forming component is usually 20% to 100% by mass, but from the viewpoint of obtaining the effects of the present invention with good reproducibility, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, further preferably 80% by mass, and the upper limit is preferably 100% by mass, and the remainder may be the above-mentioned additives.

[0538] The so-called film-forming component refers to the components in a surface modifier other than the solvent (B).

[0539] Surface modifiers can be manufactured by mixing organic compound (A) and solvent (B), as well as other components as needed. In this case, a solution containing organic compound (A) can be prepared in advance, and this solution can be mixed with the solvent and other components.

[0540] In the preparation of surface modifiers, appropriate heating can be applied within a range that does not decompose or deteriorate the components.

[0541] Filtration can be performed during the manufacturing process of the surface modifier, or after all components have been mixed, using submicron-sized filters or similar equipment. Furthermore, regardless of the type of filter material used, filters made of materials such as polyethylene, nylon, fluoropolymer, or polyimide can be employed.

[0542] <Second Process>

[0543] The second step is to thin the surface modification layer precursor by contacting it with a thinning solution (X) to obtain a surface modification layer with a film thickness of less than 5 nm.

[0544] In the second step, there are no particular limitations on the method of contacting the surface-modified layer precursor with the thinning solution (X). Spin coating is preferred in terms of uniform thinning and easy management of the degree of thinning with high precision. That is, the second step is preferably a step in which the surface-modified layer precursor is thinned by spin coating the surface-modified layer precursor with the thinning solution (X) to obtain a surface-modified layer with a film thickness of 5 nm or less.

[0545] There are no particular limitations on the conditions for spin coating. For example, it may include a coating process for applying a thinning solution (X) to a semiconductor substrate on which a surface-modified layer precursor has been formed, and a spin process for rotating the semiconductor substrate.

[0546] For coating processes, for example, when coating a surface-modified layer precursor with a thinning solution (X), the semiconductor substrate is rotated without rotation or at a low speed (e.g., below 1000 rpm). During the coating process, the thinning solution (X) is brought into contact with the surface-modified layer precursor, causing components in the surface-modified layer precursor to migrate into the thinning solution (X).

[0547] For example, in a rotational process, the semiconductor substrate is rotated at a high speed (e.g., more than 1,000 rpm and less than 5,000 rpm) to remove the thinning liquid (X) from the semiconductor substrate on which the surface modification layer precursor has been formed.

[0548] By doing so, the surface-modified layer precursor is thinned in accordance with the components that move into the thinning liquid (X), resulting in a surface-modified layer with a film thickness of less than 5 nm.

[0549] Examples of coating treatment times include, for example, 10 seconds to 2 minutes.

[0550] Examples of rotation processing times include, for instance, 5 seconds to 1 minute.

[0551] In addition, during rotation, for example, an axis orthogonal to the surface of the semiconductor substrate is set as the axis of rotation.

[0552] In the second step, it is preferable to reduce the film thickness of the surface modification layer precursor to 0.5 nm or more and 10 nm or less, and more preferably to 1 nm or more and 5 nm or less.

[0553] <<Thinning liquid (X)>>

[0554] As for the thinning solution (X), there are no particular limitations as long as it is a liquid that can thin the surface-modified layer precursor by contacting it with the thinning solution (X). Examples include organic solvents, water, acidic solutions, and alkaline solutions. Furthermore, diluents used in the RRC (reducing resist comsumption) process or the EBR (edge ​​bead removal) process can be used. They can be used alone or in combination of two or more.

[0555] Examples of organic solvents include alcohols, alkylene glycol alkyl ethers, and alkylene glycol monoalkyl ether carboxylic esters.

[0556] Examples of alcohols include monohydric alcohol solvents and polyhydric alcohol solvents.

[0557] Examples of monohydric alcohol solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecanol, trimethylnonanol, sec-tetradecanol, sec-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylmethanol, diacetone alcohol, cresol, etc.

[0558] Examples of polyol solvents include ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol.

[0559] Examples of alkylene glycol alkyl ethers include, for example, alkylene glycol monoalkyl ethers and alkylene glycol dialkyl ethers.

[0560] Examples of monoalkylene glycol monoalkyl ethers include, for example, 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 methanol, and propylene glycol monobutyl ether.

[0561] Examples of alkylene glycol dialkyl ethers include, for example, 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, etc.

[0562] Examples of alkylene glycol monoalkyl ether carboxylic esters include, for example, Alkylene glycol monoalkyl ether acetate.

[0563] Examples of alkylene glycol monoalkyl ether acetates include, for example, methyl cellosolve acetate, ethyl cellosolve acetate, 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, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether acetate.

[0564] Specific examples of other organic solvents include toluene, xylene, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl lactate, propyl lactate, and lactic acid. Isopropyl acetate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyrate Esters, isobutyl butyrate, ethyl hydroxybutyrate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxyisobutyrate, methyl 3-hydroxyisobutyrate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, methyl 3-methoxybutylacetate, methyl 3-methoxypropylacetate, methyl 3-methoxybutylacetate, methyl 3-methoxybutylpropionate, methyl 3-methoxybutylbutyrate, methyl acetoacetate, methyl methylpropyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, etc.

[0565] Examples of acidic solutions include aqueous solutions of inorganic acids, aqueous solutions of organic acids, and solutions of organic acids. Examples of aqueous solutions of inorganic acids include aqueous solutions of hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, and perchloric acid. Examples of aqueous solutions of organic acids include aqueous solutions of acetic acid, trifluoroacetic acid, camphor sulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid. Examples of solutions of organic acids are substances in which the water in the above-mentioned aqueous solutions of organic acids is replaced by an organic solvent. Examples of organic solvents include alkylene glycol alkyl ethers and alkylene glycol monoalkyl ether carboxylic esters.

[0566] Examples of alkaline aqueous solutions include, for instance, the developing solution used in photolithography processes.

[0567] Examples of alkaline aqueous solutions include, for example, inorganic alkaline aqueous solutions and organic alkaline aqueous solutions. Examples of inorganic alkaline aqueous solutions include potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, sodium bicarbonate aqueous solution, potassium bicarbonate aqueous solution, sodium phosphate aqueous solution, potassium phosphate aqueous solution, etc. Examples of organic alkaline aqueous solutions include tetramethylammonium hydroxide aqueous solution, tetraethylammonium hydroxide aqueous solution, tetrabutylammonium hydroxide aqueous solution, monoethanolamine aqueous solution, diethanolamine aqueous solution, triethanolamine aqueous solution, etc.

[0568] There are no particular restrictions on the concentration of alkali in an alkaline aqueous solution.

[0569] The so-called RRC (reducing resist consumption) process is a process used to reduce the amount of photoresist used. It is a process of uniformly coating a small amount of photoresist onto the entire surface of the substrate by treating the substrate surface with a diluent before coating the photoresist.

[0570] The so-called EBR (edge ​​bead removal) process is a process used to remove unwanted photoresist residues and other contaminants that were coated on the ends or backs of the substrate during the coating process.

[0571] Examples of diluents used in the RRC and EBR processes include, for example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, cyclohexanone, ethyl lactate, γ-butyrolactone, ethyl 3-ethoxypropionate or methyl hydroxyisobutyrate, and mixtures thereof.

[0572] In one embodiment of the present invention, an organic underlayer film may be disposed between the semiconductor substrate and the surface modification layer in the stack.

[0573] There are no particular restrictions on the organic underlying film used here; any material that has been conventionally used in photolithography processes to date can be selected.

[0574] By employing a scheme in which an organic underlayer film is formed on a substrate, a surface modification layer is formed thereon, and a resist film (described later) is formed thereon, substrate processing can be performed even when the pattern width of the resist film is narrowed and the resist film is thinly coated to prevent pattern collapse. For example, the underlayer resist film can be processed using a fluorine-based gas with a sufficiently fast etching rate relative to the resist film; the organic underlayer film can be processed using an oxygen-based gas with a sufficiently fast etching rate relative to the resist underlayer film; and the substrate can be processed using a fluorine-based gas with a sufficiently fast etching rate relative to the organic underlayer film.

[0575] Furthermore, the substrates and coating methods that can be used at this time are the same as those described above.

[0576] (Semiconductor device manufacturing methods)

[0577] The semiconductor device manufacturing method of the present invention includes the following steps: forming a resist film on a stack obtained by the manufacturing method of the present invention; and exposing and developing the resist film to obtain a resist pattern.

[0578] A layer (resist film) of, for example, photoresist material is formed on the surface-modified layer. The formation of the resist film can be carried out using a well-known method, namely, by coating a coating-type resist material (resist film forming composition) onto the surface-modified layer and then firing it.

[0579] The 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.

[0580] As a photoresist material used to form a resist film on a surface-modified layer, there are no particular limitations on the photosensitive light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.). Both negative and positive photoresist materials can be used. Examples include positive photoresist materials composed of phenolic varnish resin and 1,2-naphthoquinone diazonyl sulfonate; chemically amplified photoresist materials composed of a binder having groups that increase the alkali dissolution rate through acid decomposition and a photoacid generator; chemically amplified photoresist materials composed of a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist material through acid decomposition and an alkali-soluble binder and a photoacid generator; and chemically amplified photoresist materials composed of a binder having groups that increase the alkali dissolution rate of the photoresist material through acid decomposition and a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist material through acid decomposition and a photoacid generator.

[0581] Specific examples that can be obtained as commercially available products include APEX-E manufactured by Shiple Co., Ltd., PAR710 manufactured by Sumitomo Chemical Co., Ltd., AR2772JN manufactured by JSR Co., Ltd., and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd., but are not limited to these. In addition, examples such as fluorinated atom polymer-based photoresist materials described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000) can be cited.

[0582] Furthermore, in the resist film formed on the surface modification layer, an electron beam lithography resist film (also known as an electron beam resist film) or an EUV lithography resist film (also known as an EUV resist film) can be used instead of a photoresist film.

[0583] As electron beam resist materials for forming electron beam resist films, both negative and positive materials can be used. Specific examples include chemically amplified resist materials composed of an acid-generating agent and a binder having groups that change the rate of alkali dissolution through acid decomposition; chemically amplified resist materials composed of an alkali-soluble binder, an acid-generating agent, and a low-molecular-weight compound that changes the rate of alkali dissolution through acid decomposition; chemically amplified resist materials composed of an acid-generating agent, a binder having groups that change the rate of alkali dissolution through acid decomposition, and a low-molecular-weight compound that changes the rate of alkali dissolution through acid decomposition; non-chemically amplified resist materials composed of a binder having groups that change the rate of alkali dissolution through electron beam decomposition; and non-chemically amplified resist materials composed of a binder having portions where the rate of alkali dissolution changes when the electron beam is cut off. Even when using these electron beam resist materials, the resist film pattern can be formed in the same way as when a photoresist material is used with an electron beam as the irradiation source.

[0584] In addition, as EUV resist materials for forming EUV resist films, methacrylate resin-based resist materials, polyhydroxystyrene resin-based resist materials, and mixed methacrylate / polyhydroxystyrene resin-based resist materials can be used.

[0585] The resist film can be a resist film containing metal.

[0586] The metal-containing resist film is not particularly limited, but preferably contains at least one element selected from Si, Ge, Sn, Ti, Zr, Hf, Al and Co.

[0587] Metal-containing resist films are formed, for example, by metal-containing resists.

[0588] Metal-containing photoresists are also known as metal oxide photoresists (MOR), with tin oxide photoresists being a representative example.

[0589] As a metal oxide resist material, examples include, for instance, the coating composition disclosed in Japanese Patent Application Publication No. 2019-113855, which contains a metal oxygen-hydroxyl network having organic ligands through metal carbon bonds and / or metal carboxylate bonds.

[0590] One example of a metal-containing corrosion resist uses a peroxide ligand as a radiation-sensitive stabilizing ligand. The peroxide-based metal oxygen-hydroxy compound is described in detail in, for example, paragraph

[0011] of Japanese Publication No. 2019-532489. Examples of such patent documents include, for instance, U.S. Patent No. 9,176,377B2, U.S. Patent Application Publication No. 2013 / 0224652A1, U.S. Patent No. 9,310,684B2, U.S. Patent Application Publication No. 2016 / 0116839A1, and U.S. Patent Application Publication No. 15 / 291738.

[0591] Other examples of metal-containing corrosion inhibitors include the compositions described in Japanese Patent Application Publication No. 2011-253185, WO2015 / 026482, WO2016 / 065120, WO2017 / 066319, WO2017 / 156388, WO2018 / 031896, Japanese Patent Application Publication No. 2020-122959, Japanese Patent Application Publication No. 2020-122960, WO2019 / 099981, WO2019 / 199467, WO2019 / 195522, WO2019 / 195522, WO2020 / 210660, WO2021 / 011367 and WO2021 / 016229.

[0592] These contents are incorporated in this specification to the same extent as all of them expressly stated.

[0593] There are no particular limitations on the method of forming a metal-containing resist film from a metal-containing resist. For example, a method of coating a coating type resist material (a composition for forming a metal-containing resist film) as a metal-containing resist and then firing it can be cited.

[0594] Furthermore, a metal-containing resist film can be formed by vapor deposition. As a method for forming a metal-containing resist film by vapor deposition, for example, the method described in Japanese Patent Application Publication No. 2017-116923 is included in this specification to the same extent as all of which are explicitly stated. In Japanese Patent Application Publication No. 2017-116923, the metal-containing resist film of the present invention is referred to as a film containing metal oxides.

[0595] Next, the resist film formed on top of the surface-modified layer is exposed through a specified mask. During exposure, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), EUV (wavelength 13.5nm), electron beam, etc., can be used.

[0596] Alternatively, post-exposure baking can be performed as needed after exposure. Post-exposure baking can be performed under conditions where the heating temperature is appropriately selected from 70°C to 150°C and the heating time is from 0.3 minutes to 10 minutes.

[0597] Next, development is performed using a developer (e.g., an alkaline developer). Thus, in the case of using, for example, a positive photoresist film, the exposed portions of the photoresist film are removed, forming a pattern of the photoresist film.

[0598] Examples of alkaline developers 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 can be added to these developers. The developing conditions are appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0599] Furthermore, in this invention, an organic solvent can be used as the developer, and development is performed using the developer (solvent) after exposure. Thus, when using, for example, a negative photoresist film, the unexposed portions of the photoresist film are removed, forming a pattern on the photoresist film.

[0600] Examples of organic solvents used as developers 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, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate. Butyl 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 Examples of developing solutions include propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, and propyl-3-methoxypropionate. Furthermore, surfactants may be added to these developing solutions. For developing conditions, the temperature is appropriately selected from 5°C to 50°C, and the time from 10 seconds to 600 seconds.

[0601] For example, the pattern of the resist film (upper layer) formed in this way is used as a protective film to remove the surface modification layer, and then the patterned resist film and the patterned surface modification layer are used as protective films to process the substrate.

[0602] The removal (patterning) of the surface modification layer, which uses the pattern of the resist film (upper layer) as a protective film, can be performed, for example, by dry etching, using gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane.

[0603] Furthermore, halogen-based gases are preferred for dry etching of the surface-modified layer. With halogen-based gases, the photoresist film (photoresist film), which is essentially composed of organic matter, is difficult to remove. In contrast, the surface-modified layer, which contains a large number of silicon atoms, is rapidly removed by halogen-based gases. Therefore, the reduction in the thickness of the photoresist film accompanying the dry etching of the surface-modified layer can be suppressed. Consequently, the photoresist film can be used as a thin film. Therefore, fluorine-based gases are preferred for dry etching of the surface-modified layer. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2), but are not limited to these.

[0604] The processing (patterning) of the (semiconductor) substrate, which uses a patterned surface modification layer as a protective film, is preferably performed by dry etching using fluorine-based gases.

[0605] Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0606] After the substrate is processed (patterned), the surface modification layer can be removed. The removal of the surface modification layer can be carried out by dry etching or wet etching.

[0607] The dry etching of the surface modification layer preferably uses a fluorine-based gas, as exemplified in patterning, such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), etc., but is not limited to these.

[0608] Examples of solutions used for wet etching of surface modification layers include dilute hydrofluoric acid, buffered hydrofluoric acid (a mixture of HF and NH4F), aqueous solutions containing hydrochloric acid and hydrogen peroxide (SC-2 solution), aqueous solutions containing sulfuric acid and hydrogen peroxide (SPM solution), aqueous solutions containing hydrofluoric acid and hydrogen peroxide (FPM solution), and alkaline solutions containing ammonia and hydrogen peroxide (SC-1 solution). In addition to the ammonia-hydrogen peroxide aqueous solution (SC-1 solution) obtained by mixing ammonia and hydrogen peroxide with water, other alkaline solutions include those containing ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, and 1-butyl-1-methylpyrrolidone. Hydroxide, 1-propyl-1-methylpyrrolidine Hydroxide, 1-Butyl-1-methylpiperidine Hydroxide, 1-propyl-1-methylpiperidine Hydroxides, mepiquat chloride Aqueous solutions of hydroxides, trimethylsulfonium hydroxides, hydrazines, ethylenediamines, or guanidines, ranging from 1% to 99% by mass. These solutions can also be used in combination.

[0609] Example

[0610] The present invention will be described in more detail below with examples of synthesis and embodiments, but the present invention is not limited to the following embodiments.

[0611] In addition, in the embodiments, the apparatus and conditions used for the analysis of the physical properties of the samples are described below.

[0612] (1) Molecular weight determination

[0613] The molecular weight of the polymer used in this invention is the molecular weight obtained by GPC analysis and converted to polystyrene.

[0614] The GPC determination conditions were as follows: a GPC apparatus (trade name HLC-8220GPC, manufactured by Higashi Sou Corporation), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko Corporation), a column temperature of 40°C, tetrahydrofuran as the eluent, a flow rate of 1.0 mL / min, and polystyrene (manufactured by Showa Denko Corporation) as the standard sample.

[0615] (2) AFM observation

[0616] The surface roughness was evaluated by observing a 10μm × 10μm area using a Hitachi Hightech AFM5500M microscope.

[0617] (3) Film thickness measurement

[0618] The film thickness was measured using an elliptic film thickness measuring device RE-3100 (manufactured by SCREEN).

[0619] The film thickness of the surface-modified layer precursor was measured as follows. First, after measuring the film thickness of the SiO2 oxide film formed on the substrate, a surface modifier was applied. After the surface-modified layer precursor was formed, the film thickness was measured, and the difference was taken as the film thickness of the surface-modified layer precursor.

[0620] The thickness of the surface-modified layer was measured as follows. First, after measuring the thickness of the SiO2 oxide film formed on the substrate, the thickness of the surface modifier was measured after coating / thinning, and the difference was set as the thickness of the surface-modified layer.

[0621] [1] Polymer synthesis

[0622] (Synthesis example 1)

[0623] 20.0 g of 2-hydroxyethyl methacrylate, 1.0 g of azobisisobutyronitrile, and 84.0 g of propylene glycol monomethyl ether were added to a 500 mL flask and reacted at 60 °C for 24 hours to obtain an acrylic polymer (vinyl polymer) solution (solid content concentration 20% by mass). GPC analysis showed that the obtained acrylic polymer (vinyl polymer) had a Mw of 4,000 and an Mw / Mn ratio of 1.6. The obtained acrylic polymer (vinyl polymer) has the unit structure shown in the following formula.

[0624]

[0625] (Synthesis example 2)

[0626] 20.0 g of 2-hydroxypropyl methacrylate, 1.0 g of azobisisobutyronitrile, and 84.0 g of propylene glycol monomethyl ether were added to a 500 mL flask and reacted at 60 °C for 24 hours to obtain an acrylic polymer (vinyl polymer) solution (solid content concentration 20% by mass). GPC analysis showed that the Mw of the obtained acrylic polymer (vinyl polymer) was 3,800, and the Mw / Mn ratio was 1.7. The obtained acrylic polymer (vinyl polymer) has the unit structure shown in the following formula.

[0627]

[0628] (Synthesis example 3)

[0629] 20.0 g of 4-hydroxystyrene, 1.0 g of azobisisobutyronitrile (AIB), and 84.0 g of propylene glycol monomethyl ether were added to a 500 mL flask and reacted at 60 °C for 24 hours to obtain a polymer (vinyl polymer) solution (solid content concentration 20% by mass). GPC analysis showed that the obtained polymer (vinyl polymer) had a Mw of 2,500 and an Mw / Mn ratio of 1.7. The obtained polymer (vinyl polymer) has the unit structure shown in the following formula.

[0630]

[0631] (Synthesis Example 4)

[0632] 40.0 g of epoxy resin (manufactured by Daiser Chemical Industry Co., Ltd., trade name: EHPE3150), 20.3 g of 9-anthracarboxylic acid, and 308.4 g of propylene glycol monomethyl ether were added to a 500 mL flask and dissolved. Then, 1.5 g of benzyltriethylammonium was added, and the mixture was refluxed for 24 hours to allow the reaction to proceed. The resulting solution was purified by ion exchange to obtain a polymer solution (solid content concentration 20% by mass). GPC analysis showed that the Mw of the obtained polymer was 4500. The obtained polymer has the unit structure shown in the following formula.

[0633]

[0634] (Synthesis Example 5)

[0635] 40.0 g of epoxy resin (manufactured by Daiser Chemical Industry Co., Ltd., trade name: EHPE3150), 20.3 g of 9-anthracarboxylic acid, 13.7 g of benzoic acid, and 302.0 g of propylene glycol monomethyl ether were added to a 500 mL flask and dissolved. Then, 1.5 g of benzyltriethylammonium was added, and the mixture was refluxed for 24 hours to allow the reaction to proceed. The resulting solution was purified by ion exchange to obtain a polymer solution (solid content concentration 20% by mass). GPC analysis showed that the Mw of the obtained polymer was 4100. The obtained polymer has the unit structure shown in the following formula.

[0636]

[0637] (Synthesis Example 6)

[0638] 70.0 g of 2,2'-biphenol, 86.6 g of 1-pyrenecarboxaldehyde, 10.8 g of methanesulfonic acid, and 167.4 g of propylene glycol monomethyl ether were added to a 500 mL flask and reacted at 120 °C for 24 hours. The reaction solution was then redetermined in 2500 g of methanol. The resulting precipitate was filtered and dried under reduced pressure at 50 °C for 10 hours. It was then redissolved in propylene glycol monomethyl ether to obtain a polymer solution (solid content concentration 20% by mass). GPC analysis showed that the resulting polymer had a Mw of 1400 and an Mw / Mn ratio of 1.5. The resulting polymer possesses the composite structural unit shown in the following formula.

[0639]

[0640] (Synthesis Example 7)

[0641] 7.5 g of 2,2'-biphenol, 12.6 g of 1-naphthaldehyde, 1.5 g of methanesulfonic acid, and 26.4 g of propylene glycol monomethyl ether were added to a 100 mL flask and reacted at 120 °C for 24 hours. The reaction solution was then redetermined in 2500 g of methanol. The resulting precipitate was filtered and dried under reduced pressure at 50 °C for 10 hours. It was then redissolved in propylene glycol monomethyl ether to obtain a polymer solution (solid content concentration 20% by mass). GPC analysis showed that the resulting polymer had a Mw of 1690 and an Mw / Mn ratio of 2.3. The resulting polymer possessed a composite unit structure as shown in the following formula.

[0642]

[0643] (Synthesis Example 8)

[0644] 25.0 g of 2,2'-biphenol, 10.5 g of 1-naphthaldehyde, 15.5 g of 1-pyrenealdehyde, 3.8 g of methanesulfonic acid, and 54.8 g of propylene glycol monomethyl ether were added to a 500 mL flask and reacted at 120 °C for 24 hours. The reaction solution was then redetermined in 2500 g of methanol. The resulting precipitate was filtered and dried under reduced pressure at 50 °C for 10 hours. It was then redissolved in propylene glycol monomethyl ether to obtain a polymer solution (solid content concentration 20% by mass). GPC analysis showed that the resulting polymer had a Mw of 2000 and an Mw / Mn ratio of 2.1. The resulting polymer has a composite unit structure as shown in the following formula.

[0645]

[0646] (Synthesis Example 9)

[0647] 10.0 g of 1,6-bis(2,3-epoxypropane-1-yloxy)naphthalene, 5.1 g of 3,3'-dithiodipropionic acid, and ethyltriphenyl bromide were added. 0.7 g of propylene glycol monomethyl ether and 62.9 g of propylene glycol monomethyl ether were added to a 500 mL flask and reacted at 105 °C for 24 hours to obtain a polymer solution (solid content concentration 20% by mass). GPC analysis showed that the resulting polymer had a Mw of 3000 and an Mw / Mn ratio of 1.4. The resulting polymer had the unit structure shown in the following formula.

[0648]

[0649] (Synthesis Example 10)

[0650] 15.00 g of 1,6-bis(2,3-epoxypropane-1-yloxy)naphthalene, 23.10 g of monoallyl diglycidyl isocyanurate, 31.72 g of 3,3'-dithiodipropionic acid, and ethyltriphenyl bromide were added. 2.55 g of propylene glycol monomethyl ether and 54.8 g of propylene glycol monomethyl ether were added to a 500 mL flask and reacted at 105 °C for 24 hours to obtain a polymer solution (solid content concentration 20% by mass). GPC analysis showed that the resulting polymer had a Mw of 3300 and an Mw / Mn ratio of 1.4. The resulting polymer has the unit structure shown in the following formula.

[0651]

[0652] (Comparative Synthesis Example 1)

[0653] 20.0 g of methyl methacrylate, 1.0 g of azobisisobutyronitrile (AIB), and 84.0 g of propylene glycol monomethyl ether were added to a 500 mL flask and reacted at 60 °C for 24 hours to obtain an acrylic polymer solution (solid content concentration 20% by mass). GPC analysis showed that the Mw of the obtained acrylic polymer was 3,500, and the Mw / Mn ratio was 1.4. The obtained acrylic polymer has the unit structure shown in the following formula.

[0654]

[0655] (Comparative Synthesis Example 2)

[0656] Carbazole 6.69g, 9-fluorenone 7.28g, p-toluenesulfonic acid monohydrate 0.76g and 1,4-dioxane were added. 6.69 g of alkane was added to a 500 mL flask, and the mixture (manufactured by Kanto Chemical Co., Ltd.) was stirred and reacted at 100 °C for 24 hours. After the reaction, 34 g of chloroform was added to the solution for dilution, and the diluted mixture was then reprecipitated in 168 g of methanol. The resulting precipitate was filtered and dried under reduced pressure at 50 °C for 10 hours. It was then redissolved in propylene glycol monomethyl ether to obtain a polymer solution (solid content concentration 20% by mass). GPC analysis showed that the resulting polymer had a Mw of 2,800 and an Mw / Mn ratio of 1.8. The resulting polymer has a composite unit structure as shown in the following formula.

[0657]

[0658] [2] Preparation of surface modifier (coating solution)

[0659] The surface modifiers (coating solutions) were prepared by mixing the polymers and solvents obtained in the above synthesis examples in the proportions shown in Table 1 and filtering them through a 0.1 μm fluoropolymer filter. The amounts added in Tables 1-1 and 1-2 are expressed in parts by mass.

[0660] In addition, the polymer is used as a polymer solution obtained in the synthesis example for the preparation of the composition, but the polymer addition ratio in Table 1 does not represent the amount of polymer solution added, but rather the amount of polymer itself added.

[0661] The meanings of the abbreviations in Tables 1-1 and 1-2 are as follows.

[0662] <Solvent>

[0663] PGME: Propylene Glycol Monomethyl Ether

[0664] PGEE: Propylene Glycol Monoethyl Ether

[0665] PGMEA: Propylene glycol monomethyl ether acetate

[0666] <Additives>

[0667] Py-PTS: Pyridine p-toluenesulfonic acid

[0668] PL-LI: 1,3,4,6-Tetra(methoxymethyl)tetrahydroimidazo[4,5-d]imidazo-2,5(1H,3H)-dione

[0669] TMOM-BP: 3,3',5,5'-Tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol

[0670] [3] Thin film formation test

[0671] The prepared coating solutions 1–26 were applied onto silicon wafers using a spin coater. Each wafer was heated at an arbitrary temperature for 1 minute on a hot plate to form a surface modification layer precursor. Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V): thinning solution) was applied to each surface modification layer precursor, and the coating was allowed to stand for 60 seconds. The wafer was then rotated to remove the solvent and baked at 100 degrees Celsius for 30 seconds to dry. The film thickness of the surface modification layer after applying the thinning solution was measured. A reduction in film thickness to below 30 Å was defined as "good," and a surface modifier that produced a smooth surface in the AFM evaluation was defined as "uneven coating." The results are shown in Table 2.

[0672]

[0673] [4] Substrate surface modification test

[0674] Coating solutions 1 through 26 were applied to Bare-Si (bare silicon wafers). Specifically, using CLEANTRACK ACT8 (registered trademark) (Tokyo Electron), each of coating solutions 1 through 26 was applied to 1 ml of wafer, and after spin coating at 1500 rpm for 60 seconds, it was fired at the firing temperature described in Table 3. Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was applied to each surface modification layer precursor, followed by spin drying to form a surface modification layer with a thickness of less than 30 Å. The water contact angle was then measured on the Bare-Si substrate with the surface modification layers of coating solutions 1 through 26 formed. The water contact angle was measured in a constant temperature and humidity environment (23℃±2℃, 45%RH±5%) using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.). The liquid volume was 3 μl, and the measurement was taken after the liquid had settled for 5 seconds. Since the water contact angle of Bare-Si was below 20 degrees, a water contact angle less than 30 degrees was defined as not suitable for surface modification ("poor"), and a water contact angle above 30 degrees was defined as suitable for surface modification ("good"). The measurement results are recorded in Table 3 below.

[0675]

[0676] [5] Formation of resist patterns using EB exposure

[0677] Spin-coating solution 1 was applied to Bare-Si and heated at 215°C for 1 minute. Then, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was applied to the coating film, followed by spin drying to form a surface modified layer (1-3 nm) with a film thickness of less than 30 Å.

[0678] By further spinning an EUV resist solution (methacrylate / PHS-based resist) onto it and heating it at 110°C for 1 minute, an EUV resist film (C layer) is formed. Then, it is exposed using an ERIONIX EB painting apparatus (ELS-G130).

[0679] After exposure, post-exposure heating (PEB, 90°C for 1 minute) is performed, followed by cooling on a cooling plate to room temperature. Then, development is carried out using TMAH 2.38% developer for 30 seconds, followed by rinsing to form a resist pattern.

[0680] Using the same steps, a resist pattern was formed on a substrate having a surface modification layer obtained from each of coating solutions 2 to 26. Furthermore, as Comparative Example 13, a resist pattern was formed on a Bare-Si wafer without surface modification coating. Additionally, the heating temperature (firing temperature) after spin coating was set to the firing temperatures shown in Table 4.

[0681] Furthermore, regarding the obtained patterns, the ability to form a pattern with a spacing of 50 nm and a line width of 25 nm was evaluated by confirming the pattern shape observed from the pattern cross-section.

[0682] In observing the pattern shape, a shape that extends from the foot to the bottom and has no significant residue in the gaps is rated as "good," while an undesirable state where the resist pattern collapses is rated as "collapsed." The results are shown in Table 4.

[0683] .

Claims

1. A method for manufacturing a laminate having a surface modification layer and a semiconductor substrate, comprising the following steps: In the first step, after coating a surface modifier containing an organic compound (A) and a solvent (B) onto a semiconductor substrate, a firing process is performed to obtain a surface-modified layer precursor. The organic compound (A) has hydroxyl groups that can be protected by deprotected protecting groups. The second step involves contacting the surface-modified layer precursor with a thinning solution (X) to thin the surface-modified layer precursor, thereby obtaining a surface-modified layer with a film thickness of less than 5 nm.

2. The method for manufacturing a laminate according to claim 1, wherein the organic compound (A) is any one of a vinyl polymer having hydroxyl groups (A1), a polymer having a unit structure shown in formula (Y) (A2), a resin (A3), a polymer having a unit structure shown in formula (Z1) (A4), and a compound (A5) having two or more of the following structures (M). The resin (A3) is a resin with a composite unit structure, which has: a unit structure (A) having an aromatic ring and a unit structure (B) having one or more carbon atoms. The resin (A3) is obtained by reacting a carbon atom in the aromatic ring constituting unit structure (A) with a carbon atom in unit structure (B) to form a covalent bond. In formula (Y), T represents a divalent group with an aliphatic ring; Q represents a divalent organic group with a hydroxyl group, indicating that T is combined with R. 11 Connected divalent organic groups; R 11 Indicates a 1-valent base; In formula (Z1), A independently represents a hydrogen atom, a methyl atom, or an ethyl atom, and Q... 1 and Q 2 Each can be represented independently as a divalent base; In structure (M), R 101 * indicates a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms; * indicates a bonding bond.

3. The method for manufacturing a laminate according to claim 1, wherein the solvent (B) comprises at least one selected from carboxylic acids having hydroxyl groups, straight-chain or cyclic alkyl ketones, cyclic lactones, alkylene glycol monoalkyl ethers, monocarboxylic acid esters of alkylene glycol monoalkyl ethers, and alkoxycarboxylic acid esters of alkylene glycol monoalkyl ethers.

4. The method for manufacturing a laminate according to claim 1, wherein the thinning liquid (X) comprises at least one of an organic solvent and water.

5. The method for manufacturing a laminate according to claim 1, wherein the surface modifier further comprises at least one compound (C) selected from acids, their salts, and acid-producing agents.

6. The method for manufacturing a stacked body according to claim 1, wherein the semiconductor substrate is an inorganic or organic substrate, or a substrate having a film of inorganic or organic material.

7. The method for manufacturing a laminate according to claim 6, wherein the inorganic material is selected from at least one of metals, metal oxides, metal nitrides, metal carbides, metal oxynitrides, metal oxycarbides, and metal carbonitrides.

8. The method for manufacturing a multilayer according to claim 6, wherein the organic material is selected from at least one of amorphous carbon, graphite, fullerene, carbon nanotubes, diamond, diamond-like carbon, polyimide, and organic films that have been partially doped or replaced with boron, oxygen, nitrogen, phosphorus, silicon, sulfur, or halogen.

9. The method for manufacturing a laminate according to claim 1, wherein the laminate further comprises a resist underlayer film.

10. The method for manufacturing a laminate according to claim 1, wherein the second step is to thin the surface-modified layer precursor by spin-coating the thinning liquid (X) onto the surface-modified layer precursor to obtain a surface-modified layer with a film thickness of less than 5 nm.

11. The method for manufacturing a stack according to claim 1, wherein the stack is used for EUV or electron beam lithography.

12. A method for manufacturing a semiconductor device, comprising the following steps: The step of forming a resist film on a laminate obtained by the manufacturing method of any one of claims 1 to 11; and The process of exposing and developing the resist film to obtain a resist pattern.

13. A stack having a semiconductor substrate and a surface-modified layer with a thickness of less than 5 nm formed using a surface modifier containing an organic compound (A) and a solvent (B), wherein the organic compound (A) has hydroxyl groups that can be protected by a deprotected protecting group.

14. The stack according to claim 13, which is used for EUV or electron beam lithography.

15. A surface modifier comprising an organic compound (A) and a solvent (B), wherein the organic compound (A) has hydroxyl groups that can be protected by a deprotecting group. The surface modifier is used in the method for manufacturing the laminate according to any one of claims 1 to 11.

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