Composition for forming silicon-containing resist underlayer film

Abstract

A composition for forming a silicon-containing resist underlayer film, which contains component [A]: a polysiloxane that contains a structural unit derived from a hydrolyzable silane (A), and component [C]: a solvent. The hydrolyzable silane (A) has at least one of an aryl sulfonyl group having an iodine atom directly bonded to an aromatic ring and an aryl thioester group having an iodine atom directly bonded to an aromatic ring.

Description

Technical Field

[0001] The present invention relates to a silicon-containing composition for forming a resist underlayer film. Background Art

[0002] Traditionally, microfabrication has been performed in semiconductor device manufacturing through photolithography using photoresist. Microfabrication involves forming a thin film of photoresist on a semiconductor substrate, such as a silicon wafer. This thin film is then irradiated with active light, such as ultraviolet light, through a mask pattern depicting the semiconductor device pattern, followed by development. The resulting photoresist pattern acts as a protective film, and the substrate is etched to create fine irregularities corresponding to the pattern on the substrate surface.

[0003] In recent years, with the advancement of semiconductor device integration, the wavelength of active light used has also been trending towards shorter wavelengths, from KrF excimer lasers (248nm) to ArF excimer lasers (193nm). With the shortening of active light wavelengths, the effects of active light reflection from semiconductor substrates have become a major concern. For this reason, the use of a bottom anti-reflective coating (BARC) as a resist underlayer between the photoresist and the substrate being processed has become increasingly common.

[0004] As a cutting-edge microfabrication technology, double patterning using ArF immersion lithography has enabled mass production of devices at the 10nm node. As a next-generation technology, preparations are underway for mass production of double patterning using ArF immersion lithography at the 7nm node. Extreme ultraviolet (EUV) lithography with a wavelength of 13.5nm is a potential candidate for mass production at the 5nm node, the next-generation technology.

[0005] As a resist underlayer film-forming composition for EUV lithography, a silicon-containing resist underlayer film-forming composition for EUV lithography has been proposed, which contains a thermosetting silicon-containing material having a specific repeating unit containing iodine and a crosslinking catalyst (Patent Document 1).

[0006] Prior art literature Patent Literature Patent Document 1: Japanese Patent Application Laid-Open No. 2020-84175 Summary of the Invention

[0007] Technical problem to be solved by the invention In semiconductor device processing, increasing the sensitivity of resists is a key method for improving productivity and shortening exposure times. This demand is particularly strong in semiconductor device processing using cutting-edge EB (electron beam) or EUV (extreme ultraviolet) lithography, where EB irradiation time and EUV exposure time affect productivity.

[0008] The present invention has been made in view of such circumstances, and an object of the present invention is to provide a silicon-containing resist underlayer film-forming composition for forming a resist underlayer film capable of improving the sensitivity of the resist.

[0009] Technical solutions to technical problems The present inventors have conducted intensive studies to solve the above-mentioned technical problems, and as a result, have found that the above-mentioned technical problems can be solved, and have completed the present invention having the following gist.

[0010] That is, the present invention includes the following contents.

[0011] [1] A silicon-containing resist underlayer film-forming composition comprising: [A] Ingredients: Polysiloxane, and [C] ingredient: solvent, The polysiloxane includes a structural unit derived from a hydrolyzable silane (A) having at least one of an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring and an arylthioester group having an iodine atom directly bonded to an aromatic ring.

[0012] [2] A silicon-containing resist underlayer film-forming composition comprising: [A'] ingredient: polysiloxane; Component [B]: a hydrolyzable silane (A) having at least one of an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring and an arylthioester group having an iodine atom directly bonded to an aromatic ring; and [C] Component: Solvent.

[0013] [3] The silicon-containing resist underlayer film-forming composition according to [1] or [2], wherein the hydrolyzable silane (A) is a compound represented by the following formula (A-1).

[0014] [Chemistry 1]

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

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

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

[0018] R 1 It represents an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring or an arylthioester group having an iodine atom directly bonded to an aromatic ring.

[0019] R 2represents a single bond or a divalent linking group.

[0020] R 3 represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or R 3 It represents an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof.

[0021] X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0022] In R 1 、R 2 、R 3 If there are multiple R 1 、R 2 、R 3 and X may be the same or different.) [4] The silicon-containing resist underlayer film-forming composition according to [3], wherein R in the formula (A-1) 1 It is represented by the following formula (A-1-1) or the following formula (A-1-2).

[0023] [Chemistry 2]

[0024] [In formulae (A-1-1) and (A-1-2), Ar each independently represents an aromatic hydrocarbon group which may have a substituent.

[0025] m represents an integer of 1 to x (x represents the number of substituents capable of bonding to the aromatic hydrocarbon ring in Ar).

[0026] Indicates a bond.] [5] The silicon-containing resist underlayer film-forming composition according to [4], wherein, in the formulas (A-1-1) and (A-1-2), Ar represents a benzene ring, and m represents an integer of 1 to 5.

[0027] [6] The silicon-containing resist underlayer film-forming composition according to any one of [1] to [5], wherein the component [C] contains an alcohol solvent.

[0028] [7] The silicon-containing resist underlayer film-forming composition according to [6], wherein the component [C] contains propylene glycol monoalkyl ether.

[0029] [8] The silicon-containing resist underlayer film-forming composition according to any one of [1] to [7], further comprising component [D]: a curing catalyst.

[0030] [9] The silicon-containing resist underlayer film-forming composition according to any one of [1] to [8], further comprising component [E]: nitric acid.

[0031]

[10] A resist underlayer film which is a cured product of the silicon-containing resist underlayer film-forming composition according to any one of [1] to [9].

[0032]

[11] A semiconductor processing substrate comprising: a semiconductor substrate; and the resist underlayer film described in

[10] .

[0033]

[12] A method for manufacturing a semiconductor device, comprising the following steps: forming an organic lower layer film on a substrate; a step of forming a resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film-forming composition described in any one of [1] to [9]; and a step of forming a resist film on the resist underlayer film.

[0034]

[13] A pattern forming method comprising the following steps: forming an organic lower layer film on a semiconductor substrate; A step of coating the silicon-containing resist underlayer film-forming composition described in any one of [1] to [9] on the organic underlayer film and firing the composition to form a resist underlayer film; forming a resist film on the resist underlayer film; exposing and developing the resist film to obtain a resist pattern; a step of etching the resist underlayer film using the resist pattern as a mask; and A step of etching the organic underlayer film using the patterned resist underlayer film as a mask.

[0035]

[14] The pattern forming method according to

[13] , further comprising the following steps: After the step of etching the organic underlayer film, the step of removing the resist underlayer film by a wet method using a chemical solution is performed.

[0036]

[15] A hydrolyzable silane comprising at least one of an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring and an arylthioester group having an iodine atom directly bonded to an aromatic ring.

[0037]

[16] The hydrolyzable silane according to

[15] , which is a compound represented by the following formula (A-1).

[0038] [Chemistry 3]

[0039] (In formula (A-1), a represents an integer of 1 to 3.

[0040] b represents an integer from 0 to 2.

[0041] a+b represents an integer of 1 to 3.

[0042] R 1 It represents an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring or an arylthioester group having an iodine atom directly bonded to an aromatic ring.

[0043] R 2 represents a single bond or a divalent linking group.

[0044] R 3 represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or R 3 It represents an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof.

[0045] X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, In R 1 、R 2 、R 3 If there are multiple R 1 、R 2 、R 3 and X may be the same or different.)

[17] The hydrolyzable silane according to

[16] , wherein R in the formula (A-1) 1 It is represented by the following formula (A-1-1) or the following formula (A-1-2), [Chemistry 4]

[0046] [In formulae (A-1-1) and (A-1-2), Ar each independently represents an aromatic hydrocarbon group which may have a substituent.

[0047] m represents an integer of 1 to x (x represents the number of substituents capable of bonding to the aromatic hydrocarbon ring in Ar).

[0048] Indicates a bond.]

[18] A polysiloxane comprising a structural unit derived from the hydrolyzable silane according to any one of

[15] to

[17] .

[0049] Effects of the Invention According to the present invention, a silicon-containing resist underlayer film-forming composition for forming a resist underlayer film capable of improving the sensitivity of a resist can be provided. DETAILED DESCRIPTION

[0050] (Silicon-Containing Resist Underlayer Film-Forming Composition) <First embodiment> The first embodiment of the silicon-containing resist underlayer film-forming composition of the present invention contains polysiloxane as the component [A] and a solvent as the component [C], and further contains other components as needed.

[0051] The polysiloxane as the component [A] contains structural units (monomer units or repeating units) derived from a hydrolyzable silane (A) having at least one of an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring and an arylthioester group having an iodine atom directly bonded to an aromatic ring.

[0052] In addition, this polysiloxane is also the subject of the present invention.

[0053] Furthermore, the hydrolyzable silane (A) having at least one of an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring and an arylthioester group having an iodine atom directly bonded to an aromatic ring is also an object of the present invention.

[0054] <Second embodiment> A second embodiment of the silicon-containing resist underlayer film-forming composition of the present invention comprises a polysiloxane as component [A′], a hydrolyzable silane (A) as component [B], and a solvent as component [C], and further comprises other components as needed, wherein the hydrolyzable silane (A) has at least one of an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring and an arylthioester group having an iodine atom directly bonded to an aromatic ring.

[0055] The resist underlayer film formed from the silicon-containing resist underlayer film-forming composition of the present invention comprises at least one of an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring and an arylthioester group having an iodine atom directly bonded to an aromatic ring, thereby improving the sensitivity of the resist.

[0056] The present inventors believe that both the iodine atom and the sulfonyl bond [—S(O) 2 —] contribute to the improvement of the sensitivity of the resist.

[0057] The present inventors believe that both the iodine atom and the thioester bond [—S(═O)C—] contribute to improvement in the sensitivity of the resist.

[0058] Hereinafter, the “arylsulfonyl group having an iodine atom directly bonded to an aromatic ring” and the “arylthioester group having an iodine atom directly bonded to an aromatic ring” may be referred to as an “iodine atom-containing group”.

[0059] <Hydrolyzable silane (A)> The "iodine atom-containing group" (specifically, the arylsulfonyl group having an iodine atom directly bonded to the aromatic ring or the arylthioester group having an iodine atom directly bonded to the aromatic ring) possessed by the hydrolyzable silane (A) (hereinafter sometimes referred to as "hydrolyzable silane (A)") having at least one of an arylsulfonyl group having an iodine atom directly bonded to the aromatic ring or an arylthioester group having an iodine atom directly bonded to the aromatic ring) may be directly bonded to the silicon atom (single bond) or may be bonded via a linking group, preferably via a linking group. Examples of the linking group include a hydrocarbon group having 1 to 20 carbon atoms that may be interrupted by an oxygen atom, a sulfur atom, or an amide bond, -O-, -S-, -NHCO-, or -CONH-.

[0060] The hydrolyzable silane (A) may have two or more iodine-containing groups. In this case, the two or more "iodine-containing groups" may have the same structure or different structures. In addition, the two or more "iodine-containing groups" may each be bonded to a linking group bonded to a silicon atom. The two or more "iodine-containing groups" may each be directly bonded to a silicon atom or bonded to a silicon atom via different linking groups.

[0061] In one "iodine atom-containing group", the number of iodine atoms directly bonded to the aromatic ring may be one or two or more.

[0062] The arylsulfonyl group having an iodine atom directly bonded to an aromatic ring is represented by, for example, the following formula (A-1-1).

[0063] The arylthioester group having an iodine atom directly bonded to an aromatic ring is represented by, for example, the following formula (A-1-2).

[0064] [Chemistry 5]

[0065] [In formulae (A-1-1) and (A-1-2), Ar each independently represents an aromatic hydrocarbon group which may have a substituent.

[0066] m represents an integer of 1 to x (x represents the number of substituents capable of bonding to the aromatic hydrocarbon ring in Ar).

[0067] Indicates a bond.] Examples of Ar in formulas (A-1-1) and (A-1-2) include a benzene ring that may have a substituent, a naphthalene ring that may have a substituent, and an anthracene ring that may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms.

[0068] When Ar in formula (A-1-1) and (A-1-2) is a benzene ring, examples of m include integers of 1 to 5.

[0069] When Ar in formulae (A-1-1) and (A-1-2) is a naphthalene ring, examples of m include integers of 1 to 7.

[0070] Ar in formula (A-1-1) and (A-1-2) preferably represents a benzene ring. In this case, m in formula (A-1-1) and (A-1-2) preferably represents an integer of 1 to 5.

[0071] The hydrolyzable silane (A) is preferably a compound represented by the following formula (A-1).

[0072] [Chemistry 6]

[0073] (In formula (A-1), a represents an integer of 1 to 3.

[0074] b represents an integer from 0 to 2.

[0075] a+b represents an integer of 1 to 3.

[0076] R 1 It represents an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring or an arylthioester group having an iodine atom directly bonded to an aromatic ring.

[0077] R 2 represents a single bond or a divalent linking group.

[0078] R 3represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or R 3 It represents an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof.

[0079] X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0080] In R 1 、R 2 、R 3 If there are multiple R 1 、R 2 、R 3 and X may be the same or different.) It should be noted that R 1 -R 2 -Base and R 3 -groups are different groups.

[0081] As R 1 Specific examples and preferred embodiments of the arylsulfonyl group having an iodine atom directly bonded to an aromatic ring include the specific examples and preferred embodiments described for the arylsulfonyl group having an iodine atom directly bonded to an aromatic ring contained in the hydrolyzable silane (A).

[0082] As R 1 Specific examples and preferred embodiments of the arylthioester group having an iodine atom directly bonded to an aromatic ring include the specific examples and preferred embodiments described for the arylthioester group having an iodine atom directly bonded to an aromatic ring possessed by the hydrolyzable silane (A).

[0083] R in formula (A-1) 1 It is preferably represented by the above formula (A-1-1) or formula (A-1-2).

[0084] As R in formula (A-1) 2 Examples of the divalent linking group include a hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom or an amide bond, -O- (ether bond), -S- (thioether bond), -NHCO- or -CONH- (each an amide bond).

[0085] Examples of hydrocarbon groups having 1 to 20 carbon atoms include alkylene groups having 1 to 20 carbon atoms. Alkylene groups having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination of two or more thereof. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6. Examples of such alkylene groups include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene.

[0086] Examples of the hydrocarbon group having 1 to 20 carbon atoms include o-phenylene, m-phenylene, and p-phenylene.

[0087] Examples of the hydrocarbon group having 1 to 20 carbon atoms include groups in which one or more methylene groups in an alkylene group are substituted with o-phenylene, m-phenylene, or p-phenylene groups.

[0088] Among them, the linking group is preferably a methylene group, an ethylene group, or a trimethylene group.

[0089] Examples of the hydrocarbon group having 1 to 20 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom or an amide bond include groups containing the structural units -CH2-O-, -CH2-S-, -CH2-NHCO- or -CH2-CONH-.

[0090] Specifically, examples include divalent groups obtained by removing one hydrogen atom from a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a methylcarbonylamino group, an ethylcarbonylamino group, a propylcarbonylamino group, a butylcarbonylamino group, a methylaminocarbonyl group, an ethylaminocarbonyl group, a propylaminocarbonyl group, a butylaminocarbonyl group, and the like. Further examples include divalent groups obtained by removing one hydrogen atom from a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, or an octadecyl group, and groups obtained by replacing one or more hydrogen atoms possessed by each of these groups with a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a methylcarbonylamino group, an ethylcarbonylamino group, a methylaminocarbonyl group, an ethylaminocarbonyl group, and the like.

[0091] <<R in formula (A-1) 3 >> The alkyl group may be linear, branched, or cyclic, and the number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and even more preferably 10 or less.

[0092] Specific examples of the linear or branched alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-butyl, n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl and 1-ethyl-2-methyl-n-propyl, etc.

[0093] In this specification, “iso” refers to “iso”, “secondary” refers to “sec”, and “tertiary” refers to “tert”.

[0094] Specific examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclohexyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl, 1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl Cycloalkyl groups such as cyclobutyl, 2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl, 2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-isopropylcyclopropyl, 1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl, 2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl, 2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl and 2-ethyl-3-methylcyclopropyl; cross-linked cyclic cycloalkyl groups such as bicyclobutyl, bicyclopentyl, bicyclohexyl, bicycloheptyl, bicyclooctyl, bicyclononyl and bicyclodecyl;

[0095] The aryl group may be any one of a phenyl group, a monovalent group derived from a condensed ring aromatic hydrocarbon compound by removing a hydrogen atom, and a monovalent group derived from a ring-linked aromatic hydrocarbon compound by removing a hydrogen atom. The number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0096] For example, the aryl group includes an aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, 1-naphthyl, 2-naphthyl, 5-naphthyl, 2-chrysyl, 1-pyrenyl, 2-pyrenyl, pentacene, benzopyrenyl, triphenylene; biphenyl-2-yl (o-biphenyl), biphenyl-3-yl (m-biphenyl), biphenyl-4-yl (p-biphenyl), p-terphenyl-4-yl, m-terphenyl-4-yl, o-terphenyl-4-yl, 1,1′-binaphthyl-2-yl, and 2,2′-binaphthyl-1-yl, but are not limited thereto.

[0097] The aralkyl group is an alkyl group substituted with an aryl group. Specific examples of such aryl groups and alkyl groups include the same specific examples as above. The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0098] Specific examples of the aralkyl group include, but are not limited to, phenylmethyl (benzyl), 2-phenylethylene, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, 8-phenyl-n-octyl, 9-phenyl-n-nonyl, and 10-phenyl-n-decyl.

[0099] The halogenated alkyl group, halogenated aryl group and halogenated aralkyl group are alkyl groups, aryl groups and aralkyl groups, respectively, substituted with one or more halogen atoms. Specific examples of such alkyl groups, aryl groups and aralkyl groups include the same specific examples as described above.

[0100] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0101] The number of carbon atoms in the haloalkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and even more preferably 10 or less.

[0102] Specific examples of the haloalkyl group include, but are not limited to, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a bromodifluoromethyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 1,1-difluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a 2-chloro-1,1,2-trifluoroethyl group, a pentafluoroethyl group, a 3-bromopropyl group, a 2,2,3,3-tetrafluoropropyl group, a 1,1,2,3,3,3-hexafluoropropyl group, a 1,1,1,3,3,3-hexafluoropropane-2-yl group, a 3-bromo-2-methylpropyl group, a 4-bromobutyl group, and a perfluoropentyl group.

[0103] The number of carbon atoms in the halogenated aryl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and further preferably 20 or less.

[0104] Specific examples of the halogenated aryl group include 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl, pentafluorophenyl, 2-fluoro-1-naphthyl, 3-fluoro-1-naphthyl, The present invention also includes 4-fluoro-1-naphthyl, 6-fluoro-1-naphthyl, 7-fluoro-1-naphthyl, 8-fluoro-1-naphthyl, 4,5-difluoro-1-naphthyl, 5,7-difluoro-1-naphthyl, 5,8-difluoro-1-naphthyl, 5,6,7,8-tetrafluoro-1-naphthyl, heptafluoro-1-naphthyl, 1-fluoro-2-naphthyl, 5-fluoro-2-naphthyl, 6-fluoro-2-naphthyl, 7-fluoro-2-naphthyl, 5,7-difluoro-2-naphthyl, heptafluoro-2-naphthyl, and the like. In addition, examples include those in which the fluorine atom (fluoro group) in these groups is arbitrarily substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group), but the present invention is not limited thereto.

[0105] The number of carbon atoms in the halogenated aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and further preferably 20 or less.

[0106] Specific examples of the halogenated aralkyl group include 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl, 2,5-difluorobenzyl, 2,6-difluorobenzyl, 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2,3,4-trifluorobenzyl, 2,3,5-trifluorobenzyl, 2,3,6-trifluorobenzyl, 2,4,5-trifluorobenzyl, 2,4,6-trifluorobenzyl, 2,3,4,5-tetrafluorobenzyl, 2,3,4,6-tetrafluorobenzyl, 2,3,5,6-tetrafluorobenzyl, and 2,3,4,5,6-pentafluorobenzyl. In addition, examples include groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group), but the present invention is not limited thereto.

[0107] The alkoxyalkyl group, alkoxyaryl group and alkoxyaralkyl group are respectively an alkyl group, an aryl group and an aralkyl group substituted with one or more alkoxy groups. Specific examples of such alkyl groups, aryl groups and aralkyl groups include the same specific examples as described above.

[0108] Examples of the alkoxy group as a substituent include alkoxy groups having at least one of a linear, branched, and cyclic alkyl moiety having 1 to 20 carbon atoms.

[0109] Examples of the linear or branched alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentoxy group, a 2-methyl-n-pentoxy group, a 3-methyl-n-butoxy group, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy and 1-ethyl-2-methyl-n-propoxy, etc.

[0110] Examples of the cyclic alkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a 1-methylcyclopropyloxy group, a 2-methylcyclopropyloxy group, a cyclopentyloxy group, a 1-methylcyclobutyloxy group, a 2-methylcyclobutyloxy group, a 3-methylcyclobutyloxy group, a 1,2-dimethylcyclopropyloxy group, a 2,3-dimethylcyclopropyloxy group, a 1-ethylcyclopropyloxy group, a 2-ethylcyclopropyloxy group, a cyclohexyloxy group, a 1-methylcyclopentyloxy group, a 2-methylcyclopentyloxy group, a 3-methylcyclopentyloxy group, a 1-ethylcyclobutyloxy group, a 2-ethylcyclobutyloxy group, a 3-ethylcyclobutyloxy group, a 1,2-dimethylcyclobutyloxy group, a 1,3- Dimethylcyclobutoxy, 2,2-dimethylcyclobutoxy, 2,3-dimethylcyclobutoxy, 2,4-dimethylcyclobutoxy, 3,3-dimethylcyclobutoxy, 1-n-propylcyclopropoxy, 2-n-propylcyclopropoxy, 1-isopropylcyclopropoxy, 2-isopropylcyclopropoxy, 1,2,2-trimethylcyclopropoxy, 1,2,3-trimethylcyclopropoxy, 2,2,3-trimethylcyclopropoxy, 1-ethyl-2-methylcyclopropoxy, 2-ethyl-1-methylcyclopropoxy, 2-ethyl-2-methylcyclopropoxy and 2-ethyl-3-methylcyclopropoxy, etc.

[0111] Specific examples of the alkoxyalkyl group include lower (having about 5 or less carbon atoms) alkoxy lower (having about 5 or less carbon atoms) alkyl groups such as methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, and ethoxymethyl, but are not limited thereto.

[0112] Specific examples of the alkoxyaryl group include, but are not limited to, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(1-ethoxy)phenyl, 3-(1-ethoxy)phenyl, 4-(1-ethoxy)phenyl, 2-(2-ethoxy)phenyl, 3-(2-ethoxy)phenyl, 4-(2-ethoxy)phenyl, 2-methoxynaphth-1-yl, 3-methoxynaphth-1-yl, 4-methoxynaphth-1-yl, 5-methoxynaphth-1-yl, 6-methoxynaphth-1-yl, and 7-methoxynaphth-1-yl.

[0113] Specific examples of the alkoxyaralkyl group include 3-(methoxyphenyl)benzyl and 4-(methoxyphenyl)benzyl, but are not limited thereto.

[0114] The alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and even more preferably 10 or less.

[0115] Specific examples of alkenyl groups include ethenyl (vinyl), 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl. vinyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl , 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3- Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-methyl-1-ethyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-isopropyl-1-propenyl, 1-isopropyl-2-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl, 2-methyl-3-cyclopentenyl , 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylenecyclopentyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylenecyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl and 3-cyclohexenyl, and cross-linked ring alkenyl groups such as bicycloheptenyl (norbornyl) can also be mentioned.

[0116] In addition, examples of substituents in the alkyl group, aryl group, aralkyl group, haloalkyl group, haloaryl group, haloarylalkyl group, alkoxyalkyl group, alkoxyaryl group, alkoxyarylalkyl group, and alkenyl group include alkyl group, aryl group, aralkyl group, haloalkyl group, haloaryl group, haloarylalkyl group, alkoxyalkyl group, aryloxy group, alkoxyaryl group, alkoxyarylalkyl group, alkenyl group, alkoxy group, aralkyloxy group, and the like. Specific examples of these and preferred carbon atom numbers thereof are the same as those described above or below.

[0117] In addition, the aryloxy group mentioned in the substituent is a group in which an aryl group is bonded via an oxygen atom (-O-). Specific examples of such aryl groups include the same specific examples as described above. The number of carbon atoms in the oxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples include, but are not limited to, phenoxy and naphth-2-yloxy.

[0118] When there are two or more substituents, the substituents may be bonded to each other to form a ring.

[0119] Examples of the organic group having an epoxy group include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, and an epoxycyclohexyl group.

[0120] Examples of the organic group having an acryloyl group include an acryloylmethyl group, an acryloylethyl group, and an acryloylpropyl group.

[0121] Examples of the organic group having a methacryloyl group include a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group.

[0122] Examples of the organic group having a mercapto group include a mercaptoethyl group, a mercaptobutyl group, a mercaptohexyl group, a mercaptooctyl group, and a mercaptophenyl group.

[0123] Examples of the organic group having an amino group include, but are not limited to, amino, aminomethyl, aminoethyl, aminophenyl, dimethylaminoethyl, and dimethylaminopropyl groups.

[0124] Examples of the organic group having an alkoxy group include, but are not limited to, a methoxymethyl group and a methoxyethyl group, and do not include groups in which an alkoxy group is directly bonded to a silicon atom.

[0125] Examples of the organic group having a sulfonyl group include a sulfonylalkyl group and a sulfonylaryl group, but the group is not limited thereto.

[0126] Examples of the organic group having a cyano group include a cyanoethyl group, a cyanopropyl group, a cyanophenyl group, and a thiocyanate group.

[0127] Examples of organic groups containing amino groups include those containing at least one of primary, secondary, and tertiary amino groups. Preferred examples include hydrolysis-condensation products obtained by hydrolyzing a hydrolyzable silane containing a tertiary amino group with a strong acid to form a counter cation containing a tertiary ammonium group. Furthermore, in addition to the nitrogen atom constituting the amino group, the organic group may also contain heteroatoms such as oxygen and sulfur atoms.

[0128] As a preferred example of the organic group having an amino group, a group represented by the following formula (A1) can be mentioned.

[0129] [Chemistry 7]

[0130] In formula (A1), R 101 and R 102 Each of them independently represents a hydrogen atom or a hydrocarbon group, and each of them independently represents an alkylene group which may be substituted. Indicates a bond.

[0131] Examples of the hydrocarbon group include, but are not limited to, alkyl, alkenyl, and aryl groups. Specific examples of these alkyl, alkenyl, and aryl groups include: 3 The same specific example as above.

[0132] The alkylene group may be either linear or branched, and the number of carbon atoms thereof is usually 1 to 10, preferably 1 to 5. Examples thereof include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene.

[0133] Examples of the organic group having an amino group include, but are not limited to, an amino group, an aminomethyl group, an aminoethyl group, an aminophenyl group, a dimethylaminoethyl group, and a dimethylaminopropyl group.

[0134] <<X in formula (A-1)>> Examples of the alkoxy group in X include R 3 The alkoxy group exemplified in the description of .

[0135] Examples of the halogen atom in X include R 3 The halogen atoms exemplified in the description of .

[0136] The aralkyloxy group is a monovalent group derived by removing a hydrogen atom from a hydroxyl group of an aralkyl alcohol. Specific examples of the aralkyl group in the aralkyloxy group include the same specific examples as described above.

[0137] The number of carbon atoms in the aralkyloxy group is not particularly limited, and can be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less.

[0138] Specific examples of the aralkyloxy group include, but are not limited to, phenylmethoxy (benzyloxy), 2-phenylethyleneoxy, 3-phenyl-n-propoxy, 4-phenyl-n-butoxy, 5-phenyl-n-pentoxy, 6-phenyl-n-hexyloxy, 7-phenyl-n-heptyloxy, 8-phenyl-n-octyloxy, 9-phenyl-n-nonyloxy, and 10-phenyl-n-decyloxy.

[0139] An acyloxy group is a monovalent group derived from the carboxyl group (-COOH) of a carboxylic acid compound by removing a hydrogen atom. Typical examples include, but are not limited to, alkylcarbonyloxy, arylcarbonyloxy, and aralkylcarbonyloxy groups derived from the carboxyl group of an alkylcarboxylic acid, an arylcarboxylic acid, or an aralkylcarboxylic acid by removing a hydrogen atom. Specific examples of the alkyl, aryl, and aralkyl groups in such alkylcarboxylic acids, arylcarboxylic acids, and aralkylcarboxylic acids include the same specific examples as described above.

[0140] Specific examples of the acyloxy group include acyloxy groups having 2 to 20 carbon atoms, such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, n-pentylcarbonyloxy, 1-methyl-n-butylcarbonyloxy, 2-methyl-n-butylcarbonyloxy, 3-methyl-n-butylcarbonyloxy, 1,1-dimethyl-n-propylcarbonyloxy, 1,2-dimethyl-n-propylcarbonyloxy, 2,2-dimethyl-n-propylcarbonyloxy, 1-ethyl-n-propylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl-n-pentylcarbonyloxy, 2-methyl-n-pentylcarbonyloxy, 3-methyl-n-pentylcarbonyloxy, 4-methyl-n-pentylcarbonyloxy, 1,1-dimethyl-n-butylcarbonyloxy, 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, phenylcarbonyloxy and tosylcarbonyloxy, etc.

[0141] Specific examples of the hydrolyzable silane (A) include the following compounds, but the hydrolyzable silane (A) is not limited to these compounds.

[0142] [Chemistry 8]

[0143] In the formula, R represents a methyl group or an ethyl group.

[0144] The method for synthesizing the hydrolyzable silane (A) is not particularly limited, and the hydrolyzable silane (A) can be produced, for example, by the method for producing a silane compound having a sulfonyl bond described in International Publication No. 2015 / 198945.

[0145] In the first embodiment, the amount of the hydrolyzable silane (A) when synthesizing a polysiloxane [A] containing a structural unit derived from the hydrolyzable silane (A) is preferably 0.01 to 100 parts by mass, or 0.05 to 50 parts by mass, or 0.1 to 30 parts by mass, or 0.1 to 20 parts by mass, or 0.1 to 10 parts by mass, or 0.5 to 10 parts by mass, 1 to 8 parts by mass, 2 to 7 parts by mass, or 3 to 6 parts by mass, relative to 100 parts by mass of the total amount of the hydrolyzable silane used in the synthesis of the polysiloxane, from the viewpoint of more fully achieving the effects of the present invention.

[0146] In the second embodiment, from the viewpoint of more fully achieving the effects of the present invention, the content of the hydrolyzable silane (A) as the component [B] in the silicon-containing resist underlayer film-forming composition is preferably 0.01 to 100 parts by mass, or 0.05 to 50 parts by mass, or 0.1 to 30 parts by mass, or 0.1 to 20 parts by mass, or 0.1 to 10 parts by mass, or 0.5 to 10 parts by mass, 1 to 8 parts by mass, 2 to 7 parts by mass, or 3 to 6 parts by mass, relative to 100 parts by mass of the polysiloxane [A′].

[0147] <Component [A] and component [A′]: polysiloxane> The polysiloxane as the component [A] is not particularly limited as long as it is a polymer containing a structural unit derived from the hydrolyzable silane (A) and having a siloxane bond.

[0148] The polysiloxane as the component [A'] is not particularly limited as long as it is a polymer having a siloxane bond. The polysiloxane as the component [A'] may be the polysiloxane as the component [A].

[0149] The polysiloxane may be a modified polysiloxane in which a part of the silanol groups is modified, for example, a modified polysiloxane in which a part of the silanol groups is modified with an alcohol or protected with an acetal.

[0150] As an example, the polysiloxane may be a hydrolysis condensate of a hydrolyzable silane, or a modified product in which at least a portion of the silanol groups of the hydrolysis condensate are modified with an alcohol or protected with an acetal (hereinafter sometimes referred to as a "modified product of the hydrolysis condensate"). The hydrolyzable silane involved in the hydrolysis condensate may include one or more hydrolyzable silanes.

[0151] The polysiloxane as the component [A] or [A'] may have a main chain structure of any of cage, ladder, linear, and branched types. Furthermore, commercially available polysiloxanes may be used as the component [A'].

[0152] It should be noted that, in the present invention, the "hydrolysis-condensation product" of a hydrolyzable silane, i.e., the product of hydrolysis-condensation, includes not only completely condensed condensates, i.e., polysiloxane polymers, but also partially hydrolyzed condensates, i.e., polysiloxane polymers, in which condensation is not completely completed. These partially hydrolyzed condensates, like completely condensed condensates, are polymers obtained by hydrolysis and condensation of the hydrolyzable silane. However, since the partial hydrolysis is terminated and condensation does not occur, Si-OH groups remain. Furthermore, the silicon-containing resist underlayer film-forming composition may contain, in addition to the hydrolysis-condensation product, uncondensed hydrolyzates (completely hydrolyzed, partially hydrolyzed) and monomers (hydrolyzable silane).

[0153] In addition, in this specification, "hydrolyzable silane" may be simply referred to as "silane compound".

[0154] Examples of the polysiloxane of the component [A] include hydrolysis-condensation products of hydrolyzable silanes including the hydrolyzable silane (A) or modified products thereof.

[0155] Examples of the polysiloxane of the component [A] include hydrolyzable silane (A) and a hydrolysis-condensation product of a hydrolyzable silane containing at least one hydrolyzable silane represented by the following formula (1), or a modified product thereof.

[0156] Examples of the polysiloxane of the component [A'] include hydrolysis-condensation products of hydrolyzable silanes containing at least one type of hydrolyzable silane represented by the following formula (1) or modified products thereof.

[0157] <<Formula (1)>> [Chemistry 9]

[0158] In formula (1), R 1 is a group bonded to a silicon atom, each independently representing an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or R 1 It represents an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof.

[0159] In addition, R 2 is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0160] a represents an integer from 0 to 3.

[0161] As R in formula (1) 1 Specific examples of the groups and atoms in the formula (A-1) and their preferred carbon number are as follows: 3 The group and the number of carbon atoms described.

[0162] As R in formula (1) 2 Specific examples of the groups and atoms in the formula (A-1) and their preferred carbon atom numbers include the groups and atoms and carbon atom numbers described for X in the formula (A-1).

[0163] <<<Specific examples of the hydrolyzable silane represented by formula (1)>>> Specific examples of the hydrolyzable silane represented by formula (1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltripentoxysilane, methyltriphenoxysilane, methyltripenzyloxysilane, methyltriphenethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α -Glycidoxyethyltrimethoxysilane, α -Glycidoxyethyltriethoxysilane, β -Glycidoxyethyltrimethoxysilane, β -Glycidoxyethyltriethoxysilane, α -Glycidoxypropyltrimethoxysilane, α -Glycidoxypropyltriethoxysilane, β -Glycidoxypropyltrimethoxysilane, β -Glycidoxypropyltriethoxysilane, c -Glycidoxypropyltrimethoxysilane, c -Glycidoxypropyltriethoxysilane, c -Glycidoxypropyltripropoxysilane, c -Glycidoxypropyltributoxysilane, c -Glycidoxypropyl triphenoxysilane, α -Glycidoxybutyltrimethoxysilane, α -Glycidoxybutyltriethoxysilane, β -Glycidoxybutyltriethoxysilane, c -Glycidoxybutyltrimethoxysilane, c -Glycidoxybutyltriethoxysilane, d -Glycidoxybutyltrimethoxysilane, d -Glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, β -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β -(3,4-epoxycyclohexyl)ethyltriethoxysilane, β -(3,4-epoxycyclohexyl)ethyltripropoxysilane, β -(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, c -(3,4-epoxycyclohexyl)propyltrimethoxysilane, c -(3,4-epoxycyclohexyl)propyltriethoxysilane, d -(3,4-epoxycyclohexyl)butyltrimethoxysilane, d -(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α -Glycidoxyethylmethyldimethoxysilane, α -Glycidoxyethylmethyldiethoxysilane, β -Glycidoxyethylmethyldimethoxysilane, β -Glycidoxyethylethyldimethoxysilane, α -Glycidoxypropylmethyldimethoxysilane, α -Glycidoxypropylmethyldiethoxysilane, β -Glycidoxypropylmethyldimethoxysilane, β -Glycidoxypropylethyldimethoxysilane, c -Glycidoxypropylmethyldimethoxysilane, c -Glycidoxypropylmethyldiethoxysilane, c -Glycidoxypropylmethyldipropoxysilane, c -Glycidoxypropylmethyldibutoxysilane, c -Glycidoxypropylmethyldiphenoxysilane, c -Glycidoxypropylethyldimethoxysilane, c -Glycidoxypropylethyldiethoxysilane, c -Glycidoxypropylvinyldimethoxysilane, c - Glycidoxypropyl vinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldichlorosilane, divinyldiacetoxysilane, c -Glycidoxypropylvinyldimethoxysilane, c-Glycidoxypropylvinyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldichlorosilane, allylmethyldiacetoxysilane, allyldimethylmethoxysilane, allyldimethylethoxysilane, allyldimethylchlorosilane, allyldimethylacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldichlorosilane, diallyldiacetoxysilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyltriethoxysilane, p-phenylenyltrimethoxysilane, phenyltrimethoxysilane, phenyl Triethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiacetoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylacetoxysilane, triphenylchlorosilane, 3-phenylaminopropyltrimethoxysilane, 3-phenylaminopropyl Triethoxysilane, dimethoxymethyl-3-(3-phenoxypropylthiopropyl) silane, triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, benzyldimethylchlorosilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, phenethyltrichlorosilane, phenethyltriacetoxysilane, phenethylmethyldimethoxysilane, phenethylmethyldiethoxysilane, phenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyl Triacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane, methoxyphenethyltrimethoxysilane, methoxyphenethyltriethoxysilane, methoxyphenethyltriacetoxysilane, methoxyphenethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriacetoxysilane, ethoxyphenyltrichlorosilane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane,Isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane, tert-butoxyphenyltrimethoxysilane, tert-butoxyphenyltriethoxysilane, tert-butoxyphenyltriacetoxysilane, tert-butoxyphenyltrichlorosilane, tert-butoxybenzyltrimethoxysilane, tert-butoxybenzyltriethoxysilane, tert-butoxybenzyltriacetoxysilane, tert-butoxybenzyltrichlorosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, c -Chloropropyltrimethoxysilane, c -Chloropropyltriethoxysilane, c -Chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, c -Methacryloxypropyltrimethoxysilane, c -Mercaptopropyltrimethoxysilane, c -Mercaptopropyltriethoxysilane, β -Cyanoethyl triethoxysilane, thiocyanate propyl triethoxysilane, chloromethyl trimethoxysilane, chloromethyl triethoxysilane, triethoxysilylpropyl diallyl isocyanurate, bicyclo[2,2,1]heptenyl triethoxysilane, phenylsulfonylpropyl triethoxysilane, phenylsulfonamidopropyl triethoxysilane, dimethylaminopropyl trimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, c -Chloropropylmethyldimethoxysilane, c -Chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, c -Methacryloxypropylmethyldimethoxysilane, c -Methacryloxypropylmethyldiethoxysilane, c -Mercaptopropylmethyldimethoxysilane, c -mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, silanes represented by the following formulas (A-1) to (A-41), silanes represented by the following formulas (1-1) to (1-294), etc., but are not limited thereto.

[0164] [Chemistry 10]

[0165] [Chemistry 11]

[0166] [Chemistry 12]

[0167] [Chemistry 13]

[0168] [Chemistry 14]

[0169] [Chemistry 15]

[0170] [Chemistry 16]

[0171] [Chemistry 17]

[0172] [Chemistry 18]

[0173] [Chemistry 19]

[0174] [Chemistry 20]

[0175] [Chemistry 21]

[0176] [Chemistry 22]

[0177] [Chemistry 23]

[0178] [Chemistry 24]

[0179] [Chemistry 25]

[0180] [Chemistry 26]

[0181] [Chemistry 27]

[0182] [Chemistry 28]

[0183] [Chemistry 29]

[0184] [Chemistry 30]

[0185] [Chemistry 31]

[0186] [Chemistry 32]

[0187] [Chemistry 33]

[0188] [Chemistry 34]

[0189] [Chemistry 35]

[0190] [Chemistry 36]

[0191] [Chemistry 37]

[0192] [Chemistry 38]

[0193] [Chemistry 39]

[0194] [Chemistry 40]

[0195] [Chemistry 41]

[0196] [Chemistry 42]

[0197] [Chemistry 43]

[0198] [Chemistry 44]

[0199] [Chemistry 45]

[0200] [Chemistry 46]

[0201] [Chemistry 47]

[0202] [Chemistry 48]

[0203] [Chemistry 49]

[0204] [Chemistry 50]

[0205] [Chemistry 51]

[0206] [Chemistry 52]

[0207] [Chemistry 53]

[0208] [Chemistry 54]

[0209] [Chemistry 55]

[0210] [Chemistry 56]

[0211] [Chemistry 57]

[0212] [Chemistry 58]

[0213] [Chemistry 59]

[0214] In formulae (1-1) to (1-294), T independently represents an alkoxy group, an acyloxy group, or a halogen group, and preferably represents a methoxy group or an ethoxy group, for example.

[0215] Examples of the polysiloxane [A] include hydrolysis-condensation products of hydrolyzable silanes containing the hydrolyzable silane (A) and a hydrolyzable silane represented by the following formula (2), or modified products thereof.

[0216] Examples of the polysiloxane [A] include hydrolysis condensates of hydrolyzable silanes including the hydrolyzable silane (A), the hydrolyzable silane represented by formula (1), and the hydrolyzable silane represented by the following formula (2), or modified products thereof.

[0217] Examples of the polysiloxane [A′] include hydrolysis condensates of hydrolyzable silanes, which contain a hydrolyzable silane represented by formula (1) and a hydrolyzable silane represented by the following formula (2), or a hydrolyzable silane represented by the following formula (2) in place of the hydrolyzable silane represented by formula (1), or modified products thereof.

[0218] <Formula (2)> [Chemistry 60]

[0219] In formula (2), R 3 is a group bonded to a silicon atom, each independently representing an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or R 3 It represents an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more thereof.

[0220] In addition, R 4 is a group or atom bonded to a silicon atom, and each independently represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0221] R 5 is a group bonded to a silicon atom, and each independently represents an alkylene group or an arylene group.

[0222] b represents 0 or 1, and c represents 0 or 1.

[0223] As R 3 Specific examples of the groups and atoms in the formula (A-1) and their preferred carbon number are as follows: 3 The group and the number of carbon atoms described.

[0224] As R 4 Specific examples of the groups and atoms in the formula (A-1) and their preferred carbon atom numbers include the groups and atoms and carbon atom numbers described for X in the formula (A-1).

[0225] As R 5Specific examples of the alkylene group in the group include straight-chain alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched-chain alkylene groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; and methanetriyl, ethane-1,1,2-triyl, ethane-1,2,2-triyl, ethane-2,2,2 Alkane triyl groups include, but are not limited to, alkane triyl groups such as butane-1,1,1-triyl, propane-1,1,2-triyl, propane-1,2,3-triyl, propane-1,2,2-triyl, propane-1,1,3-triyl, butane-1,1,1-triyl, butane-1,1,2-triyl, butane-1,1,3-triyl, butane-1,2,3-triyl, butane-1,2,4-triyl, butane-1,2,2-triyl, butane-2,2,3-triyl, 2-methylpropane-1,1,1-triyl, 2-methylpropane-1,1,2-triyl, and 2-methylpropane-1,1,3-triyl.

[0226] As R 5 Specific examples of the arylene group in include: 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; groups derived from the aromatic ring of a condensed-ring aromatic hydrocarbon compound by removing two hydrogen atoms from the aromatic ring of a condensed-ring aromatic hydrocarbon compound, such as 1,5-naphthalenediyl, 1,8-naphthalenediyl, 2,6-naphthalenediyl, 2,7-naphthalenediyl, 1,2-anthracenediyl, 1,3-anthracenediyl, 1,4-anthracenediyl, 1,5-anthracenediyl, 1,6-anthracenediyl, 1,7-anthracenediyl, 1,8-anthracenediyl, 2,3-anthracenediyl, 2,6-anthracenediyl, 2,7-anthracenediyl, 2,9-anthracenediyl, 2,10-anthracenediyl, and 9,10-anthracenediyl; and groups derived from the aromatic ring of a ring-linked aromatic hydrocarbon compound by removing two hydrogen atoms from the aromatic ring, such as 4,4′-biphenyldiyl and 4,4′′-p-terphenyldiyl, but are not limited thereto.

[0227] b is preferably 0.

[0228] c is preferably 1.

[0229] Specific examples of the hydrolyzable silane represented by formula (2) include: methylenebistrimethoxysilane, methylenebistrichlorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebistrichlorosilane, ethylenebistriacetoxysilane, propylenebistriethoxysilane, butylenebistrimethoxysilane, phenylenebistrimethoxysilane, phenylenebistriethoxysilane, phenylenebismethyldiethoxysilane, phenylenebismethyldimethoxysilane, naphthylenebistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, bismethyldimethoxydisilane, etc., but are not limited to these.

[0230] Examples of the polysiloxane [A] include hydrolysis condensates of hydrolyzable silanes, which include hydrolyzable silane (A), a hydrolyzable silane represented by formula (1), and / or a hydrolyzable silane represented by formula (2), and other hydrolyzable silanes listed below, or modified products thereof.

[0231] Examples of the polysiloxane [A'] include hydrolysis condensates of hydrolyzable silanes including the hydrolyzable silane represented by formula (1) and / or the hydrolyzable silane represented by formula (2) and other hydrolyzable silanes listed below, or modified products thereof.

[0232] Examples of other hydrolyzable silanes include, but are not limited to, silane compounds having an onium group in the molecule, silane compounds having a sulfonic group, silane compounds having a sulfonamide group, and silane compounds having a cyclic urea skeleton in the molecule.

[0233] <<Silane compounds having an onium group in the molecule (hydrolyzable organosilane)>> It is expected that a silane compound having an onium group in the molecule can effectively and efficiently promote the cross-linking reaction of a hydrolyzable silane.

[0234] A preferred example of the silane compound having an onium group in the molecule is represented by formula (3).

[0235] [Chemistry 61]

[0236] R 11 is a group bonded to a silicon atom and represents an onium group or an organic group having the onium group.

[0237] R 12is a group bonded to a silicon atom, each independently representing an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or R 12 It represents an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, or an organic group having a cyano group, or a combination of two or more thereof.

[0238] R 13 The groups or atoms bonded to the silicon atom independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0239] f represents 1 or 2, g represents 0 or 1, and 1≤f+g≤2 is satisfied.

[0240] Specific examples of alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, organic groups having an epoxy group, organic groups having an acryloyl group, organic groups having a methacryloyl group, organic groups having a mercapto group, organic groups having an amino group, and organic groups having a cyano group, alkoxy groups, aralkyloxy groups, acyloxy groups, and halogen atoms, as well as specific examples of substituents for alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, and alkenyl groups, and their preferred carbon atom numbers, with respect to R 12 , for R in formula (A-1) 3 The specific examples and carbon number described, about R 13 , the specific examples and carbon number described for X in formula (A-1) can be given.

[0241] More specifically, specific examples of the onium group include a cyclic ammonium group or a chain ammonium group, and a tertiary ammonium group or a quaternary ammonium group is preferred.

[0242] Specifically, preferred examples of the onium group or the organic group having an onium group include a cyclic ammonium group or a chain ammonium group or an organic group having at least one of these, preferably a tertiary ammonium group or a quaternary ammonium group or an organic group having at least one of these.

[0243] It should be noted that when the onium group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as an atom constituting the ring. In this case, there are cases where the nitrogen atom constituting the ring is bonded to the silicon atom directly or via a divalent linking group, and cases where the carbon atom constituting the ring is bonded to the silicon atom directly or via a divalent linking group.

[0244] In one preferred embodiment, R as a group bonded to a silicon atom is 11 It is a heteroaromatic cyclic ammonium group represented by the following formula (S1).

[0245] [Chemistry 62]

[0246] In formula (S1), A 1 、A 2 、A 3 and A 4 Each independently represents a group represented by any one of the following formulas (J1) to (J3), A 1 ~A 4 At least one of them is a group represented by the following formula (J2), and the silicon atom and A in formula (3) are 1 ~A 4 The aromaticity of the ring formed by any one of the bonds in 1 ~A 4 Whether the bond between the atoms adjacent to each other and forming a ring together is a single bond or a double bond. Indicates a bond.

[0247] [Chemistry 63]

[0248] In formulas (J1) to (J3), R 10 Each of the groups independently represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a haloalkyl group, a haloaryl group, a haloarylalkyl group or an alkenyl group. Specific examples of the alkyl group, the aryl group, the aralkyl group, the haloalkyl group, the haloaryl group, the haloarylalkyl group and the alkenyl group and their preferred carbon atom numbers are the same as those mentioned above. Indicates a bond.

[0249] In formula (S1), R 14 independently represent an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group or a hydroxyl group, and in R 14 If there are more than 2, 2 R 14 Can bond to each other to form a ring, two R 14 The formed ring may be a cross-linked ring structure. In this case, the cyclic ammonium group has an adamantane ring, a norbornene ring, a spiro ring, or the like.

[0250] Specific examples of such alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, and alkenyl groups, and preferred carbon atom numbers thereof include the same specific examples and carbon atom numbers as described above.

[0251] In formula (S1), n 1 is an integer from 1 to 8, m 1 is 0 or 1, m 2 is a positive integer from 0 or 1 to the maximum number that can be substituted with a monocyclic or polycyclic ring.

[0252] In m 1 When it is 0, the structure includes A 1 ~A 4 (4+n 1 )-membered ring. That is, n 1 When it is 1, it forms a 5-membered ring, n 1 When it is 2, it forms a 6-membered ring, n 1 When it is 3, it forms a 7-membered ring, n 1 When it is 4, it forms an 8-membered ring, n 1 When it is 5, it forms a 9-membered ring, n 1 When it is 6, it forms a 10-membered ring, n 1 When it is 7, it forms an 11-membered ring, n 1 When it is 8, it forms a 12-membered ring.

[0253] In m 1 When it is 1, the 1 ~A 3 (4+n 1 ) membered ring and containing A 4 A condensed ring formed by condensation of a 6-membered ring.

[0254] A 1 ~A 4 According to any one of formulae (J1) to (J3), there are cases where the atoms constituting the ring have hydrogen atoms or cases where the atoms do not have hydrogen atoms. 1 ~A 4 When there is a hydrogen atom on an atom constituting the ring, the hydrogen atom may be replaced by R 14 Alternatively, you can also 1 ~A 4 Substitution of R on a ring-constituting atom other than the ring-constituting atom in 14 According to this situation, as mentioned above, m 2 An integer selected from 0 or 1 to the maximum number capable of substitution into a monocyclic or polycyclic ring.

[0255] The bond of the heteroaromatic cyclic ammonium group represented by formula (S1) exists on any carbon atom or nitrogen atom present in such a monocyclic or condensed ring, and is directly bonded to the silicon atom, or is bonded to a linking group to form an organic group having cyclic ammonium, which is bonded to the silicon atom.

[0256] Examples of such a linking group include, but are not limited to, an alkylene group, an arylene group, and an alkenylene group.

[0257] Specific examples of the alkylene group and the arylene group and their preferred carbon atom numbers include the same specific examples and carbon atom numbers as described above.

[0258] In addition, an alkenylene group is a divalent group derived by removing one hydrogen atom from an alkenyl group. Specific examples of such alkenyl groups include the same specific examples as described above. The number of carbon atoms in the alkenylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less.

[0259] Specific examples thereof include vinylene, 1-methylvinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, and 2-pentenylene, but are not limited thereto.

[0260] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (3) having a heteroaromatic cyclic ammonium group represented by formula (S1) include, but are not limited to, silanes represented by the following formulas (I-1) to (I-50).

[0261] [Chemistry 64]

[0262] [Chemistry 65]

[0263] [Chemistry 66]

[0264] In another example, the group bonded to the silicon atom in formula (3), namely, R 11 It may be a heteroaliphatic cyclic ammonium group represented by the following formula (S2).

[0265] [Chemistry 67]

[0266] In formula (S2), A 5 、A 6 、A 7 and A 8 Each independently represents a group represented by any one of the following formulas (J4) to (J6), A 5 ~A 8 At least one of them is a group represented by the following formula (J5). 5 ~A 8 In any of the bonds, the ring formed shows non-aromaticity, and A is determined 5 ~A 8 Whether the bonds with the atoms adjacent to them and forming the ring together are single bonds or double bonds. Indicates a bond.

[0267] [Chemistry 68]

[0268] In formulas (J4) to (J6), R 10 Each of the groups independently represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a haloalkyl group, a haloaryl group, a haloarylalkyl group or an alkenyl group. Specific examples of the alkyl group, the aryl group, the aralkyl group, the haloalkyl group, the haloaryl group, the haloarylalkyl group and the alkenyl group and their preferred carbon atom numbers are the same as those mentioned above. Indicates a bond.

[0269] In formula (S2), R 15 independently represent an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group or a hydroxyl group, and in R 15 If there are more than 2, 2 R 15 Can bond to each other to form a ring, two R 15 The formed ring may be a cross-linked ring structure. In this case, the cyclic ammonium group has an adamantane ring, a norbornene ring, a spiro ring, or the like.

[0270] Specific examples of the alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group and alkenyl group and their preferred carbon atom numbers include the same specific examples and carbon atom numbers as described above.

[0271] In formula (S2), n 2 is an integer from 1 to 8, m 3 is 0 or 1, m 4 is a positive integer from 0 or 1 to the maximum number that can be substituted with a monocyclic or polycyclic ring.

[0272] In m 3 When it is 0, the structure includes A 5 ~A 8 (4+n 2 )-membered ring. That is, n 2 When it is 1, it forms a 5-membered ring, n 2 When it is 2, it forms a 6-membered ring, n 2 When it is 3, it forms a 7-membered ring, n 2 When it is 4, it forms an 8-membered ring, n 2 When it is 5, it forms a 9-membered ring, n 2 When it is 6, it forms a 10-membered ring, n 2 When it is 7, it forms an 11-membered ring, n 2 When it is 8, it forms a 12-membered ring.

[0273] In m 3 When it is 1, the5 ~A 7 (4+n 2 ) membered ring and containing A 8 A condensed ring formed by condensation of a 6-membered ring.

[0274] A 5 ~A 8 According to any one of formulae (J4) to (J6), there are cases where the atoms constituting the ring have hydrogen atoms or cases where the atoms do not have hydrogen atoms. 5 ~A 8 When there is a hydrogen atom on an atom constituting the ring, the hydrogen atom may be replaced by R 15 Alternatively, you can also 5 ~A 8 Substitution of R on a ring-constituting atom other than the ring-constituting atom in 15 .

[0275] According to this situation, as mentioned above, m 4 An integer selected from 0 or 1 to the maximum number capable of substitution into a monocyclic or polycyclic ring.

[0276] The bonding bond of the heteroaliphatic cyclic ammonium group represented by formula (S2) exists on any carbon atom or nitrogen atom present in such a monocyclic or condensed ring, and is directly bonded to the silicon atom, or is bonded to a linking group to form an organic group having cyclic ammonium, which is bonded to the silicon atom.

[0277] Examples of such a linking group include an alkylene group, an arylene group, and an alkenylene group. Specific examples of the alkylene group, the arylene group, and the alkenylene group and their preferred carbon atom numbers are the same as those described above.

[0278] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (3) and having a heteroaliphatic cyclic ammonium group represented by formula (S2) include, but are not limited to, silanes represented by the following formulas (II-1) to (II-30).

[0279] [Chemistry 69]

[0280] [Chemistry 70]

[0281] Furthermore, in another example, the group bonded to the silicon atom in formula (3), namely, R 11 It can be a chain ammonium group represented by the following formula (S3).

[0282] [Chemistry 71]

[0283] In formula (S3), R 10 Each independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a haloalkyl group, a haloaryl group, a haloarylalkyl group or an alkenyl group. Specific examples of the alkyl group, aryl group, aralkyl group, a haloalkyl group, a haloaryl group, a haloarylalkyl group and an alkenyl group and their preferred carbon atom numbers are the same as those mentioned above. Indicates a bond.

[0284] The chain ammonium group represented by formula (S3) is directly bonded to a silicon atom, or is bonded to a linking group to form an organic group having a chain ammonium group, which is bonded to a silicon atom.

[0285] Examples of such a linking group include an alkylene group, an arylene group, and an alkenylene group. Specific examples of the alkylene group, the arylene group, and the alkenylene group include the same specific examples as described above.

[0286] Specific examples of the silane compound (hydrolyzable organosilane) represented by formula (3) having a chain ammonium group represented by formula (S3) include silanes represented by the following formulas (III-1) to (III-28), but are not limited thereto.

[0287] [Chemistry 72]

[0288] [Chemistry 73]

[0289] <<Silane compound having a sulfonic group or a sulfonamide group (hydrolyzable organosilane)>> Examples of the silane compound having a sulfonic group and the silane compound having a sulfonamide group include compounds represented by the following formulas (B-1) to (B-36), but are not limited thereto.

[0290] In the following formulae, Me represents a methyl group, and Et represents an ethyl group.

[0291] [Chemistry 74]

[0292] [Chemistry 75]

[0293] [Chemistry 76]

[0294] <<Silane compounds having a cyclic urea skeleton in the molecule (hydrolyzable organosilane)>> Examples of the hydrolyzable organosilane having a cyclic urea skeleton in the molecule include hydrolyzable organosilane represented by the following formula (4-1).

[0295] [Chemistry 77]

[0296] In formula (4-1), R 401 is a group bonded to a silicon atom, and each independently represents a group represented by the following formula (4-2).

[0297] R 402 is a group bonded to a silicon atom, and represents an alkyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, a haloalkyl group which may be substituted, a haloaryl group which may be substituted, a haloaralkyl group which may be substituted, an alkoxyalkyl group which may be substituted, an alkoxyaryl group which may be substituted, an alkoxyaralkyl group which may be substituted, or an alkenyl group which may be substituted, or R 402 It represents an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, or an organic group having a cyano group, or a combination of two or more thereof.

[0298] R 403 The groups or atoms bonded to the silicon atom independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom.

[0299] x is 1 or 2, y is 0 or 1, and x+y≤2.

[0300] R 402 alkyl, aryl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl, and organic groups having epoxy groups, organic groups having acryloyl groups, organic groups having methacryloyl groups, organic groups having mercapto groups, and organic groups having cyano groups, and R 403 The alkoxy group, aralkyloxy group, acyloxy group and halogen atom, as well as specific examples of these substituents, preferred carbon atom numbers, etc., can be given as for R in formula (A-1): 3 The specific example and the number of carbon atoms are the same as those described for X.

[0301] [Chemistry 78]

[0302] In formula (4-2), R 404 independently represent a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, an organic group having an epoxy group, or an organic group having a sulfonyl group, and R 405 Each independently represents an alkylene group, a hydroxyalkylene group, a sulfide bond (—S—), an ether bond (—O—), or an ester bond (—CO—O— or —O—CO—). Indicates a bond.

[0303] It should be noted that R 404 Specific examples and preferred carbon number of the alkyl group which may be substituted, the organic group having an alkenyl group and an epoxy group which may be substituted, etc. can be given as those for R in formula (A-1). 3 The specific examples and carbon number are the same as those described above, except that R 404 The alkyl group which may be substituted is preferably an alkyl group in which the terminal hydrogen atom is replaced by a vinyl group. Specific examples thereof include allyl group, 2-vinylethyl group, 3-vinylpropyl group, and 4-vinylbutyl group.

[0304] The organic group having a sulfonyl group is not particularly limited as long as it contains a sulfonyl group, and examples thereof include an alkylsulfonyl group which may be substituted, an arylsulfonyl group which may be substituted, an aralkylsulfonyl group which may be substituted, a halogenated alkylsulfonyl group which may be substituted, a halogenated arylsulfonyl group which may be substituted, a halogenated aralkylsulfonyl group which may be substituted, an alkoxyalkylsulfonyl group which may be substituted, an alkoxyarylsulfonyl group which may be substituted, an alkoxyaralkylsulfonyl group which may be substituted, and an alkenylsulfonyl group which may be substituted.

[0305] Specific examples and preferred carbon number of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl and alkenyl groups and their substituents in these groups can be given as those for R in formula (A-1). 3 The specific examples and carbon atom numbers described are the same as those described above.

[0306] An alkylene group is a divalent group derived by removing one hydrogen atom from an alkyl group. It may be linear, branched, or cyclic. Specific examples of such an alkylene group include the same examples as described above. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less.

[0307] In addition, R 405 The alkylene group may have one or more selected from the group consisting of a thioether bond, an ether bond, and an ester bond at its terminal or in the middle, preferably in the middle.

[0308] Specific examples of the alkylene group include: linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as methylethylene, 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; cyclic alkylene groups such as 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, 1,3-cyclobutanediyl, 1,2-cyclohexanediyl, and 1,3-cyclohexanediyl; Alkylene groups such as CH2OCH2-, -CH2CH2OCH2-, -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2OCH2CH2CH2-, -CH2CH2CH2OCH2CH2CH2-, -CH2SCH2-, -CH2CH2SCH2-, -CH2CH2SCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2SCH2CH2-, -CH2OCH2CH2SCH2CH2-, etc. contain ether groups, but are not limited to these.

[0309] The hydroxyalkylene group is obtained by replacing at least one hydrogen atom of the alkylene group with a hydroxyl group. Specific examples thereof include hydroxymethylene, 1-hydroxyethylene, 2-hydroxyethylene, 1,2-dihydroxyethylene, 1-hydroxytrimethylene, 2-hydroxytrimethylene, 3-hydroxytrimethylene, 1-hydroxytetramethylene, 2-hydroxytetramethylene, 3-hydroxytetramethylene, 4-hydroxytetramethylene, 1,2-dihydroxytetramethylene, 1,3-dihydroxytetramethylene, 1,4-dihydroxytetramethylene, 2,3-dihydroxytetramethylene, 2,4-dihydroxytetramethylene, and 4,4-dihydroxytetramethylene, but are not limited thereto.

[0310] In formula (4-2), X 401 Each of the following formulae (4-3) to (4-5) independently represents any one of the groups, and the carbon atom of the ketone group in the following formulae (4-4) and (4-5) and R in the formula (4-2) are mutually independent. 405 The bonded nitrogen atoms are bonded.

[0311] [Chemistry 79]

[0312] In formula (4-3) to formula (4-5), R 406 ~R 410Each of the following independently represents a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an organic group having an epoxy group or a sulfonyl group. Specific examples and preferred carbon number of organic groups having an alkyl group which may be substituted, an alkenyl group which may be substituted, and an epoxy group or a sulfonyl group can be given by referring to the same examples as those for R in formula (A-1). 3 The specific examples and carbon number of the organic group having a sulfonyl group can be the same as those for R. 404 The specific examples and carbon atom numbers described are the same as those described above. Indicates a bond.

[0313] Among them, from the viewpoint of achieving excellent lithographic properties with good reproducibility, X 401 Preferred is a group represented by formula (4-5).

[0314] From the perspective of achieving excellent lithographic properties with good reproducibility, R 404 and R 406 ~R 410 At least one of the alkyl groups is preferably an alkyl group in which a terminal hydrogen atom is replaced by a vinyl group.

[0315] The hydrolyzable organosilane represented by formula (4-1) may be a commercially available product or may be synthesized by a known method described in International Publication No. 2011 / 102470 or the like.

[0316] Specific examples of the hydrolyzable organosilane represented by the formula (4-1) include silanes represented by the following formulas (4-1-1) to (4-1-29), but the present invention is not limited thereto.

[0317] [Chemistry 80]

[0318] [Chemistry 81]

[0319] [Chemistry 82]

[0320] [A] Polysiloxane and [A′] Polysiloxane may be hydrolysis-condensation products of hydrolyzable silanes containing silane compounds other than those exemplified above, or modified products thereof, within a range not impairing the effects of the present invention.

[0321] As described above, the polysiloxanes [A] and [A′] can be modified products of hydrolysis-condensation products in which at least a portion of the silanol groups are modified. For example, products in which a portion of the silanol groups are modified with alcohol or protected with acetal can be used.

[0322] Examples of the modified polysiloxane include: a reaction product obtained by reacting at least a portion of the silanol groups in the hydrolyzable silane hydrolysis condensate with the hydroxyl group of an alcohol; a dehydration reaction product of the condensate with an alcohol; and a modified product obtained by protecting at least a portion of the silanol groups in the condensate with an acetal group.

[0323] As the alcohol, a monohydric alcohol can be used, for example, methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-pentanol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-hexanol, cyclopentanol, 1-hexanol, 2-hexanol, 3 ... -dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol and cyclohexanol.

[0324] In addition, for example, alkoxy group-containing alcohols such as 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), and propylene glycol monobutyl ether (1-butoxy-2-propanol) can be used.

[0325] The reaction between the silanol groups of the hydrolysis-condensation product and the hydroxyl groups of the alcohol is carried out by contacting the hydrolysis-condensation product with an alcohol and reacting the alcohol at a temperature of 40 to 160° C., for example, 60° C., for 0.1 to 48 hours, for example, 24 hours, to obtain a modified product in which the silanol groups are blocked. In this case, the alcohol serving as the blocking agent can be used as a solvent in the composition containing the polysiloxane.

[0326] The dehydration reaction product of the hydrolysis condensate of hydrolyzable silane and alcohol can be produced by reacting the hydrolysis condensate with alcohol in the presence of an acid as a catalyst to cap the silanol groups with the alcohol and removing the water generated by dehydration to the outside of the reaction system.

[0327] The acid used may be an organic acid having an acid dissociation constant (pka) of -1 to 5, preferably 4 to 5. Examples of the acid include trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, and acetic acid, and particularly benzoic acid, isobutyric acid, and acetic acid.

[0328] As the acid, an acid having a boiling point of 70 to 160° C. can be used, and examples thereof include trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid.

[0329] Thus, the acid preferably has an acid dissociation constant (pka) of 4 to 5 or a boiling point of 70 to 160° C. That is, an acid with weak acidity or an acid with strong acidity but low boiling point can be used.

[0330] Then, as an acid, any of the properties of the acid dissociation constant and the boiling point can be utilized.

[0331] Acetal protection of the silanol group in the hydrolysis condensate can be performed using vinyl ethers, for example, vinyl ether represented by the following formula (5). By reacting these vinyl ethers, a partial structure represented by the following formula (6) can be introduced into the polysiloxane.

[0332] [Chemistry 83]

[0333] In formula (5), R 1a 、R 2a and R 3a Each represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 4a represents an alkyl group having 1 to 10 carbon atoms, R 2a and R 4a They may be bonded to each other to form a ring. Examples of the alkyl group include those exemplified above.

[0334] [Chemistry 84]

[0335] In formula (6), R 1 ′、R 2 ′ and R 3 ' represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 4 ' represents an alkyl group with 1 to 10 carbon atoms, R 2 ′ and R 4 ' can be bonded to each other to form a ring. In formula (6), The adjacent atoms include, for example, oxygen atoms in siloxane bonds, oxygen atoms in silanol groups, and R 1 Examples of the alkyl group include the above-mentioned examples.

[0336] As the vinyl ether represented by formula (5), for example, aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, tert-butyl vinyl ether, and cyclohexyl vinyl ether; and cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran can be used. In particular, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, and 2,3-dihydrofuran are preferably used.

[0337] Acetal protection of the silanol group can be carried out using a hydrolysis condensate, vinyl ether, an aprotic solvent such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, 1,4-dioxane, etc., and a catalyst such as pyridine p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, or sulfuric acid.

[0338] In addition, the blocking of these silanol groups with alcohols and the acetal protection can be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silane described later.

[0339] The weight average molecular weight of the hydrolysis-condensation product of the hydrolyzable silane or its modified product can be, for example, 500 to 1,000,000. From the viewpoint of suppressing the precipitation of the hydrolysis-condensation product or its modified product in the composition, the weight average molecular weight can be preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of achieving a balance between storage stability and coating properties, the weight average molecular weight can be preferably 700 or more, and more preferably 1,000 or more.

[0340] The weight-average molecular weight is a molecular weight calculated in terms of polystyrene by GPC analysis. GPC analysis can be performed, for example, as follows: a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), GPC columns (trade names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate (flow rate) of 1.0 mL / min, and polystyrene (Shodex (registered trademark) manufactured by Showa Denko K.K.) as the standard sample.

[0341] The hydrolysis-condensation product of the hydrolyzable silane is obtained by hydrolyzing and condensing the above-mentioned silane compound (hydrolyzable silane).

[0342] The silane compound (hydrolyzable silane) contains an alkoxy group, aralkyloxy group, acyloxy group, or halogen atom directly bonded to a silicon atom, i.e., an alkoxysilyl group, aralkyloxysilyl group, acyloxysilyl group, or halogenated silicon group (hereinafter referred to as a hydrolyzable group).

[0343] In the hydrolysis of these hydrolyzable groups, water is usually used in an amount of 0.1 to 100 mol, for example 0.5 to 100 mol, preferably 1 to 10 mol, based on 1 mol of the hydrolyzable groups.

[0344] During the hydrolysis and condensation, a hydrolysis catalyst may be used for the purpose of promoting the reaction, or the hydrolysis and condensation may be carried out without using a hydrolysis catalyst. When a hydrolysis catalyst is used, the amount of the hydrolysis catalyst used is usually 0.0001 to 10 mol, preferably 0.001 to 1 mol, per 1 mol of the hydrolyzable group.

[0345] The reaction temperature during hydrolysis and condensation is usually at least room temperature and not more than the reflux temperature of the organic solvent used for hydrolysis at normal pressure, and can be, for example, 20 to 110°C, or 20 to 80°C.

[0346] The hydrolysis may be complete, that is, all the hydrolyzable groups are converted into silanol groups, or partial, that is, unreacted hydrolyzable groups remain.

[0347] Examples of the hydrolysis catalyst that can be used for hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0348] Examples of the metal chelate compound as the hydrolysis catalyst include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-isopropoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-tert-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, di-isopropoxy bis(acetylacetonate)titanium, di-n-butoxy bis(acetylacetonate)titanium, Titanium, di-sec-butoxy·bis(acetylacetonate)titanium, di-tert-butoxy·bis(acetylacetonate)titanium, monoethoxy·tris(acetylacetonate)titanium, mono-n-propoxy·tris(acetylacetonate)titanium, monoisopropoxy·tris(acetylacetonate)titanium, mono-n-butoxy·tris(acetylacetonate)titanium, mono-sec-butoxy·tris(acetylacetonate)titanium, mono-tert-butoxy·tris(acetylacetonate)titanium, tetrakis(acetylacetonate)titanium, triethoxy·mono(ethyl acetoacetate)titanium, tri-n-propoxy·mono(ethyl acetoacetate)titanium, triisopropoxy Titanium chelate compounds such as mono(ethyl acetoacetate)titanium, tri-n-butoxymono(ethyl acetoacetate)titanium, tri-sec-butoxymono(ethyl acetoacetate)titanium, tri-tert-butoxymono(ethyl acetoacetate)titanium, diethoxybis(ethyl acetoacetate)titanium, di-n-propoxybis(ethyl acetoacetate)titanium, di-isopropoxybis(ethyl acetoacetate)titanium, di-n-butoxybis(ethyl acetoacetate)titanium, di-sec-butoxybis(ethyl acetoacetate)titanium, di-tert-butoxybis(ethyl acetoacetate)titanium, monoethoxytris(ethyl acetoacetate)titanium, mono-n-propoxytris(ethyl acetoacetate)titanium, mono-isopropoxytris(ethyl acetoacetate)titanium, mono-n-butoxytris(ethyl acetoacetate)titanium, mono-sec-butoxytris(ethyl acetoacetate)titanium, mono-tert-butoxytris(ethyl acetoacetate)titanium, tetra(ethyl acetoacetate), mono(acetylacetonato)tris(ethyl acetoacetate)titanium, bis(acetylacetonato)bis(ethyl acetoacetate)titanium, and tris(acetylacetonato)mono(ethyl acetoacetate)titanium;Triethoxy mono(acetylacetonate) zirconium, tri-n-propoxy mono(acetylacetonate) zirconium, tri-isopropoxy mono(acetylacetonate) zirconium, tri-n-butoxy mono(acetylacetonate) zirconium, tri-sec-butoxy mono(acetylacetonate) zirconium, tri-tert-butoxy mono(acetylacetonate) zirconium, diethoxy bis(acetylacetonate) zirconium, di-n-propoxy bis(acetylacetonate) zirconium, di-isopropoxy bis(acetylacetonate) zirconium, di-n-butoxy bis(acetylacetonate) zirconium, di-sec-butoxy bis(acetylacetonate) zirconium, di-tert-butoxy bis(acetylacetonate) Zirconium tetrakis(acetylacetonate), zirconium triethoxy, zirconium tris(acetylacetonate), zirconium tris(acetylacetonate), zirconium triisopropoxy, zirconium tris(acetylacetonate), ... Zirconium chelate compounds such as sec-butoxy mono(ethyl acetoacetate) zirconium, tri-tert-butoxy mono(ethyl acetoacetate) zirconium, diethoxy bis(ethyl acetoacetate) zirconium, di-n-propoxy bis(ethyl acetoacetate) zirconium, diisopropoxy bis(ethyl acetoacetate) zirconium, di-n-butoxy bis(ethyl acetoacetate) zirconium, di-sec-butoxy bis(ethyl acetoacetate) zirconium, di-tert-butoxy bis(ethyl acetoacetate) zirconium, monoethoxy tris(ethyl acetoacetate) zirconium, mono-n-propoxy tris(ethyl acetoacetate) zirconium, monoisopropoxy tris(ethyl acetoacetate) zirconium, mono-n-butoxy tris(ethyl acetoacetate) zirconium, mono-sec-butoxy tris(ethyl acetoacetate) zirconium, mono-tert-butoxy tris(ethyl acetoacetate) zirconium, tetrakis(ethyl acetoacetate) zirconium, mono(acetylacetonato) tris(ethyl acetoacetate) zirconium, bis(acetylacetonato) bis(ethyl acetoacetate) zirconium, and tris(acetylacetonato) mono(ethyl acetoacetate) zirconium; and aluminum chelate compounds such as tris(acetylacetonato)aluminum and tris(ethyl acetoacetate)aluminum; and the like, but are not limited thereto. ;

[0349] Examples of the organic acid used as the hydrolysis catalyst include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

[0350] Examples of the inorganic acid as the hydrolysis catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, and the like, but are not limited thereto.

[0351] Examples of the organic base serving as the hydrolysis catalyst include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide.

[0352] Examples of the inorganic base as the hydrolysis catalyst include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

[0353] Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and these may be used alone or in combination of two or more.

[0354] Among them, nitric acid can be preferably used as a hydrolysis catalyst in the present invention. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, the molecular weight change of the hydrolysis-condensation product or its modified product can be suppressed. It is known that the stability of the hydrolysis-condensation product or its modified product in a liquid depends on the pH of the solution. After in-depth research, it was found that the pH of the solution is stabilized by the appropriate amount of nitric acid.

[0355] Furthermore, as described above, nitric acid can also be used when obtaining a modified product of a hydrolysis-condensation product, for example, when capping silanol groups with alcohols. Therefore, it is also preferred from the viewpoint of being a substance that can contribute to both the hydrolysis and condensation of the hydrolyzable silane and the alcohol-capping of the hydrolysis-condensation product.

[0356] In the case of hydrolysis and condensation, an organic solvent may be used as a solvent. Specific examples thereof include: aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, and n-pentylnaphthalene; methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, n-pentanol, isopentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylbutanol, tert-pent ... Monohydric alcohol solvents such as methylpentanol, secondary hexanol, 2-ethylbutanol, n-heptanol, secondary heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, secondary octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, secondary undecyl alcohol, trimethyl nonanol, secondary tetradecyl alcohol, secondary heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; 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 and other polyol solvents; acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol, acetophenone, fenchone and other ketone solvents; ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl Ether solvents such as butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, etc.; diethyl carbonate, methyl acetate, ethyl acetate, c -Butyrolactone, c-Valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diethyl Ester solvents such as esters, methoxytriglycol acetate, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone, but are not limited thereto. These solvents can be used alone or in combination of two or more.

[0357] After the hydrolysis and condensation reactions are completed, the reaction solution can be neutralized, diluted, concentrated, or treated with an ion exchange resin to remove the hydrolysis catalyst, such as the acid or base, used in the hydrolysis and condensation. Furthermore, before or after such treatment, by-products such as alcohol, water, and the hydrolysis catalyst used can be removed from the reaction solution by vacuum distillation or the like.

[0358] The hydrolysis-condensation product or its modified product (hereinafter also referred to as polysiloxane) thus obtained is obtained in the form of a polysiloxane varnish dissolved in an organic solvent and can be used directly to prepare the silicon-containing resist underlayer film-forming composition. In other words, the reaction solution can be used directly (or diluted) to prepare the silicon-containing resist underlayer film-forming composition. In this case, the hydrolysis catalyst and byproducts used in the hydrolysis and condensation processes may remain in the reaction solution as long as they do not impair the effects of the present invention. For example, nitric acid used to catalyze the hydrolysis and alcohol-terminate the silanol groups may remain in the polymer varnish solution at a level of approximately 100 to 5000 ppm.

[0359] The resulting polysiloxane varnish may be solvent-replaced or diluted with an appropriate solvent. It should be noted that, provided the storage stability of the resulting polysiloxane varnish is not deteriorated, the organic solvent may be distilled off to reduce the concentration of the film-forming component to 100%. The film-forming component refers to the component after removing the solvent component from all the components of the composition.

[0360] The organic solvent used for solvent replacement, dilution, etc. of the polysiloxane varnish may be the same as or different from the organic solvent used for the hydrolysis and condensation reaction of the hydrolyzable silane. The dilution solvent is not particularly limited, and one or more solvents may be arbitrarily selected and used.

[0361] <[C] Component: Solvent> In the first embodiment, any solvent for the component [C] can be used without particular limitation as long as it can dissolve and mix the component [A] and, if necessary, other components contained in the silicon-containing resist underlayer film-forming composition.

[0362] In the second embodiment, any solvent for component [C] can be used without particular limitation as long as it can dissolve and mix component [A'] and component [B] and, if necessary, other components contained in the silicon-containing resist underlayer film-forming composition.

[0363] The solvent [C] is preferably an alcoholic solvent, more preferably an alkylene glycol monoalkyl ether, and still more preferably a propylene glycol monoalkyl ether. These solvents also serve as end-capping agents for the silanol groups of the hydrolysis-condensation product. Therefore, a silicon-containing resist underlayer film-forming composition can be prepared from the solution obtained by preparing the polysiloxane [A] or polysiloxane [A′] without the need for solvent replacement or the like.

[0364] Examples of the alkylene glycol monoalkyl ether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl carbinol, and propylene glycol monobutyl ether.

[0365] Specific examples of other solvents [C] include 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, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethyl Ethyl oxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate , isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-ethoxy ethyl propionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, c -Butyrolactone etc. Solvents can be used alone or in combination of two or more.

[0366] The silicon-containing resist underlayer film-forming composition of the present invention may contain water as a solvent. When water is contained as a solvent, its content can be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less, relative to the total mass of the solvent contained in the composition.

[0367] Component [D]: Curing catalyst The silicon-containing resist underlayer film-forming composition may be a composition not containing a curing catalyst, but preferably contains a curing catalyst (component [D]).

[0368] As the curing catalyst, ammonium salts, phosphines, phosphonium salts, sulfonium salts, etc. can be used. It should be noted that the salts described below as an example of the curing catalyst may be added in the form of a salt or may be any of substances that form a salt in the composition (substances that are added as other compounds and form a salt in the system when added).

[0369] Examples of the ammonium salt include: quaternary ammonium salts having a structure represented by formula (D-1); [Chemistry 85]

[0370] (where m a Integer from 2 to 11, n a represents an integer from 2 to 3, R 21 represents an alkyl group, an aryl group, or an aralkyl group, Y - represents an anion.) A quaternary ammonium salt having a structure represented by formula (D-2); [Chemistry 86]

[0371] (Where R 22 、R 23 、R 24 and R 25 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion, and R 22 、R 23 、R 24 and R 25 are bonded to nitrogen atoms.) A quaternary ammonium salt having a structure represented by formula (D-3); [Chemistry 87]

[0372] (Where R 26 and R 27 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion.) A quaternary ammonium salt having a structure represented by formula (D-4); [Chemistry 88]

[0373] (Where R 28 represents an alkyl group, an aryl group, or an aralkyl group, Y - represents an anion.) A quaternary ammonium salt having a structure represented by formula (D-5); [Chemistry 89]

[0374] (Where R 29 and R 30 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion.) A tertiary ammonium salt having a structure represented by formula (D-6); [Chemistry 90]

[0375] (where m a Integer from 2 to 11, n a represents an integer from 2 to 3, Y - represents an anion. ).

[0376] In addition, as the phosphonium salt, there can be mentioned a quaternary phosphonium salt represented by formula (D-7); [Chemistry 91]

[0377] (Where R 31 、R 32 、R 33 and R 34 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion, and R 31 、R 32 、R 33 and R 34 bonded to phosphorus atoms respectively. ).

[0378] In addition, as the sulfonium salt, a tertiary sulfonium salt represented by formula (D-8) can be mentioned; [Chemistry 92]

[0379] (Where R 35 、R 36 and R 37 independently represent an alkyl group, an aryl group, or an aralkyl group, and Y - represents an anion, and R 35 、R 36 and R 37 are bonded to sulfur atoms respectively. ).

[0380] The compound of formula (D-1) is a quaternary ammonium salt derived from an amine, m a Integer from 2 to 11, n a represents an integer of 2 to 3.21 represents, for example, an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, for example, a linear alkyl group such as ethyl, propyl, butyl, benzyl, cyclohexyl, cyclohexylmethyl, dicyclopentadienyl, etc. - ) can be exemplified by: chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - ) and other acid groups.

[0381] The compound of formula (D-2) is R 22 R 23 R 24 R 25 N + Y - The quaternary ammonium salt R 22 、R 23 、R 24 and R 25 , for example, an alkyl group having 1 to 18 carbon atoms, such as ethyl, propyl, butyl, cyclohexyl, cyclohexylmethyl, an aryl group having 6 to 18 carbon atoms, such as phenyl, or an aralkyl group having 7 to 18 carbon atoms, such as benzyl. - ) can be exemplified by: chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - The quaternary ammonium salt can be obtained as a commercial product, for example, tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, etc.

[0382] The compound of formula (D-3) is a quaternary ammonium salt derived from 1-substituted imidazole, R 26 and R 27 The number of carbon atoms is, for example, 1 to 18, R 26 and R 27 The total number of carbon atoms in is preferably 7 or more. 26 Examples include alkyl groups such as methyl, ethyl, and propyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. 27 Examples include aralkyl groups such as benzyl, alkyl groups such as octyl and octadecyl. -) can be exemplified by: chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - The compound can also be obtained as a commercial product, for example, by reacting an imidazole compound such as 1-methylimidazole or 1-benzylimidazole with a halogenated aralkyl group, a halogenated alkyl group, or a halogenated aryl group such as benzyl bromide, methyl bromide or bromobenzene.

[0383] The compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, R 28 For example, it is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples thereof include butyl, octyl, benzyl, and lauryl. - ) can be exemplified by: chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - ) or other acid groups. This compound can also be obtained as a commercial product, for example, by reacting pyridine with a haloalkyl or haloaryl group such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0384] The compound of formula (D-5) is a quaternary ammonium salt derived from a substituted pyridine represented by methylpyridine, etc. 29 For example, it is an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples thereof include methyl, octyl, lauryl, and benzyl. 30 For example, it is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. For example, when the compound represented by formula (D-5) is a quaternary ammonium derived from methylpyridine, R 30 Methyl. Anion (Y - ) can be exemplified by: chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O -) or other acid groups. This compound can also be obtained as a commercial product, for example, by reacting a substituted pyridine such as picoline with a haloalkyl or halogenated aryl group such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, or benzyl bromide. Examples of this compound include N-benzyl picoline chloride, N-benzyl picoline bromide, and N-lauryl picoline chloride.

[0385] The compound of formula (D-6) is a quaternary ammonium salt derived from an amine, m a Integer from 2 to 11, n a Indicates 2 or 3. In addition, the anion (Y - ) can be exemplified by: chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - ) and other acid groups. The compound can be produced by the reaction of an amine with a weak acid such as a carboxylic acid or phenol. As carboxylic acids, formic acid and acetic acid can be cited. In the case of formic acid, the anion (Y - ) is (HCOO - ), in the case of acetic acid, the anion (Y - ) is (CH3COO - ). In addition, when using phenol, the anion (Y - ) is (C6H5O - ).

[0386] The compound of formula (D-7) is a compound having R 31 R 32 R 33 R 34 P + Y - The structure of the quaternary phosphonium salt. 31 、R 32 、R 33 and R 34 For example, it is an alkyl group having 1 to 18 carbon atoms, such as ethyl, propyl, butyl, cyclohexylmethyl, an aryl group having 6 to 18 carbon atoms, such as phenyl, or an aralkyl group having 7 to 18 carbon atoms, such as benzyl. 31 ~R 34 Three of the four substituents are unsubstituted phenyl or substituted phenyl, for example, phenyl and tolyl, and the remaining one is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. - ) can be exemplified by: chloride ion (Cl - ), bromide ion (Br -), iodide ion (I - ) and other halide ions, carboxylates (-COO - ), sulfonate (-SO3 - ), alcohol radical (-O - ) and other acid groups. This compound can be obtained as a commercially available product, and examples thereof include: halogenated tetraalkylphosphoniums such as halogenated tetra-n-butylphosphonium and halogenated tetra-n-propylphosphonium, halogenated trialkylbenzylphosphoniums such as halogenated triethylbenzylphosphonium; halogenated triphenylmonoalkylphosphoniums such as halogenated triphenylmethylphosphonium and halogenated triphenylethylphosphonium; halogenated triphenylbenzylphosphonium, halogenated tetraphenylphosphonium, halogenated tritolylmonoarylphosphonium, or halogenated tritolylmonoalkylphosphonium (in the above, the halogen atom is a chlorine atom or a bromine atom). Particularly preferred are halogenated triphenylmonoalkylphosphoniums such as halogenated triphenylmethylphosphonium and halogenated triphenylethylphosphonium; halogenated triphenylmonoarylphosphoniums such as halogenated triphenylbenzylphosphonium; halogenated trimethylphenylmonoarylphosphoniums such as halogenated trimethylphenylmonophenylphosphonium; and halogenated trimethylphenylmonoalkylphosphoniums such as halogenated trimethylphenylmonomethylphosphonium (the halogen atom is a chlorine atom or a bromine atom).

[0387] Phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisopentylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0388] The compound of formula (D-8) is a compound having R 35 R 36 R 37 S + Y - The structure of tertiary sulfonium salt. 35 、R 36 and R 37 For example, it is an alkyl group having 1 to 18 carbon atoms, such as ethyl, propyl, butyl, cyclohexylmethyl, an aryl group having 6 to 18 carbon atoms, such as phenyl, or an aralkyl group having 7 to 18 carbon atoms, such as benzyl. 35 ~R 37 Two of the three substituents are unsubstituted phenyl or substituted phenyl, for example, phenyl and tolyl, and the remaining one is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. - ) can be exemplified by: chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ) and other halide ions; carboxylate (-COO - ), sulfonate (-SO3 - ), alkoxide (-O -), maleate anion, nitrate anion and other acid groups. This compound can be obtained as a commercial product, for example, a halogenated trialkylsulfonium such as a halogenated tri-n-butylsulfonium and a halogenated tri-n-propylsulfonium; a halogenated dialkylbenzylsulfonium such as a halogenated diethylbenzylsulfonium; a halogenated diphenylmonoalkylsulfonium such as a halogenated diphenylmethylsulfonium and a halogenated diphenylethylsulfonium; a halogenated triphenylsulfonium (in the above, the halogen atom is a chlorine atom or a bromine atom), a trialkylsulfonium carboxylate such as a tri-n-butylsulfonium carboxylate and a tri-n-propylsulfonium carboxylate; a dialkylbenzylsulfonium carboxylate such as a diethylbenzylsulfonium carboxylate; a diphenylmonoalkylsulfonium carboxylate such as a diphenylmethylsulfonium carboxylate and a diphenylethylsulfonium carboxylate; a triphenylsulfonium carboxylate. In addition, a halogenated triphenylsulfonium and a triphenylsulfonium carboxylate can be preferably used.

[0389] Furthermore, a nitrogen-containing silane compound may be added as a curing catalyst. Examples of the nitrogen-containing silane compound include imidazole ring-containing silane compounds such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0390] The content of the curing catalyst [D] in the silicon-containing resist underlayer film-forming composition of the first embodiment is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, and even more preferably 1 to 20 parts by mass relative to 100 parts by mass of the polysiloxane [A], from the viewpoint of more fully achieving the effects of the present invention.

[0391] The content of the curing catalyst [D] in the silicon-containing resist underlayer film-forming composition of the second embodiment is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, and even more preferably 1 to 20 parts by mass relative to 100 parts by mass of the [A′] polysiloxane, from the viewpoint of more fully achieving the effects of the present invention.

[0392] <[E] Ingredient: Nitric acid> The silicon-containing resist underlayer film-forming composition preferably contains [E] nitric acid.

[0393] [E] Nitric acid can be added during the preparation of the silicon-containing resist underlayer film-forming composition, or can be used as a hydrolysis catalyst during the production of the above-mentioned polysiloxane or during the alcohol-capping of silanol groups, and the residue remaining in the polysiloxane varnish can be treated as [E] nitric acid.

[0394] The amount of nitric acid [E] blended (residual nitric acid amount) can be, for example, 0.0001 to 1% by mass, or 0.001 to 0.1% by mass, or 0.005 to 0.05% by mass based on the total mass of the silicon-containing resist underlayer film-forming composition.

[0395] <Other additives> The silicon-containing resist underlayer film-forming composition may be blended with various additives depending on the application of the composition.

[0396] Examples of additives include crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymers, acid generators, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorine-based surfactants, UV-curable surfactants, etc.), pH adjusters, metal oxides, rheology modifiers, adhesion aids, and the like, and known additives that are added to materials (compositions) for forming various films that can be used in the manufacture of semiconductor devices such as resist underlayer films, antireflective films, and pattern reversal films.

[0397] In addition, although various additives are shown below as examples, they are not limited to these.

[0398] <<Stabilizer>> The stabilizer can be added for the purpose of stabilizing the hydrolysis-condensation product of the hydrolyzable silane, and specific examples thereof include organic acids, water, alcohols, or combinations thereof.

[0399] Examples of organic acids include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. Oxalic acid and maleic acid are preferred. When an organic acid is added, the amount thereof is 0.1 to 5.0% by mass relative to the mass of the hydrolyzed condensate of the hydrolyzable silane. These organic acids can also function as pH adjusters.

[0400] As water, pure water, ultrapure water, ion-exchanged water, or the like can be used. When water is used, the amount thereof added can be 1 to 20 parts by mass relative to 100 parts by mass of the silicon-containing resist underlayer film-forming composition.

[0401] The alcohol is preferably one that easily disperses by heating after coating, and examples thereof include methanol, ethanol, propanol, isopropanol, butanol, etc. When an alcohol is added, the amount thereof can be 1 to 20 parts by mass relative to 100 parts by mass of the silicon-containing resist underlayer film-forming composition.

[0402] <<Organic polymer>> By adding an organic polymer to the silicon-containing resist underlayer film-forming composition, it is possible to adjust the dry etching rate (the amount of film thickness reduction per unit time), attenuation coefficient, refractive index, etc. of the film (resist underlayer film) formed from the composition. The organic polymer is not particularly limited and can be appropriately selected from various organic polymers (condensation polymers and addition polymers) depending on the purpose of addition.

[0403] Specific examples thereof include addition polymers and condensation polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate.

[0404] In the present invention, organic polymers containing aromatic rings or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing sites can also be preferably used when such functions are required. Specific examples of such organic polymers include, but are not limited to, addition polymers containing addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthracene methacrylate, anthracene methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as structural units, and condensation polymers such as phenol novolac and naphthol novolac.

[0405] When an addition polymer is used as the organic polymer, the polymer may be either a homopolymer or a copolymer.

[0406] Addition polymerizable monomers can be used in the production of addition polymerizable polymers. Specific examples of such addition polymerizable monomers 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, and acrylonitrile.

[0407] Specific examples of the acrylate compound include, but are not limited to, methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthracenemethyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-acryloyloxypropyltriethoxysilane, and glycidyl acrylate.

[0408] Specific examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracenemethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone, 3-methacryloyloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenyl methacrylate, but are not limited thereto.

[0409] Specific examples of the acrylamide compound include acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthracrylamide, but are not limited thereto.

[0410] Specific examples of the methacrylamide compound include methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-anthrylmethacrylamide, but are not limited thereto.

[0411] Specific examples of the vinyl compound include vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, and vinylanthracene, but are not limited thereto.

[0412] Specific examples of the styrene compound include styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene, but are not limited thereto.

[0413] Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide, but are not limited thereto.

[0414] When a polycondensation polymer is used as the polymer, examples of such polymers include polycondensation polymers of a diol compound and a dicarboxylic acid compound. Examples of the diol compound include diethylene glycol, hexamethylene glycol, and butanediol. Examples of the dicarboxylic acid compound include succinic acid, adipic acid, terephthalic acid, and maleic anhydride. Examples of other polyesters, polyamides, and polyimides include, but are not limited to, polypyromellitimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate.

[0415] When the organic polymer contains a hydroxyl group, the hydroxyl group can undergo a cross-linking reaction with a hydrolysis condensate or the like.

[0416] The weight average molecular weight of the organic polymer can generally be set to 1000 to 1000000. When an organic polymer is added, the weight average molecular weight can be set to, for example, 3000 to 300000, 5000 to 300000, or 10000 to 200000, from the viewpoint of fully achieving the functional effect of the polymer and suppressing precipitation in the composition.

[0417] Such organic polymers may be used alone or in combination of two or more.

[0418] When the silicon-containing resist underlayer film-forming composition contains an organic polymer, its content is appropriately determined in consideration of the functions of the organic polymer and cannot be generally specified. Generally, it can be in the range of 1 to 200 mass % relative to the mass of [A] polysiloxane or [A′] polysiloxane. From the viewpoint of suppressing precipitation in the composition, for example, it can be 100 mass % or less, preferably 50 mass % or less, and more preferably 30 mass % or less. From the viewpoint of fully achieving its effects, for example, it can be 5 mass % or more, preferably 10 mass % or more, and more preferably 30 mass % or more.

[0419] <<Acid Generator>> Examples of the acid generator include thermal acid generators and photoacid generators, and preferably, a photoacid generator can be used.

[0420] Examples of photoacid generators include, but are not limited to, onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds. It should be noted that photoacid generators, such as nitrates, carboxylates such as maleates, and hydrochlorides among the onium salt compounds described below, can also function as curing catalysts depending on their type.

[0421] Examples of the thermal acid generator include, but are not limited to, tetramethylammonium nitrate.

[0422] Specific examples of the onium salt compound include, but are not limited to, iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride.

[0423] Specific examples of the sulfonyl imide compound include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-n-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0424] Specific examples of the disulfonyldiazomethane compound include, but are not limited to, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0425] When the silicon-containing resist underlayer film-forming composition contains an acid generator, the content thereof is appropriately determined in consideration of the type of the acid generator and the like, and therefore cannot be unambiguously specified. However, it is generally in the range of 0.01 to 5% by mass relative to the mass of [A] polysiloxane or [A′] polysiloxane. From the viewpoint of suppressing the precipitation of the acid generator in the composition, it is preferably 3% by mass or less, more preferably 1% by mass or less. From the viewpoint of fully achieving its effect, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more.

[0426] In addition, the acid generator can be used individually by 1 type or in combination of 2 or more types, and a photoacid generator and a thermal acid generator can also be used together.

[0427] <<Surfactants>> Surfactants are effective in suppressing the generation of pinholes, streaks (Japanese: ストラレーション), etc. when the composition for forming a silicon-containing resist underlayer film is applied to a substrate. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, silicone surfactants, fluorine-based surfactants, and UV-curable surfactants. More specifically, examples include: polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, and other polyoxyethylene alkylaryl ethers; polyoxyethylene-polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate. Sorbitan fatty acid esters such as sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, trade names EFTOP (registered trademark) EF301, EF303, EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd. (formerly Tochem Products Co., Ltd.), trade names Megafac (registered trademark) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by 3M Japan Co., Ltd.), trade name AsahiGuard (registered trademark) AG710 (manufactured by AGC Corporation), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), but are not limited to these.

[0428] The surfactant can be used alone or in combination of two or more.

[0429] When the silicon-containing resist underlayer film-forming composition contains a surfactant, the content thereof is usually 0.0001 to 5 mass %, preferably 0.001 to 4 mass %, and more preferably 0.01 to 3 mass % relative to the mass of [A] polysiloxane or [A′] polysiloxane.

[0430] <<Rheology Modifier>> Rheology modifiers are added primarily to improve the fluidity of the silicon-containing resist underlayer film-forming composition, particularly to enhance the thickness uniformity of the formed film and improve the composition's ability to fill pores during the baking process. Specific examples include: phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as n-butyl stearate and glyceryl stearate.

[0431] When these rheology control agents are used, the amount added is usually less than 30% by mass based on all film-forming components of the silicon-containing resist underlayer film-forming composition.

[0432] <<Adhesion aid>> The adhesion aid is mainly added for the purpose of improving the adhesion between the substrate or resist and the film (resist underlayer film) formed from the silicon-containing resist underlayer film-forming composition, particularly for the purpose of suppressing or preventing the peeling of the resist during development. Specific examples include: chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane; silazanes such as hexamethyldisilazane, N,N′-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; c -Chloropropyltrimethoxysilane, c -aminopropyltriethoxysilane, c - Other silanes such as glycidoxypropyltrimethoxysilane, heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, ureaazole, thiouracil, mercaptoimidazole, and mercaptopyrimidine, urea such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds.

[0433] When using these adhesion aids, the amount added is usually less than 5 mass %, preferably less than 2 mass %, based on the film-forming components of the silicon-containing resist underlayer film-forming composition.

[0434] <<pH Adjuster>> Examples of pH adjusters include acids having one or more carboxylic acid groups, such as the organic acids listed above as stabilizers. When a pH adjuster is used, the amount added can be 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass relative to 100 parts by mass of the [A] polysiloxane or [A′] polysiloxane.

[0435] <<Metal Oxides>> In addition, examples of metal oxides that can be added to the silicon-containing resist underlayer film-forming composition include, but are not limited to, oxides of one or more metals such as tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and W (tungsten), and semimetals such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0436] The concentration of the film-forming component in the silicon-containing resist underlayer film-forming composition can be, for example, 0.1 to 50 mass %, 0.1 to 30 mass %, 0.1 to 25 mass %, or 0.5 to 20.0 mass % relative to the total mass of the composition.

[0437] The content of [A] polysiloxane or [A′] polysiloxane in the film-forming component is generally 20% to 100% by mass. From the viewpoint of achieving the effects of the present invention with good reproducibility, the lower limit is preferably 50% by mass, more preferably 60% by mass, further preferably 70% by mass, and further preferably 80% by mass. The upper limit is preferably 99% by mass, and the remainder can be used as additives described below.

[0438] Furthermore, the silicon-containing resist underlayer film-forming composition preferably has a pH of 2 to 5, and more preferably has a pH of 3 to 4.

[0439] The silicon-containing resist underlayer film-forming composition of the first embodiment can be produced by mixing [A] polysiloxane, [C] solvent, and, if desired, other components. In this case, a solution containing [A] polysiloxane may be prepared in advance and then mixed with [C] solvent and other components.

[0440] The mixing order is not particularly limited. For example, the solvent [C] may be added to the solution containing the polysiloxane [A] and mixed, and then the other components may be added to the mixture. Alternatively, the solution containing the polysiloxane [A], the solvent [C], and the other components may be mixed simultaneously.

[0441] If necessary, the solvent [C] may be added at the end, or components that are relatively soluble in the solvent [C] may not be pre-included in the mixture but added at the end. From the perspective of suppressing aggregation and separation of the constituent components and reproducibly producing a composition with excellent uniformity, it is preferable to pre-prepare a solution containing a good solution of the polysiloxane [A] and use this solution to prepare the composition. However, it should be noted that the polysiloxane [A] may aggregate or precipitate during mixing, depending on the type and amount of the co-mixed solvent [C], the amount and properties of the other components, and other factors. Furthermore, when preparing a composition using a solution containing the polysiloxane [A], it is necessary to determine the concentration and amount of the polysiloxane [A] solution to achieve the desired amount of polysiloxane [A] in the final composition.

[0442] During the preparation of the composition, heating may be performed appropriately within a range in which the components do not decompose or deteriorate.

[0443] The silicon-containing resist underlayer film-forming composition of the second embodiment can be produced by mixing [A'] polysiloxane, [B] hydrolyzable silane (A), [C] solvent, and, if desired, other components. In this case, a solution containing [A'] polysiloxane can be prepared in advance, and this solution can be mixed with [B] hydrolyzable silane (A), [C] solvent, and other components.

[0444] The order of mixing is not particularly limited. For example, [B] the hydrolyzable silane (A) and [C] the solvent may be added to a solution containing [A′] the polysiloxane and mixed, and then other components may be added to this mixture. Alternatively, the solution containing [A′] the polysiloxane, [B] the hydrolyzable silane (A), [C] the solvent, and other components may be mixed simultaneously.

[0445] If necessary, the solvent [C] may be added at the end, or a component that is relatively soluble in the solvent [C] may be added at the end rather than initially included in the mixture. From the perspective of suppressing aggregation and separation of the constituent components and reproducibly preparing a composition with excellent uniformity, it is preferable to prepare a solution containing a good solution of the polysiloxane [A'] and use this solution to prepare the composition. However, it should be noted that the polysiloxane [A'] may aggregate or precipitate when mixed, depending on the type and amount of the co-mixed hydrolyzable silane (A) and the solvent [C], as well as the amount and properties of other components. Furthermore, when preparing a composition using a solution containing the polysiloxane [A'], it is necessary to determine the concentration and amount of the polysiloxane [A'] solution to achieve the desired amount of polysiloxane [A'] in the final composition.

[0446] During the preparation of the composition, heating may be performed appropriately within a range in which the components do not decompose or deteriorate.

[0447] In the present invention, filtration can be performed using a submicron filter or the like during the production of the silicon-containing resist underlayer film-forming composition or after all components are mixed. The material of the filter used in this case is not limited, and for example, nylon filters, fluororesin filters, etc. can be used.

[0448] The silicon-containing resist underlayer film-forming composition of the present invention can be suitably used as a resist underlayer film-forming composition used in a photolithography process.

[0449] (Resist underlayer film, semiconductor processing substrate, pattern forming method, and semiconductor device manufacturing method) Hereinafter, as one embodiment of the present invention, a resist underlayer film, a semiconductor processing substrate, a pattern forming method, and a method for manufacturing a semiconductor device using the silicon-containing resist underlayer film-forming composition of the present invention will be described.

[0450] The resist underlayer film of the present invention is a cured product of the silicon-containing resist underlayer film-forming composition of the present invention.

[0451] The semiconductor processing substrate of the present invention includes the resist underlayer film of the present invention.

[0452] The method for manufacturing a semiconductor device of the present invention comprises the following steps: forming an organic lower layer film on a substrate; a step of forming a resist underlayer film on an organic underlayer film using the silicon-containing resist underlayer film-forming composition of the present invention; and A step of forming a resist film on the resist underlayer film.

[0453] The pattern forming method of the present invention comprises the following steps: forming an organic lower layer film on a semiconductor substrate; A step of coating the silicon-containing resist underlayer film-forming composition of the present invention on an organic underlayer film and firing the composition to form a resist underlayer film; forming a resist film on the resist underlayer film; The process of exposing and developing the resist film to obtain a resist pattern; a step of etching the resist underlayer film using the resist pattern as a mask; and A step of etching the organic underlayer film using the patterned resist underlayer film as a mask.

[0454] First, the silicon-containing resist underlayer film-forming composition of the present invention is applied to a substrate used in the manufacture of precision integrated circuit elements (e.g., semiconductor substrates such as silicon wafers coated with a silicon oxide film, a silicon nitride film, or a silicon nitride oxide film, silicon nitride substrates, quartz substrates, glass substrates (including alkali-free glass, low-alkali glass, and crystallized glass), glass substrates formed with an ITO (indium tin oxide) film or an IZO (indium zinc oxide) film, plastic substrates (polyimide, PET, etc.), substrates coated with a low-k dielectric constant material (low-k material), flexible substrates, etc.) by an appropriate coating method such as a spin coater or coater. The composition is then fired by heating means such as a hot plate to form a cured product, thereby forming a resist underlayer film. Hereinafter, in this specification, the resist underlayer film refers to a film formed from the silicon-containing resist underlayer film-forming composition of the present invention.

[0455] The calcination conditions are appropriately selected from a calcination temperature of 40°C to 400°C or 80°C to 250°C and a calcination time of 0.3 to 60 minutes, preferably a calcination temperature of 150°C to 250°C and a calcination time of 0.5 to 2 minutes.

[0456] The thickness of the resist underlayer film formed here is, for example, 10 nm to 1000 nm, or 20 nm to 500 nm, or 50 nm to 300 nm, or 100 nm to 200 nm, or 10 nm to 150 nm.

[0457] The silicon-containing resist underlayer film-forming composition used in forming the resist underlayer film may be a composition filtered through a nylon filter. The silicon-containing resist underlayer film-forming composition filtered through a nylon filter herein refers to a composition that has been filtered through a nylon filter during production of the silicon-containing resist underlayer film-forming composition or after all components have been mixed.

[0458] In the present invention, an organic underlayer film is formed on a substrate and then a resist underlayer film is formed thereon. However, depending on circumstances, an organic underlayer film may not be provided.

[0459] The organic underlayer film used here is not particularly limited, and any organic underlayer film conventionally used in photolithography processes can be selected and used.

[0460] By providing an organic underlayer film on a substrate, a resist underlayer film thereon, and further a resist film (described later) thereon, the pattern width of the photoresist film is narrowed. Even when the photoresist film is thinly coated to prevent pattern collapse, substrate processing can be performed by selecting an appropriate etching gas (described later). For example, using a fluorine-based gas with a sufficiently high etching rate for the photoresist film as an etching gas enables processing of the resist underlayer film. Also, using an oxygen-based gas with a sufficiently high etching rate for the resist underlayer film as an etching gas enables processing of the organic underlayer film. Furthermore, using a fluorine-based gas with a sufficiently high etching rate for the organic underlayer film as an etching gas enables processing of the substrate.

[0461] In addition, the substrate and coating method that can be used in this case include the same substrates and coating methods as those described above.

[0462] Next, a layer of a photoresist material (resist film) is formed on the resist underlayer film, for example. The resist film can be formed using a known method, that is, by applying a coating type resist material (resist film forming composition) on the resist underlayer film and firing it.

[0463] The film thickness of the resist film is, for example, 10 nm to 10000 nm, or 100 nm to 2000 nm, or 200 nm to 1000 nm, or 30 nm to 200 nm.

[0464] The photoresist material used in the resist film formed on the resist underlayer film is not particularly limited as long as it is sensitive to the light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.), and either a negative-type photoresist material or a positive-type photoresist material can be used. For example, there are positive-type photoresist materials comprising a novolac resin and 1,2-naphthoquinonediazidesulfonic acid ester, chemically amplified photoresist materials comprising a binder having a group that increases the alkali dissolution rate upon acid decomposition and a photoacid generator, chemically amplified photoresist materials comprising a low molecular weight compound that increases the alkali dissolution rate of the photoresist material upon acid decomposition, an alkali-soluble binder, and a photoacid generator, and chemically amplified photoresist materials comprising a binder having a group that increases the alkali dissolution rate upon acid decomposition, a low molecular weight compound that increases the alkali dissolution rate of the photoresist material upon acid decomposition, and a photoacid generator.

[0465] Specific examples of commercially available products include, but are not limited to, APEX-E manufactured by Shipley, PAR710 manufactured by Sumitomo Chemical Co., Ltd., AR2772JN manufactured by JSR Corporation, and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. Furthermore, for example, fluorine-containing polymer photoresist materials such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000) can be mentioned.

[0466] Furthermore, the resist film formed on the resist underlayer film can be replaced with a resist film for electron beam lithography (also referred to as an electron beam resist film) or a resist film for EUV lithography (also referred to as an EUV resist film). That is, the silicon-containing resist underlayer film-forming composition of the present invention can be used as a resist underlayer film-forming composition for electron beam lithography or a resist underlayer film-forming composition for EUV lithography. It is particularly preferably used as a resist underlayer film-forming composition for EUV lithography.

[0467] As electron beam resist materials for forming electron beam resist films, both negative and positive materials can be used. As specific examples thereof, there are: chemically amplified resist materials comprising an acid generator and an adhesive having a group that changes the alkali dissolution rate by acid decomposition, chemically amplified resist materials comprising an alkali-soluble adhesive, an acid generator, and a low molecular compound that changes the alkali dissolution rate of the resist material by acid decomposition, chemically amplified resist materials comprising an acid generator and an adhesive having a group that changes the alkali dissolution rate by acid decomposition, and a low molecular compound that changes the alkali dissolution rate of the resist material by acid decomposition, non-chemically amplified resist materials comprising an adhesive having a group that changes the alkali dissolution rate by electron beam decomposition, non-chemically amplified resist materials comprising an adhesive having a portion that changes the alkali dissolution rate by being cut by an electron beam, etc. When using these electron beam resist materials, a pattern of a resist film can be formed, similar to the case of using a photoresist material with an electron beam as the irradiation source.

[0468] In addition, as an EUV resist material for forming an EUV resist film, a methacrylate resin-based resist material or a metal oxide resist material can be used.

[0469] As a metal oxide resist material, for example, there can be mentioned a coating composition described in Japanese Patent Application Laid-Open No. 2019-113855, which contains a metal oxo-hydroxo network having an organic ligand through a metal-carbon bond and / or a metal carboxylate bond.

[0470] In EUV lithography, LWR and sensitivity are generally in a trade-off relationship. Therefore, the silicon-containing resist underlayer film-forming composition of the present invention, which can improve the sensitivity of the resist without reducing the LWR of the resist, is suitable for EUV lithography, and is more suitable for EUV lithography using a metal oxide resist.

[0471] Next, the resist film formed on the upper layer of the resist underlayer film is exposed through a predetermined mask (reticle). The exposure can be performed using a KrF excimer laser (wavelength 248nm), an ArF excimer laser (wavelength 193nm), an F2 excimer laser (wavelength 157nm), EUV (wavelength 13.5nm), an electron beam, or the like.

[0472] After exposure, post-exposure baking can be performed as needed. Post-exposure baking is performed under conditions appropriately selected from heating temperatures of 70° C. to 150° C. and heating times of 0.3 minutes to 10 minutes.

[0473] Next, the photoresist film is developed with a developer (eg, an alkaline developer). In this way, for example, when a positive photoresist film is used, the exposed portion of the photoresist film is removed, thereby forming a pattern of the photoresist film.

[0474] Examples of developing solutions (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 alkaline solutions (alkaline developers) such as aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Surfactants and the like may also be added to these developing solutions. Development conditions are appropriately selected from a temperature of 5 to 50°C and a development time of 10 to 600 seconds.

[0475] In addition, in the present invention, an organic solvent can be used as a developer, and development can be performed using the developer (solvent) after exposure. Thus, for example, when a negative photoresist film is used, the unexposed portion of the photoresist film is removed to form a pattern of the photoresist film.

[0476] Examples of the developer (organic solvent) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, methoxyethyl acetate, ethoxyethyl acetate, 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-methoxybutyl acetate -Ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate Examples include butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate. Surfactants and the like may also be added to these developers. Development conditions may be appropriately selected from a temperature of 5° C. to 50° C. and a development time of 10 seconds to 600 seconds.

[0477] The pattern of the photoresist film (upper layer) thus formed serves as a protective film, and the resist underlayer film (intermediate layer) is removed. Subsequently, the organic underlayer film (lower layer) is removed, using the film comprising the patterned photoresist film and the patterned resist underlayer film (intermediate layer) as a protective film. Finally, the substrate is processed, using the patterned resist underlayer film (intermediate layer) and the patterned organic underlayer film (lower layer) as protective films.

[0478] Removal (patterning) of the resist lower layer film (middle layer) using the pattern of the resist film (upper layer) as a protective film is performed by dry etching, and 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 can be used.

[0479] It should be noted that halogen-based gases are preferably used in the dry etching of the resist lower film. In dry etching using halogen-based gases, it is basically not easy to remove the resist film (photoresist film) containing organic substances. In contrast, the resist lower film containing a large amount of silicon atoms is quickly removed by the halogen-based gases. Therefore, the reduction in the film thickness of the photoresist film accompanying the dry etching of the resist lower film can be suppressed. Then, as a result, the photoresist film can be used in the form of a thin film. Therefore, the dry etching of the resist lower film is preferably performed using fluorine-based gases. As fluorine-based gases, for example, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), etc. can be mentioned, but are not limited to these.

[0480] When an organic underlayer film is present between the substrate and the resist underlayer film, the removal (patterning) of the organic underlayer film (lower layer) is preferably performed by dry etching using an oxygen-based gas (such as oxygen gas or an oxygen / carbonyl sulfide (COS) mixed gas) using a film comprising the patterned resist film (upper layer) (if any) and the patterned resist underlayer film (intermediate layer) as a protective film. This is because the resist underlayer film of the present invention, which contains a large amount of silicon atoms, is not easily removed by dry etching using an oxygen-based gas.

[0481] Thereafter, processing (patterning) of the (semiconductor) substrate using the patterned resist underlayer film (intermediate layer) and, if desired, the patterned organic underlayer film (underlayer) as a protective film is preferably performed by dry etching using a fluorine-based gas.

[0482] Examples of the fluorine-based gas include tetrafluoromethane (CF 4 ), perfluorocyclobutane (C 4 F 8 ), perfluoropropane (C 3 F 8 ), trifluoromethane, and difluoromethane (CH 2 F 2 ).

[0483] After the organic underlayer film is removed (patterned) or after the substrate is processed (patterned), the resist underlayer film can be removed. The resist underlayer film can be removed by dry etching or wet etching (wet method).

[0484] Dry etching of the resist lower layer film, as listed in the patterning, preferably utilizes fluorine-based gases, such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), etc., but is not limited to these.

[0485] As the chemical solution used in the wet etching of the resist lower layer film, there are alkaline solutions such as dilute hydrofluoric acid (HF), buffered hydrofluoric acid (a mixed solution of HF and NH4F), an aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 solution), an aqueous solution containing sulfuric acid and hydrogen peroxide (SPM solution), an aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM solution), and an aqueous solution containing ammonia and hydrogen peroxide (SC-1 solution). Examples of alkaline solutions include, in addition to the ammonia hydrogen peroxide aqueous solution (SC-1 solution) obtained by mixing ammonia, hydrogen peroxide solution, and water, aqueous solutions containing 1 to 99% by mass of ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidinium hydroxide, 1-propyl-1-methylpyrrolidinium hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepiquat hydroxide, trimethylsulfonium hydroxide, hydrazines, ethylenediamines, or guanidine. These solutions may also be used in combination.

[0486] Furthermore, an organic antireflective film can be formed on the upper layer of the resist underlayer film before the resist film is formed. The antireflective film composition used here is not particularly limited. For example, any antireflective film composition conventionally used in photolithography processes can be selected and used. The antireflective film can be formed by conventional methods, such as coating and firing using a spin coater or a coater.

[0487] Furthermore, the substrate coated with the silicon-containing resist underlayer film-forming composition may have an organic or inorganic antireflection film formed on its surface by a CVD method or the like, and the resist underlayer film may also be formed thereon. When the resist underlayer film of the present invention is formed thereon after forming an organic underlayer film on a substrate, the substrate used may also have an organic or inorganic antireflection film formed on its surface by a CVD method or the like.

[0488] The resist underlayer film formed from the silicon-containing resist underlayer film-forming composition may also absorb the wavelength of light used in the photolithography process. In such cases, the resist underlayer film can function as an antireflection film that prevents light reflected from the substrate.

[0489] Furthermore, the resist underlayer film can also be used as a layer for preventing the interaction between the substrate and the resist film (photoresist film, etc.), a layer having the function of preventing the adverse effects of materials used in the resist film or substances generated when the resist film is exposed on the substrate, a layer having the function of preventing substances generated from the substrate from diffusing into the resist film during heating and firing, and a barrier layer for reducing the poisoning effect of the resist film caused by the dielectric layer of the semiconductor substrate.

[0490] The resist underlayer film can be applied to substrates with through-holes used in dual damascene processes and can be used as a hole-filling material (embedding material) that can fill the holes without gaps. In addition, it can also be used as a planarizing material for planarizing the surface of a semiconductor substrate with uneven surfaces.

[0491] In addition, the resist underlayer film of the present invention, as an underlayer film of the EUV resist film, in addition to its function as a hard mask, does not mix with the EUV resist film, and can prevent unwanted exposure light, such as UV (ultraviolet) light, DUV (deep ultraviolet) light (ArF light, KrF light), from being reflected from the substrate or interface during EUV exposure (wavelength 13.5nm). Therefore, in order to form the lower anti-reflective film of the EUV resist film, the silicon-containing resist underlayer film-forming composition of the present invention can be appropriately used. That is, as the lower layer of the EUV resist film, it can effectively prevent reflection. When used as an EUV resist underlayer film, its process can be carried out in the same manner as the photoresist underlayer film.

[0492] The semiconductor substrate can be appropriately processed by using the semiconductor processing substrate including the resist underlayer film of the present invention described above and a semiconductor substrate.

[0493] In addition, according to the method for manufacturing a semiconductor element as described above, which includes a process of forming an organic underlayer film, a process of forming a resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film forming composition of the present invention, and a process of forming a resist film on the resist underlayer film, it is possible to achieve high-precision processing of semiconductor substrates with good reproducibility, and therefore stable manufacturing of semiconductor elements can be expected.

[0494] Example Hereinafter, the present invention will be described in more detail with reference to synthesis examples and examples, but the present invention is not limited to the following examples.

[0495] In addition, in the examples, the apparatus and conditions used for analyzing the physical properties of the samples are as follows.

[0496] (1) Molecular weight determination The molecular weight of the polysiloxane used in the present invention is a molecular weight obtained by GPC analysis in terms of polystyrene.

[0497] The measurement conditions of GPC can be, for example, performed using a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), GPC columns (trade names Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, an eluent (elution solvent) of tetrahydrofuran, a flow rate (flow velocity) of 1.0 mL / min, and a standard sample of polystyrene (manufactured by Showa Denko K.K.).

[0498] [1] Synthesis of compounds (Synthesis Example of Raw Materials) 4-iodobenzene-1-sulfonyl chloride 14.4g (0.048mol), sodium sulfite 9.0g (0.072mol), sodium bicarbonate 18.0g (0.215mol) and water 45.0g were placed in a 200mL eggplant flask, heated to 100°C, and reacted for 1 hour. Then, 50.0g of toluene was added, heated to reflux, and water was recovered using Dean-Stark. 9.5g (0.048mol) of 3-chloropropyltrimethoxysilane, 1.4g (0.010mol) of sodium iodide and 45.0g of N-methyl-2-pyrrolidone were added thereto, and the solvent was distilled off at 150°C while heating and stirring for 3 hours. After the reaction solution was separated by toluene and water, sodium carbonate was added to the organic phase for stirring and filtering, and toluene was removed by evaporator to obtain a crude product. The crude product was subjected to reduced pressure distillation to obtain the target compound 1 with a yield of 36%.

[0499] 1 H-NMR (500MHz, CDCl3): 0.70ppm (t, 2H), 1.82ppm (m, 2H), 3.12ppm (t, 2H), 3.53ppm (s, 9H), 7.61ppm (d, 2H), 7.93ppm (d, 2H) <Compound 1> [Chemistry 93]

[0500] Me represents a methyl group.

[0501] [2] Synthesis of polymer (hydrolysis condensate) (Synthesis example 1) 8.3 g of tetraethoxysilane, 2.5 g of methyltriethoxysilane, 1.2 g of the above-mentioned compound 1 and 14.3 g of 1-ethoxy-2-propanol were placed in a 200 mL flask and stirred. While the resulting solution was stirred with a magnetic stirrer, 7.2 g of a 0.1 mol / L nitric acid aqueous solution was added dropwise thereto.

[0502] After the dropwise addition, the flask was moved to an oil bath adjusted to 63°C and reacted for 20 hours. The reaction solution was then cooled to room temperature, and 20 g of 1-ethoxy-2-propanol was added to the reaction solution. Water, nitric acid, and methanol and ethanol, which were reaction byproducts, were distilled off under reduced pressure to obtain a concentrated solution of the hydrolysis-condensation product (polymer) using 1-ethoxy-2-propanol as the solvent. The solids content of the resulting concentrated solution, calculated as the solid residue when heated at 150°C, exceeded 20% by mass.

[0503] The obtained hydrolysis condensate (polysiloxane) corresponds to the following formula, and its weight average molecular weight (Mw) was 3800 as calculated by polystyrene conversion based on GPC.

[0504] In addition, in the following chemical formula, the number next to the siloxane unit represents the molar ratio (total 100).

[0505] [Chemistry 94]

[0506] Me represents a methyl group.

[0507] (Comparative Synthesis Example 1) 8.3 g of tetraethoxysilane, 2.5 g of methyltriethoxysilane, 0.6 g of phenyltrimethoxysilane, and 48.4 g of 1-ethoxy-2-propanol were placed in a 300 mL flask and stirred. While the resulting solution was stirred with a magnetic stirrer, 19.3 g of a 0.2 mol / L aqueous nitric acid solution was added dropwise.

[0508] After the dropwise addition, the flask was moved to an oil bath adjusted to 63°C and reacted for 20 hours. The reaction solution was then cooled to room temperature, 18 g of 1-ethoxy-2-propanol was added to the reaction solution, and water, nitric acid, and methanol and ethanol as reaction by-products were distilled off under reduced pressure to obtain a concentrated solution of a hydrolysis-condensation product (polymer) using 1-ethoxy-2-propanol as a solvent.

[0509] The obtained hydrolysis-condensation product (polysiloxane) corresponds to the following formula, and its weight average molecular weight (Mw) was 3,000 as calculated by polystyrene conversion based on GPC.

[0510] In addition, in the following chemical formula, the number next to the siloxane unit represents the molar ratio (total 100).

[0511] [Chemistry 95]

[0512] Me represents a methyl group.

[0513] [3] Example 1 and Comparative Example 1: Preparation of Silicon-Containing Resist Underlayer Film-Forming Composition (Coating Liquid) The hydrolysis condensate (polymer) obtained in Synthesis Example 1 and the hydrolysis condensate (polymer) obtained in Comparative Synthesis Example 1 were mixed with additives and solvents in the ratios shown in Table 1, and 0.02 m The mixture was filtered through a polyethylene filter of 100 μm to prepare silicon-containing resist underlayer film-forming compositions. The amounts added in Table 1 are expressed in parts by mass.

[0514] In addition, in Table 1, 1 part by mass of each synthesis example described in the column of composition means 1 part by mass of the hydrolysis-condensation product.

[0515] In Table 1, MA represents maleic acid, TPSNO 3 represents triphenylsulfonium nitrate, PGEE represents propylene glycol monoethyl ether, and PGME represents propylene glycol monomethyl ether.

[0516] [Table 1]

[0517] * Example 1 and Comparative Example 1 also contained nitric acid contained in the polymer solution prepared in the Synthesis Example.

[0518] [4] Preparation of organic underlayer film-forming composition Under nitrogen, a 100-ml four-necked flask was charged with carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fluorenone (7.28 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and p-toluenesulfonic acid monohydrate (0.76 g, 0.0040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.). 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was added and stirred. The mixture was heated to 100°C to dissolve the mixture, thereby initiating polymerization. After 24 hours, the mixture was cooled to 60°C.

[0519] Chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.) was added to the cooled reaction mixture for dilution, and the diluted mixture was added to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) for precipitation.

[0520] The obtained precipitate was recovered by filtration, and the recovered solid was dried at 80° C. for 24 hours in a reduced pressure dryer to obtain 9.37 g of the target polymer represented by formula (X) (hereinafter abbreviated as PCzFL).

[0521] It should be noted that PCzFL 1 The measurement results of H-NMR are shown below.

[0522] 1 H-NMR (400 MHz, DMSO-d6): d 7.03-7.55 (br, 12H), d 7.61-8.10 (br, 4H), d 11.18 (br, 1H) Furthermore, the weight average molecular weight Mw of PCzFL, as calculated by polystyrene conversion based on GPC, was 2800, and the polydispersity Mw / Mn was 1.77.

[0523] [Chemistry 96]

[0524] 20 g of PCzFL, 3.0 g of tetramethoxymethyl glycoluril (manufactured by Cytec Industries, Ltd. (formerly Mitsui Cytec Co., Ltd.), trade name Powder link 1174) as a crosslinking agent, 0.30 g of pyridinium p-toluenesulfonate as a catalyst, and 0.06 g of Megafac R-30 (manufactured by DIC Corporation), trade name) as a surfactant were mixed and dissolved in 88 g of propylene glycol monomethyl ether acetate to prepare a solution. µ The obtained solution was filtered through a polyethylene microfilter with a pore size of 0.05 µ The mixture was filtered through a polyethylene microfilter of 100 μm to prepare a composition for forming an organic underlayer film.

[0525] [5] Formation of positive resist pattern using electron beam lithography equipment The organic underlayer film-forming composition was applied onto a silicon wafer using a spinner and heated on a hot plate at 240° C. for 60 seconds to form an organic underlayer film (layer A) (film thickness: 40 nm).

[0526] The composition of Example 1 was spin-coated thereon, and heated on a hot plate at 215° C. for 1 minute, thereby forming a silicon-containing resist underlayer film (B layer) (10 nm).

[0527] A positive-type EUV resist was then spin-coated on the film and heated on a hot plate at 110°C for 60 seconds to form a resist film (C layer) (38 nm). The film was then exposed under specified conditions using an electron beam lithography system (ELS-G130). After exposure, the film was baked (PEB) at 90°C for 60 seconds, cooled to room temperature on a cooling plate, and developed with an alkaline developer (2.38% TMAH aqueous solution). The optimal exposure was determined to produce 25 nm lines / 50 nm spaces (line / space (L / S) = 1 / 1).

[0528] According to the same procedure, a resist pattern was formed using the composition of Comparative Example 1.

[0529] The optimum exposure amount is shown in Table 2. In addition, Table 2 shows the optimum exposure amount (%) of Example 1 when the optimum exposure amount of Comparative Example 1 is set to 100%.

[0530] [Table 2]

Claims

1. A silicon-containing resist underlayer film-forming composition, characterized in that: contain: Component A: polysiloxane; and Component C: solvent, The polysiloxane includes a structural unit derived from a hydrolyzable silane (A) having at least one of an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring and an arylthioester group having an iodine atom directly bonded to an aromatic ring.

2. A silicon-containing resist underlayer film-forming composition, characterized in that: contain: A' component: polysiloxane; Component B: a hydrolyzable silane (A) having at least one of an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring and an arylthioester group having an iodine atom directly bonded to an aromatic ring; and Component C: solvent.

3. The silicon-containing resist underlayer film-forming composition according to claim 1 or 2, wherein The hydrolyzable silane (A) is a compound represented by the following formula (A-1): In formula (A-1), a represents an integer of 1 to 3, b represents an integer from 0 to 2, a+b represents an integer from 1 to 3, R 1 represents an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring or an arylthioester group having an iodine atom directly bonded to an aromatic ring, R 2 represents a single bond or a divalent linking group, R 3 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted haloalkyl group, an unsubstituted or substituted haloaryl group, an unsubstituted or substituted haloaralkyl group, an unsubstituted or substituted alkoxyalkyl group, an unsubstituted or substituted alkoxyaryl group, an unsubstituted or substituted alkoxyaralkyl group, or an unsubstituted or substituted alkenyl group, or R 3 represents an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more of these groups, X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, In R 1 、R 2 、R 3 If there are multiple R 1 、R 2 、R 3 Same as or different from X.

4. The silicon-containing resist underlayer film-forming composition according to claim 3, wherein R in the formula (A-1) 1 It is represented by the following formula (A-1-1) or the following formula (A-1-2), In formulas (A-1-1) and (A-1-2), Ar each independently represents an aromatic hydrocarbon group which may have a substituent, m represents an integer from 1 to x, wherein x represents the number of substituents capable of bonding to the aromatic hydrocarbon ring in Ar. Indicates a bond.

5. The silicon-containing resist underlayer film-forming composition according to claim 4, wherein In the formulae (A-1-1) and (A-1-2), Ar represents a benzene ring, and m represents an integer of 1 to 5.

6. The silicon-containing resist underlayer film-forming composition according to claim 1 or 2, wherein The component C contains an alcohol solvent.

7. The silicon-containing resist underlayer film-forming composition according to claim 6, wherein The component C contains propylene glycol monoalkyl ether.

8. The silicon-containing resist underlayer film-forming composition according to claim 1 or 2, wherein The silicon-containing resist underlayer film-forming composition further contains component D: a curing catalyst.

9. The silicon-containing resist underlayer film-forming composition according to claim 1 or 2, wherein The silicon-containing resist underlayer film-forming composition further contains component E: nitric acid.

10. A resist underlayer film, characterized in that: A cured product of the silicon-containing resist underlayer film-forming composition according to claim 1 or 2.

11. A semiconductor processing substrate, characterized in that: The invention comprises: a semiconductor substrate; and the resist underlayer film according to claim 10 .

12. A method for manufacturing a semiconductor element, characterized in that: The process includes the following steps: forming an organic lower layer film on a substrate; a step of forming a resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film-forming composition according to claim 1 or 2; and a step of forming a resist film on the resist underlayer film.

13. A pattern forming method, characterized in that: The process includes the following steps: forming an organic lower layer film on a semiconductor substrate; a step of coating the silicon-containing resist underlayer film-forming composition according to claim 1 or 2 on the organic underlayer film and firing the composition to form a resist underlayer film; forming a resist film on the resist underlayer film; exposing and developing the resist film to obtain a resist pattern; a step of etching the resist underlayer film using the resist pattern as a mask; as well as A step of etching the organic underlayer film using the patterned resist underlayer film as a mask.

14. The pattern forming method according to claim 13, wherein The pattern forming method further includes the step of removing the resist underlayer film by a wet method using a chemical solution after the step of etching the organic underlayer film.

15. A hydrolyzable silane, characterized in that The present invention comprises at least one of an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring and an arylthioester group having an iodine atom directly bonded to an aromatic ring.

16. The hydrolyzable silane according to claim 15, wherein The hydrolyzable silane is a compound represented by the following formula (A-1): In formula (A-1), a represents an integer of 1 to 3, b represents an integer from 0 to 2, a+b represents an integer from 1 to 3, R 1 represents an arylsulfonyl group having an iodine atom directly bonded to an aromatic ring or an arylthioester group having an iodine atom directly bonded to an aromatic ring, R 2 represents a single bond or a divalent linking group, R 3 represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted aralkyl group, an unsubstituted or substituted haloalkyl group, an unsubstituted or substituted haloaryl group, an unsubstituted or substituted haloaralkyl group, an unsubstituted or substituted alkoxyalkyl group, an unsubstituted or substituted alkoxyaryl group, an unsubstituted or substituted alkoxyaralkyl group, or an unsubstituted or substituted alkenyl group, or R 3 represents an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more of these groups, X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom, In R 1 、R 2 、R 3 If there are multiple R 1 、R 2 、R 3 Same as or different from X.

17. The hydrolyzable silane according to claim 16, wherein R in the formula (A-1) 1 It is represented by the following formula (A-1-1) or the following formula (A-1-2), In formulas (A-1-1) and (A-1-2), Ar each independently represents an aromatic hydrocarbon group which may have a substituent, m represents an integer from 1 to x, wherein x represents the number of substituents capable of bonding to the aromatic hydrocarbon ring in Ar. Indicates a bond.

18. A polysiloxane, characterized in that The hydrolyzable silane comprises a structural unit derived from the hydrolyzable silane according to any one of claims 15 to 17.

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