Composition for forming a silicon-containing resist underlayer film, and silicon-containing resist underlayer film

Abstract

A composition for forming a silicon-containing resist underlayer film, the composition containing component [A]: a carbon-carbon triple bond–containing polysiloxane, and component [C]: a solvent.

Description

[Technical Field]

[0001] The present invention relates to a silicon-containing resist underlayer film formation composition and a silicon-containing resist underlayer film. [Background technology]

[0002] In the manufacturing of semiconductor devices, microfabrication using lithography with photoresists has been performed conventionally. Microfabrication is a processing method in which a thin film of photoresist is formed on a semiconductor substrate such as a silicon wafer, and then activated light such as ultraviolet light is irradiated onto it through a mask pattern on which the pattern of the semiconductor device is drawn, developing the photoresist, and the substrate is etched using the resulting photoresist pattern as a protective film, thereby forming fine irregularities on the substrate surface corresponding to the pattern. In recent years, as semiconductor devices have become more highly integrated, the wavelengths of the active light used have tended to be shortened, from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm). With the shortening of the wavelength of the active light, the effect of reflection of the active light from the semiconductor substrate has become a major problem, and a method of applying an anti-reflective coating (Bottom Anti-Reflective Coating, BARC) as an underlayer to the resist between the photoresist and the substrate to be processed has become widely applied.

[0003] In recent years, a hard mask, a film containing metallic elements such as silicon and titanium, is used as an underlayer between the semiconductor substrate and the photoresist. In this case, because there are significant differences in the composition of the resist and the hard mask, the rate at which they are removed by dry etching depends heavily on the type of gas used for dry etching. By appropriately selecting the gas type, it is possible to remove the hard mask by dry etching without significantly reducing the thickness of the photoresist. Thus, in the manufacturing of semiconductor devices in recent years, a resist underlayer is increasingly being placed between the semiconductor substrate and the photoresist to achieve various effects, including anti-reflective properties.

[0004] While compositions for resist underlayers have been studied to date, the development of new materials for resist underlayers is desired due to the diversity of required properties. For example, a coating-type BPSG (boron phosphorus glass) film formation composition containing a structure with a specific silicate backbone, which addresses the issue of wet-etchable film formation (Patent Document 1), and a silicon-containing resist underlayer formation composition containing a carbonyl structure, which addresses the issue of chemical removal of mask residue after lithography, have been disclosed (Patent Document 2). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2016-74774 [Patent Document 2] International Publication No. 2018 / 181989 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] With the increasing miniaturization of resist patterns in cutting-edge semiconductor devices in recent years, there is a growing need for resist underlayer films that can prevent resist pattern collapse.

[0007] The present invention has been made in view of such circumstances, and aims to provide a silicon-containing resist underlayer film that can improve the resolution of a resist pattern by preventing the fine resist pattern from collapsing, and a silicon-containing resist underlayer film forming composition capable of forming the silicon-containing resist underlayer film. [Means for solving the problem]

[0008] The inventors of the present invention conducted diligent studies to solve the aforementioned problems and, as a result, found that they could solve the aforementioned problems, and completed the present invention having the following gist.

[0009] In other words, the present invention encompasses the following: [1] [A] Components: Carbon-carbon triple bond-containing polysiloxane, and [C] Component: Solvent A composition for forming a silicon-containing resist underlayer film, containing the following: [2] The silicon-containing resist underlayer film forming composition according to [1], wherein the carbon-carbon triple bond-containing polysiloxane comprises a structural unit derived from a hydrolyzable silane (A) having a carbon-carbon triple bond. [3] [A'] Ingredients: Polysiloxane, [B] Components: Hydrolyzable silane (A) having a carbon-carbon triple bond, and [C] Component: Solvent A composition for forming a silicon-containing resist underlayer film, containing the following: [4] The silicon-containing resist underlayer film forming composition according to [2] or [3], wherein the hydrolyzable silane (A) is a compound represented by the following formula (A-1). [ka] (In equation (A-1), a represents an integer from 1 to 3.) b represents an integer between 0 and 2. a+b represents an integer between 1 and 3. R 1 This represents an organic group that has a carbon-carbon triple bond and may also have ionic bonds. R 2represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group, or 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. X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. R 1 、R 2 and when there are a plurality of X respectively, the plurality of R 1 、R 2 and X may be the same or different. ) [5] The silicon-containing resist underlayer film-forming composition according to [4], wherein R 1 in the formula (A-1) is represented by the following formula (A-2a). [Chemical formula] (In the formula (A-2a), R 11 represents a single bond or a divalent organic group that may have an ionic bond. R[[ID=**********]] 12 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an optionally substituted aryl group. * represents a bond. ) [6] The silicon-containing resist underlayer film-forming composition according to [1] or [2], wherein the carbon-carbon triple bond-containing polysiloxane as the component [A] is a polysiloxane modified product in which a part of the silanol groups is alcohol-modified or acetal-protected. [[ID=**********]] [7] The silicon-containing resist underlayer film forming composition according to [3], wherein the polysiloxane, which is component [A'], is a polysiloxane modified product in which some of the silanol groups are alcohol-modified or acetal-protected. [8] The silicon-containing resist underlayer film forming composition according to any one of [1] to [7], wherein the [C] component contains an alcohol-based solvent. [9] The silicon-containing resist underlayer film forming composition according to [8], wherein the [C] component contains a propylene glycol monoalkyl ether.

[10] [D] Component: A silicon-containing resist underlayer film forming composition according to any one of [1] to [9], further comprising a curing catalyst.

[11] [E] Component: A silicon-containing resist underlayer film forming composition according to any one of [1] to

[10] , further containing nitric acid.

[12] A silicon-containing resist underlayer film forming composition according to any one of [1] to

[11] , wherein the [C] component contains water.

[13] A silicon-containing resist underlayer film formation composition according to any one of [1] to

[12] , for forming a resist underlayer film for EUV lithography.

[14] A silicon-containing resist underlayer film, which is a cured product of a silicon-containing resist underlayer film forming composition described in any of [1] to

[13] .

[15] Semiconductor substrate and,

[14] The silicon-containing resist underlayer film described above, A semiconductor processing substrate equipped with the following features.

[16] A step of forming an organic underlayer film on a substrate, A step of forming a resist underlayer on the organic underlayer using a silicon-containing resist underlayer forming composition described in any of [1] to

[13] , The steps include forming a resist film on the aforementioned resist underlayer film, A method for manufacturing semiconductor devices, including

[17] The resist film is formed from an EUV lithography resist. A method for manufacturing a semiconductor device as described in

[16] .

[18] In the step of forming the resist underlayer, a silicon-containing resist underlayer forming composition filtered with a nylon filter is used. A method for manufacturing a semiconductor device as described in

[16] or

[17] .

[19] A process of forming an organic underlayer film on a semiconductor substrate, The steps include applying a silicon-containing resist underlayer film forming composition described in any of [1] to

[13] onto the aforementioned organic underlayer film, firing it, and forming a resist underlayer film; The steps include applying a resist film-forming composition onto the resist underlayer film to form a resist 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, A step of etching the organic underlayer film using the patterned resist underlayer film as a mask, A pattern formation method, including the following.

[20] After the step of etching the organic underlayer film, a step of removing the resist underlayer film by a wet method using a chemical solution, The pattern forming method described in

[19] further includes the following:

[21] The resist film is formed from a resist for EUV lithography. The pattern formation method described in

[19] or

[20] . [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a silicon-containing resist underlayer film that can improve the resolution of a resist pattern by preventing the fine resist pattern from collapsing, and a silicon-containing resist underlayer film forming composition capable of forming the silicon-containing resist underlayer film. [Modes for carrying out the invention]

[0011] (Composition for forming a silicon-containing resist underlayer film) <First Embodiment> The first embodiment of the silicon-containing resist underlayer film forming composition of the present invention contains a polysiloxane as component [A] and a solvent as component [C], and further contains other components as needed. [A] The polysiloxane as component has a carbon-carbon triple bond.

[0012] The carbon-carbon triple bond-containing polysiloxane as component [A] (hereinafter sometimes referred to as "[A]polysiloxane") preferably contains structural units derived from hydrolyzable silane (A) having a carbon-carbon triple bond.

[0013] <Second Embodiment> A second embodiment of the silicon-containing resist underlayer film forming composition of the present invention contains a polysiloxane (hereinafter sometimes referred to as "[A']polysiloxane") as component [A'], a hydrolyzable silane (A) having a carbon-carbon triple bond as component [B], and a solvent as component [C], and further contains other components as needed.

[0014] The inventors have considered the following: The silicon-containing resist underlayer film formed from the silicon-containing resist underlayer film forming composition of the present invention has carbon-carbon triple bonds, which prevents the deformation of fine resist patterns and, as a result, improves the resolution of the resist patterns. The carbon-carbon triple bonds react with polar functional groups in the resist upon irradiation with light such as EUV, causing crosslinking and enabling a high crosslink density of the silicon-containing resist underlayer film. This prevents the deformation of fine resist patterns and, as a result, improves the resolution of the resist patterns.

[0015] <Hydrolyzable silane (A) containing a carbon-carbon triple bond> Hydrolyzable silane (A) has a carbon-carbon triple bond. In other words, hydrolyzable silane (A) has a structure represented by the following formula (AA). A hydrolyzable silane (A) having a carbon-carbon triple bond (hereinafter sometimes referred to as "hydrolyzable silane (A)") may have two or more carbon-carbon triple bonds. In other words, hydrolyzable silane (A) may have two or more structures represented by the following formula (AA). [ka] (In structure (AA), * represents a bond. Note that one of the bonds may be bonded to a hydrogen atom.) In that case, the two or more structures represented by formula (AA) may each be bonded to one linking group bonded to a silicon atom, or each of the two or more structures represented by formula (AA) may be bonded to a silicon atom directly or via different linking groups. The linking group is, for example, an organic group. The linking group may have an ionic bond. If the linking group has an ionic bond, the linking group may have the ionic bond in the sequence of atoms connecting the structure represented by formula (AA) to the silicon atom, or it may have the ionic bond in the sequence of atoms branched off from the sequence of atoms connecting the structure represented by formula (AA) to the silicon atom. The number of carbon atoms in the linking group is not particularly limited, but is preferably 1 to 30, and more preferably 1 to 20. The linking group usually has a hydrogen atom. The linking group may also have an oxygen atom or a nitrogen atom.

[0016] Hydrolyzable silane (A) having a carbon-carbon triple bond is preferably a compound represented by the following formula (A-1).

[0017] [ka] (In equation (A-1), a represents an integer from 1 to 3.) b represents an integer between 0 and 2. a+b represents an integer between 1 and 3. R 1 This represents an organic group that has a carbon-carbon triple bond and may also have ionic bonds. R 2 This represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or 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. X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. R 1 , R 2 If both and X are multiple, then multiple R 1 , R 2 (And X may be the same or different.)

[0018] <<R in equation (A-1) 1 >> R 1 The carbon-carbon triple bond present may be one or more. R 1 The number of carbon atoms is not particularly limited, but R 1 The number of carbon atoms is preferably 2 to 30, and more preferably 2 to 20. R 1 It usually contains a hydrogen atom. 1 In addition to the carbon-carbon triple bond and hydrogen atoms, it may also have oxygen atoms or nitrogen atoms. R 1 It may have an ionic bond. 1 If R has an ionic bond, 1It may have ionic bonds in the sequence of atoms connecting the carbon-carbon triple bond and the silicon atom, or it may have ionic bonds in the sequence of atoms branched off from the sequence of atoms connecting the carbon-carbon triple bond and the silicon atom.

[0019] R in equation (A-1) 1 Preferably, it is represented by the following formula (A-2a).

[0020] [ka] (In formula (A-2a), R 11 This represents a divalent organic group which may have a single bond or an ionic bond. R 12 This represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have substituents, or an aryl group which may have substituents. * represents a bond.

[0021] R 11 In the case of a divalent organic group which may have an ionic bond, R 11 The number of carbon atoms is not particularly limited, but R 11 The number of carbon atoms is preferably 1 to 25, and more preferably 1 to 15.

[0022] R 12 Examples of alkyl groups having 1 to 6 carbon atoms that may have substituents include alkyl groups having 1 to 6 carbon atoms. Examples of alkyl groups with 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, and 1-ethyl-n-propyl group. 1,1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2, 2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include 3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, and 2-ethyl-3-methylcyclopropyl group. Examples of alkyl groups having 1 to 6 carbon atoms that may have substituents include hydroxyl groups, halogen atoms, carboxyl groups, nitro groups, cyano groups, methylenedioxy groups, acetoxy groups, methylthio groups, amino groups, and alkoxy groups having 1 to 6 carbon atoms. In the present invention, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The number of these substituents may be one or two or more. In this specification, "i" means "iso," "s" means "sec," and "t" means "tert."

[0023] The aryl group in the optionally substituted aryl group may be, for example, a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused ring aromatic hydrocarbon compound, or a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound. 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. For example, aryl groups with 6 to 20 carbon atoms can be cited as aryl groups, and examples include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 5-naphthacenyl group, 2-crisenyl group, 1-pyrenyl group, 2-pyrenyl group, pentacenyl group, benzopyrenyl group, triphenylenyl group; biphenyl-2-yl group (o-biphenylyl group), biphenyl-3-yl group (m-biphenylyl group), biphenyl-4-yl group (p-biphenylyl group), paraterphenyl-4-yl group, metaterphenyl-4-yl group, orthoterphenyl-4-yl group, 1,1'-binaphthyl-2-yl group, 2,2'-binaphthyl-1-yl group, etc., but are not limited to these. Examples of substituents in an aryl group that may have substituents include hydroxyl groups, halogen atoms, carboxyl groups, nitro groups, cyano groups, methylenedioxy groups, acetoxy groups, methylthio groups, amino groups, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms. The number of these substituents may be one or two or more.

[0024] R 1 In addition to the carbon-carbon triple bond, it may also have a hydrogen atom, an oxygen atom, or a nitrogen atom. R 1 It may have an ionic bond. 1 If R has an ionic bond, 1 The atom may have an ionic bond in the sequence of atoms connecting the carbon-carbon triple bond and the silicon atom, or it may have a nitro group in the sequence of atoms branched off from the sequence of atoms connecting the carbon-carbon triple bond and the silicon atom.

[0025] << <R 11 >>> R 11 Preferably, it is either a single bond or a divalent organic group represented by formulas (A-2-1) to (A-2-6) below. [ka] [ka] (In formula (A-2-1), R 21 This represents an alkylene group with 1 to 6 carbon atoms. In formula (A-2-2), R 31 R represents an alkylene group with 1 to 6 carbon atoms. 32 R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 33 This represents a single bond or an alkylene group with 1 to 6 carbon atoms. In formula (A-2-3), R 41 R represents an alkylene group with 1 to 6 carbon atoms. 42This represents a single bond or an alkylene group with 1 to 6 carbon atoms. In formula (A-2-4), R 51 R represents an alkylene group with 1 to 6 carbon atoms. 52 This represents a single bond or an alkylene group with 1 to 6 carbon atoms. In formula (A-2-5), R 61 R represents an alkylene group with 1 to 6 carbon atoms. 62 and R 63 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 64 This represents a single bond or an alkylene group with 1 to 6 carbon atoms. In formula (A-2-6), R 71 R represents an alkylene group with 1 to 6 carbon atoms. 72 This represents a single bond or an alkylene group with 1 to 6 carbon atoms. In formulas (A-2-1) to (A-2-6), *1 represents a bond with Si. *2 represents a bond with a carbon atom constituting a carbon-carbon triple bond. *3 represents a bond with the carbon atom shown in *4 or *5.

[0026] Furthermore, in the silicon-containing resist underlayer film formation composition and the resist underlayer film, the amino group (-N(R) in formula (A-2-2) 32 The amino group (-N(R) in formula (A-2-2) may be cationized. For example, if nitric acid is added to the silicon-containing resist underlayer film forming composition, the amino group (-N(R) in formula (A-2-2) may be cationized. 32 )-) may be cationized and form a nitrate.

[0027] R 21 , R 31 , R 33 , R 41 , R 42 , R 51 , R 52 , R 61 , R 64 , R 71 , and R 72The alkylene group having 1 to 6 carbon atoms in the compound may be linear or branched. Examples of linear alkylene groups having 1 to 6 carbon atoms include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups. Among these, methylene, ethylene, trimethylene, and tetramethylene groups are preferred.

[0028] R 32 , R 62 , and R 63 The alkyl group having 1 to 4 carbon atoms can be either linear or branched. Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, and t-butyl groups. R 32 , R 62 , and R 63 Hydrogen atoms, methyl groups, and ethyl groups are preferred as the elements.

[0029] <<R in equation (A-1) 2 >> The alkyl group may be linear, branched, or cyclic, and its number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less. Specific examples of linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3 Examples include methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, and 1-ethyl-2-methyl-n-propyl group.

[0030] Specific examples of cyclic alkyl groups include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, and 2,4-dimethyl-cyclobutyl group. Examples include cycloalkyl groups such as methyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, and 2-ethyl-3-methyl-cyclopropyl group, as well as crosslinked cyclic cycloalkyl groups such as bicyclobutyl group, bicyclopentyl group, bicyclohexyl group, bicycloheptyl group, bicyclooctyl group, bicyclononyl group, and bicyclodecyl group.

[0031] The aryl group may be a phenyl group, a monovalent group derived by removing one hydrogen atom from a fused ring aromatic hydrocarbon compound, or a monovalent group derived by removing one hydrogen atom from a ring-linked aromatic hydrocarbon compound. 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. For example, aryl groups with 6 to 20 carbon atoms can be cited as aryl groups, and examples include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 5-naphthacenyl group, 2-crisenyl group, 1-pyrenyl group, 2-pyrenyl group, pentacenyl group, benzopyrenyl group, triphenylenyl group; biphenyl-2-yl group (o-biphenylyl group), biphenyl-3-yl group (m-biphenylyl group), biphenyl-4-yl group (p-biphenylyl group), paraterphenyl-4-yl group, metaterphenyl-4-yl group, orthoterphenyl-4-yl group, 1,1'-binaphthyl-2-yl group, 2,2'-binaphthyl-1-yl group, etc., but are not limited to these.

[0032] An aralkyl group is an alkyl group substituted with an aryl group, and specific examples of such aryl groups and alkyl groups are the same as those mentioned above. The number of carbon atoms in the aralkyl group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of aralkyl groups include, but are not limited to, phenylmethyl (benzyl) group, 2-phenylethylene group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group, 8-phenyl-n-octyl group, 9-phenyl-n-nonyl group, and 10-phenyl-n-decyl group.

[0033] Alkyl halogenated groups, aryl halogenated groups, and aralkyl halogenated groups are, respectively, alkyl groups, aryl groups, and aralkyl groups substituted with one or more halogen atoms. Specific examples of such alkyl groups, aryl groups, and aralkyl groups are the same as those mentioned above. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0034] The number of carbon atoms in the alkyl halogen is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less. Specific examples of halogenated alkyl groups include, but are not limited to, monofluoromethyl, difluoromethyl, trifluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoropropan-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, and perfluoropentyl groups.

[0035] The number of carbon atoms in the aryl halide group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of aryl halides 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, and 3-fluorophenyl. 1-Naphthyl group, 4-Fluoro-1-Naphthyl group, 6-Fluoro-1-Naphthyl group, 7-Fluoro-1-Naphthyl group, 8-Fluoro-1-Naphthyl group, 4,5-Difluoro-1-Naphthyl group, 5,7-Difluoro-1-Naphthyl group, 5,8-Difluoro-1-Naphthyl group, 5,6,7,8-Tetrafluoro-1-Naphthyl group, Heptafluoro-1-Naphthyl group, 1-Fluoro-2-Naphthyl group Examples include the tyl group, 5-fluoro-2-naphthyl group, 6-fluoro-2-naphthyl group, 7-fluoro-2-naphthyl group, 5,7-difluoro-2-naphthyl group, and heptafluoro-2-naphthyl group. In addition, groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodine group) are also included, but are not limited to these.

[0036] The number of carbon atoms in the aralkyl halogenated group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples of halogenated aralkyl groups include 2-fluorobenzyl group, 3-fluorobenzyl group, 4-fluorobenzyl group, 2,3-difluorobenzyl group, 2,4-difluorobenzyl group, 2,5-difluorobenzyl group, 2,6-difluorobenzyl group, 3,4-difluorobenzyl group, 3,5-difluorobenzyl group, 2,3,4-trifluorobenzyl group, 2,3,5-trifluorobenzyl group, 2,3,6-trifluorobenzyl group, and 2,4,5-trifluorobenzyl group. Examples include the refluorobenzyl group, 2,4,6-trifluorobenzyl group, 2,3,4,5-tetrafluorobenzyl group, 2,3,4,6-tetrafluorobenzyl group, 2,3,5,6-tetrafluorobenzyl group, and 2,3,4,5,6-pentafluorobenzyl group. In addition, groups in which the fluorine atom (fluoro group) in these groups is optionally substituted with a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodine group) are also included, but are not limited to these.

[0037] Alkoxyalkyl groups, alkoxyaryl groups, and alkoxyaralkyl groups are alkyl groups, aryl groups, and aralkyl groups, respectively, that are substituted with one or more alkoxy groups. Specific examples of such alkyl groups, aryl groups, and aralkyl groups are the same as those mentioned above.

[0038] Examples of alkoxy groups used as substituents include alkoxy groups having at least one alkyl moiety, such as a linear, branched, or cyclic structure with 1 to 20 carbon atoms. Examples of linear or branched alkoxy groups include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3- Examples include methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group. Examples of cyclic alkoxy groups include cyclopropoxy group, cyclobutoxy group, 1-methyl-cyclopropoxy group, 2-methyl-cyclopropoxy group, cyclopentyloxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3 Examples include dimethylcyclobutoxy group, 2,2-dimethylcyclobutoxy group, 2,3-dimethylcyclobutoxy group, 2,4-dimethylcyclobutoxy group, 3,3-dimethylcyclobutoxy group, 1-n-propylcyclopropoxy group, 2-n-propylcyclopropoxy group, 1-i-propylcyclopropoxy group, 2-i-propylcyclopropoxy group, 1,2,2-trimethylcyclopropoxy group, 1,2,3-trimethylcyclopropoxy group, 2,2,3-trimethylcyclopropoxy group, 1-ethyl-2-methylcyclopropoxy group, 2-ethyl-1-methylcyclopropoxy group, 2-ethyl-2-methylcyclopropoxy group, and 2-ethyl-3-methylcyclopropoxy group.

[0039] Specific examples of alkoxyalkyl groups include, but are not limited to, lower alkyloxy lower alkyl groups (approximately 5 or fewer carbon atoms) such as methoxymethyl group, ethoxymethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, and ethoxymethyl group. Specific examples of alkoxyaryl groups include, but are not limited to, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(1-ethoxy)phenyl, 3-(1-ethoxy)phenyl, 4-(1-ethoxy)phenyl, 2-(2-ethoxy)phenyl, 3-(2-ethoxy)phenyl, 4-(2-ethoxy)phenyl, 2-methoxynaphthalen-1-yl, 3-methoxynaphthalen-1-yl, 4-methoxynaphthalen-1-yl, 5-methoxynaphthalen-1-yl, 6-methoxynaphthalen-1-yl, and 7-methoxynaphthalen-1-yl groups. Specific examples of alkoxyaralkyl groups include, but are not limited to, the 3-(methoxyphenyl)benzyl group and the 4-(methoxyphenyl)benzyl group.

[0040] The alkenyl group may be linear or branched, and its number of carbon atoms is not particularly limited, but is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and still more preferably 10 or less. Specific examples of alkenyl groups include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethylethenyl group Tyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl -1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group , 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2- Examples include cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group, as well as bridging cyclic alkenyl groups such as bicycloheptenyl group (norbornyl group).

[0041] Furthermore, examples of substituents in the alkyl, aryl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, and alkenyl groups include alkyl, aryl, aralkyl, halogenated alkyl, halogenated aryl, halogenated aralkyl, alkoxyalkyl, aryloxy, alkoxyaryl, alkoxyaralkyl, alkenyl, alkoxy, and aralkyloxy groups. Specific examples of these substituents and their preferred number of carbon atoms are the same as those described above or below. Furthermore, the aryloxy group mentioned as a substituent is a group in which an aryl group is bonded via an oxygen atom (-O-), and specific examples of such aryl groups are the same as those mentioned above. The number of carbon atoms in the aryloxy group is not particularly limited, but is preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less. Specific examples include, but are not limited to, a phenoxy group and a naphthalene-2-yloxy group. Furthermore, if there are two or more substituents, they may bond together to form a ring.

[0042] Examples of organic groups having an epoxy group include glycidoxymethyl group, glycidoxyethyl group, glycidoxypropyl group, glycidoxybutyl group, and epoxycyclohexyl group. Examples of organic groups having an acryloyl group include acryloylmethyl group, acryloylethyl group, and acryloylpropyl group. Examples of organic groups having a methacryloyl group include methacryloylmethyl group, methacryloylethyl group, and methacryloylpropyl group. Organic groups containing a mercapto group include mercaptoethyl group, mercaptobutyl group, mercaptohexyl group, mercaptooctyl group, and mercaptophenyl group. Examples of organic groups containing an amino group include, but are not limited to, amino groups, aminomethyl groups, aminoethyl groups, aminophenyl groups, dimethylaminoethyl groups, and dimethylaminopropyl groups. More detailed information on organic groups containing an amino group will be provided later. Examples of organic groups containing an alkoxy group include, but are not limited to, the methoxymethyl group and the methoxyethyl group. However, groups in which the alkoxy group is directly bonded to a silicon atom are excluded. Examples of organic groups having a sulfonyl group include, but are not limited to, sulfonyl alkyl groups and sulfonylaryl groups. Examples of organic groups containing a cyano group include cyanoethyl group, cyanopropyl group, cyanophenyl group, and thiocyanate group.

[0043] Examples of organic groups having an amino group include organic groups having at least one of a primary amino group, a secondary amino group, and a tertiary amino group. Hydrolysis condensates obtained by hydrolyzing a hydrolyzable silane having a tertiary amino group with a strong acid to form a countercation having a tertiary ammonium group are preferably used. In addition to the nitrogen atom constituting the amino group, the organic group may also contain heteroatoms such as oxygen atoms and sulfur atoms.

[0044] A preferred example of an organic group having an amino group is the group represented by the following formula (A1).

[0045] [ka] In formula (A1), R 101 and R 102 The 'L's represent a hydrogen atom or hydrocarbon group independently of each other, and the 'L's represent an optionally substituted alkylene group independently of each other. The '*' represents a bond. Examples of hydrocarbon groups include, but are not limited to, alkyl groups, alkenyl groups, and aryl groups. Specific examples of these alkyl groups, alkenyl groups, and aryl groups include R 2 The same items mentioned above can be cited. Furthermore, the alkylene group may be linear or branched, and its number of carbon atoms is usually 1 to 10, preferably 1 to 5. Examples of linear alkylene groups include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene. Examples of organic groups having an amino group include, but are not limited to, amino groups, aminomethyl groups, aminoethyl groups, aminophenyl groups, dimethylaminoethyl groups, and dimethylaminopropyl groups.

[0046] <<X in equation (A-1)>> Examples of alkoxy groups in X include R2 An example is the alkoxy group, which was exemplified in the explanation. For example, R is a halogen atom in X. 2 The halogen atoms exemplified in the explanation are examples.

[0047] The aralkyloxy group is a monovalent group derived by removing a hydrogen atom from the hydroxyl group of an aralkyl alcohol. Specific examples of aralkyl groups in the aralkyloxy group are the same as those mentioned above. The number of carbon atoms in the aralkyloxy group is not particularly limited, but can be, for example, 40 or less, preferably 30 or less, and more preferably 20 or less. Specific examples of aralkyloxy groups include, but are not limited to, phenylmethyloxy group (benzyloxy group), 2-phenylethyleneoxy group, 3-phenyl-n-propyloxy group, 4-phenyl-n-butyloxy group, 5-phenyl-n-pentyloxy group, 6-phenyl-n-hexyloxy group, 7-phenyl-n-heptyloxy group, 8-phenyl-n-octyloxy group, 9-phenyl-n-nonyloxy group, and 10-phenyl-n-decyloxy group.

[0048] Acyloxy groups are monovalent groups derived by removing a hydrogen atom from the carboxyl group (-COOH) of a carboxylic acid compound. Typically, examples include, but are not limited to, alkylcarbonyloxy groups, arylcarbonyloxy groups, or aralkylcarbonyloxy groups derived by removing a hydrogen atom from the carboxyl group of alkylcarboxylic acids, arylcarboxylic acids, or aralkylcarboxylic acids. Specific examples of alkyl groups, aryl groups, and aralkyl groups in such alkylcarboxylic acids, arylcarboxylic acids, and aralkylcarboxylic acids are the same as those mentioned above. Specific examples of acyloxy groups include acyloxy groups with 2 to 20 carbon atoms, such as methyl carbonyloxy group, ethyl carbonyloxy group, n-propyl carbonyloxy group, i-propyl carbonyloxy group, n-butyl carbonyloxy group, i-butyl carbonyloxy group, s-butyl carbonyloxy group, t-butyl carbonyloxy group, n-pentyl carbonyloxy group, 1-methyl-n-butyl carbonyloxy group, 2-methyl-n-butyl carbonyloxy group, 3-methyl-n-butyl carbonyloxy group, 1,1-dimethyl-n-propyl carbonyloxy group, 1,2-dimethyl-n-propyl carbonyloxy group, 2,2-dimethyl-n-propyl carbonyloxy group, 1-ethyl-n-propyl carbonyloxy group, n-hexyl carbonyloxy group, 1-methyl-n-pentyl carbonyloxy group, and 2-methyl-n-pentylcarbonyloxy group. Examples include carbonyloxy group, 3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group, 1,1-dimethyl-n-butylcarbonyloxy group, 1,2-dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1,1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, 1-ethyl-1-methyl-n-propylcarbonyloxy group, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, and tosylcarbonyloxy group.

[0049] Specific examples of hydrolyzable silanes (A) having a carbon-carbon triple bond include, for example, the following compounds, but hydrolyzable silanes (A) having a carbon-carbon triple bond are not limited to these compounds. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] In the formula, R represents a methyl group or an ethyl group.

[0050] In the first embodiment, when synthesizing a polysiloxane containing a constituent unit derived from hydrolyzable silane (A) having a carbon-carbon triple bond, the amount of hydrolyzable silane (A) is preferably 0.01 to 100 parts by mass, more preferably 0.05 to 50 parts by mass, even more preferably 0.1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of hydrolyzable silane used in the synthesis of the polysiloxane.

[0051] In the second embodiment, the content of hydrolyzable silane (A) having a carbon-carbon triple bond as component [B] in the silicon-containing resist underlayer film forming composition is, from the viewpoint of more fully obtaining the effects of the present invention, preferably 0.01 to 100 parts by mass, more preferably 0.05 to 50 parts by mass, even more preferably 0.1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass, per 100 parts by mass of [A']polysiloxane.

[0052] <[A] component and [A'] component: Polysiloxane> [A] The polysiloxane as component is not particularly limited as long as it is a polymer having a carbon-carbon triple bond and a siloxane bond. The polysiloxane as component [A'] is not particularly limited as long as it is a polymer having siloxane bonds. The polysiloxane as component [A'] may also be the polysiloxane as component [A].

[0053] The polysiloxane may be a modified polysiloxane in which some of the silanol groups have been modified, for example, a modified polysiloxane in which some of the silanol groups have been alcohol-modified or acetal-protected. Furthermore, the polysiloxane may, for example, be a hydrolyzed condensate of a hydrolyzable silane, or a modified product in which at least a portion of the silanol groups of the hydrolyzed condensate are alcohol-modified or acetal-protected (hereinafter sometimes referred to as "modified hydrolyzed condensate"). The hydrolyzable silane in the hydrolyzed condensate may include one or more hydrolyzable silanes. Furthermore, the polysiloxane as component [A] or [A'] can have any of the following main chain structures: cage-type, ladder-type, linear-type, or branched-type. In addition, commercially available polysiloxanes can be used as component [A'].

[0054] In this invention, the "hydrolyzed condensate" of hydrolyzable silane, that is, the product of hydrolysis condensation, includes not only polyorganosiloxane polymers which are condensates in which condensation is completely completed, but also polyorganosiloxane polymers which are partially hydrolyzed condensates in which condensation is not completely completed. Such partially hydrolyzed condensates are polymers obtained by hydrolysis and condensation of hydrolyzable silane, just like condensates in which condensation is completely completed, but the hydrolysis stops only partially and condensation does not occur, and therefore Si-OH groups remain. In addition, the silicon-containing resist underlayer film forming composition may contain uncondensed hydrolysates (complete hydrolysates, partially hydrolysates) or monomers (hydrolyzable silanes) in addition to hydrolyzed condensates. In this specification, "hydrolyzable silane" may also be simply referred to as "silane compound."

[0055] Examples of polysiloxanes as component [A] include hydrolysis condensates or modified products thereof of hydrolyzable silanes containing a hydrolyzable silane (A) having a carbon-carbon triple bond.

[0056] Examples of polysiloxanes as component [A] include hydrolyzable silanes (A) having a carbon-carbon triple bond and hydrolyzable condensates or modified products thereof of hydrolyzable silanes containing at least one hydrolyzable silane represented by the following formula (1). As the polysiloxane component [A'], for example, a hydrolysis condensate or modified product thereof of a hydrolyzable silane containing at least one hydrolyzable silane represented by the following formula (1) can be cited.

[0057] <<Formula (1)>> [ka]

[0058] In formula (1), R 1This group is bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alkyl halide, an optionally substituted aryl halide, an optionally substituted aralkyl halide, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, an organic group having an alkoxy group, an organic group having a sulfonyl group, or an organic group having a cyano group, or a combination of two or more of these. Also R 2 These are groups or atoms bonded to a silicon atom, and independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. 'a' represents an integer between 0 and 3.

[0059] R in equation (1) 1 Specific examples of each group and atom in formula (A-1), and their preferred number of carbon atoms, are as follows: 2 The aforementioned groups and carbon atom counts can be cited. R in equation (1) 2 Specific examples of each group and atom in formula (A-1), as well as their preferred number of carbon atoms, include the groups, atoms, and number of carbon atoms mentioned above for X in formula (A-1).

[0060] <<<Specific examples of hydrolyzable silanes represented by formula (1)>>> Specific examples of hydrolyzable silanes represented by formula (1) include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriamiloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, and methyltriphenoxysilane. Netyloxysilane, Glycidoxymethyltrimethoxysilane, Glycidoxymethyltriethoxysilane, α-Glycidoxyethyltrimethoxysilane, α-Glycidoxyethyltriethoxysilane, β-Glycidoxyethyltrimethoxysilane, β-Glycidoxyethyltriethoxysilane, α-Glycidoxypropyltrimethoxysilane, α-Glycidoxypropyltriethoxysilane, β-Glycidoxypropyltrimethoxysilane, β-Glycidoxypropyltriethoxysilane, γ-Glycidoxypropyltrimethoxysilane, γ- Ricidoxypropyltriethoxysilane, γ-glycidoxypropyltrippropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxysilane (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, γ-(3,4-Epoxycyclohexyl)propyltrimethoxysilane,γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane Sisilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ- Ricidoxypropyl vinyldimethoxysilane, γ-glycidoxypropyl vinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiacetoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylacetoxysilane, divinyldimeth Xysilane, Divinyldiethoxysilane, Divinyldichlorosilane, Divinyldiacetoxysilane, γ-Glycidoxypropylvinyldimethoxysilane, γ-Glycidoxypropylvinyldiethoxysilane, Allyltrimethoxysilane, Allyltriethoxysilane, Allyltrichlorosilane, Allyltriacetoxysilane, Allylmethyldimethoxysilane, Allylmethyldiethoxysilane, Allylmethyldichlorosilane, Allylmethyldiacetoxysilane, Allyldimethylmethoxysilane, Allyldimethylethoxysilane, Allyldimethylchlorosilane,Allyldimethylacetoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldichlorosilane, diallyldiacetoxysilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyltriethoxysilane, p-styryltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiacetoxysilane , phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylacetoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiacetoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylacetoxysilane, triphenylchlorosilane, 3-phenyl Diaminopropyltrimethoxysilane, 3-phenylaminopropyltriethoxysilane, dimethoxymethyl-3-(3-phenoxypropylthiopropyl)silane, triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethylmethoxysilane, benzyldimethylethoxysilane, benzyldimethylchlorosilane, phenethyltrimethoxysilane, phenethyltriethoxy Sisilane, phenethyltrichlorosilane, phenethyltriacetoxysilane, phenethylmethyldimethoxysilane, phenethylmethyldiethoxysilane, phenethylmethyldichlorosilane, phenethylmethyldiacetoxysilane, methoxyphenyltrimethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltriacetoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriacetoxysilane, methoxybenzyltrichlorosilane,Methoxyphenethyltrimethoxysilane, Methoxyphenethyltriethoxysilane, Methoxyphenethyltriacetoxysilane, Methoxyphenethyltrichlorosilane, Ethoxyphenyltrimethoxysilane, Ethoxyphenyltriethoxysilane, Ethoxyphenyltriacetoxysilane, Ethoxyphenyltrichlorosilane, Ethoxybenzyltrimethoxysilane, Ethoxybenzyltriethoxysilane, Ethoxybenzyltriacetoxysilane, Ethoxybenzyltrichlorosilane, i-Propoxyphenyltrimethoxysilane, i-Propoxy i-Powoxyphenyltriacetoxysilane, i-Propoxyphenyltrichlorosilane, i-Propoxybenzyltrimethoxysilane, i-Propoxybenzyltriethoxysilane, i-Propoxybenzyltriacetoxysilane, i-Propoxybenzyltrichlorosilane, t-Butoxyphenyltrimethoxysilane, t-Butoxyphenyltriethoxysilane, t-Butoxyphenyltriacetoxysilane, t-Butoxyphenyltrichlorosilane, t-Butoxybenzyltrimethoxysilane, t-Butoxy Benzyltriethoxysilane, t-butoxybenzyltriacetoxysilane, t-butoxysibenzyltrichlosilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriacetoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriacetoxysilane, ethoxynaphthyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyl Reacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, thiocyanatetopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiallylisocyanurate, bicyclo[2,2,1]heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane,Examples include, but are not limited to, benzenesulfonamidopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptomethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and silanes represented by the following formulas (A-1) to (A-41), (1-1) to (1-225), and (1-246) to (1-290).

[0061] [ka]

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] [ka]

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[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] In formulas (1-1) to (1-225) and (1-246) to (1-290), T independently represents an alkoxy group, an acyloxy group, or a halogen group, preferably a methoxy group or an ethoxy group.

[0109] Furthermore, as [A]polysiloxane, examples include hydrolyzable silanes (A) having a carbon-carbon triple bond, and hydrolyzable silanes represented by the following formula (2), which are hydrolyzable condensates or modified products thereof. Furthermore, as [A]polysiloxane, examples include hydrolyzed condensates or modified products thereof of hydrolyzable silanes, which include hydrolyzable silanes having a carbon-carbon triple bond (A), hydrolyzable silanes represented by formula (1), and hydrolyzable silanes represented by the following formula (2). Examples of [A']polysiloxanes include hydrolyzed condensates or modified products thereof of hydrolyzable silanes, which include a hydrolyzable silane represented by formula (1), or, in place of the hydrolyzable silane represented by formula (1), a hydrolyzable silane represented by formula (2) below.

[0110] <Formula (2)> [ka]

[0111] In formula (2), R 3 This group is bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or 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. Also R 4 These are groups or atoms bonded to a silicon atom, and independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. R 5 These are groups that bond to a silicon atom and independently represent either an alkylene group or an arylene group. b represents 0 or 1, and c represents 0 or 1.

[0112] R 3 Specific examples of each group and atom in formula (A-1), and their preferred number of carbon atoms, are as follows: 2 The aforementioned groups and carbon atom counts can be cited. R 4 Specific examples of each group and atom in formula (A-1), as well as their preferred number of carbon atoms, include the groups, atoms, and number of carbon atoms mentioned above for X in formula (A-1). R 5 Specific examples of alkylene groups in this context include linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkylene groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; methanetriyl, ethane-1,1,2-triyl, ethane-1,2,2-triyl, and ethane. Examples of alkanetriyl groups include, but are not limited to, the -2,2,2-triyl group, propane-1,1,1-triyl group, propane-1,1,2-triyl group, propane-1,2,3-triyl group, propane-1,2,2-triyl group, propane-1,1,3-triyl group, butane-1,1,1-triyl group, butane-1,1,2-triyl group, butane-1,1,3-triyl group, butane-1,2,3-triyl group, butane-1,2,4-triyl group, butane-1,2,2-triyl group, butane-2,2,3-triyl group, 2-methylpropane-1,1,1-triyl group, 2-methylpropane-1,1,2-triyl group, and 2-methylpropane-1,1,3-triyl group. R5 Specific examples of arylene groups in this context include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group; 1,5-naphthalenediyl group, 1,8-naphthalenediyl group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group, 1,2-anthracenediyl group, 1,3-anthracenediyl group, 1,4-anthracenediyl group, 1,5-anthracenediyl group, 1,6-anthracenediyl group, 1,7-anthracenediyl group, 1,8-anthracenediyl group, 2,3- Examples include, but are not limited to, groups derived by removing two hydrogen atoms from the aromatic ring of fused ring aromatic hydrocarbon compounds such as anthracenediyl, 2,6-anthracenediyl, 2,7-anthracenediyl, 2,9-anthracenediyl, 2,10-anthracenediyl, and 9,10-anthracenediyl groups; and groups derived by removing two hydrogen atoms from the aromatic ring of ring-linked aromatic hydrocarbon compounds such as 4,4'-biphenyldiyl and 4,4''-paraterphenyldiyl groups. b is preferably 0. c is preferably 1.

[0113] Specific examples of hydrolyzable silanes represented by formula (2) include, but are not limited to, methylene bistrimethoxysilane, methylene bistrichlorosilane, methylene bistriacetoxysilane, ethylene bistriethoxysilane, ethylene bistrichlorosilane, ethylene bistriacetoxysilane, propylene bistriethoxysilane, butylene bistrimethoxysilane, phenylene bistrimethoxysilane, phenylene bistriethoxysilane, phenylene bismethyldiethoxysilane, phenylene bismethyldimethoxysilane, naphthylene bistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, and bismethyldimethoxydisilane.

[0114] [A] As the polysiloxane, a hydrolytic condensate of hydrolyzable silanes or a modified product thereof can be mentioned, which contains a hydrolyzable silane (A) having a carbon-carbon triple bond, a hydrolyzable silane represented by the formula (1) and / or a hydrolyzable silane represented by the formula (2), and other hydrolyzable silanes listed below. [A'] As the polysiloxane, a hydrolytic condensate of hydrolyzable silanes or a modified product thereof can be mentioned, which contains a hydrolyzable silane represented by the formula (1) and / or a hydrolyzable silane represented by the formula (2), and other hydrolyzable silanes listed below. Examples of other hydrolyzable silanes include, but are not limited to, silane compounds having an onium group in the molecule, silane compounds having a cyclic urea skeleton in the molecule, etc.

[0115] <<Silane compound having an onium group in the molecule (hydrolyzable organosilane)>> A silane compound having an onium group in the molecule is expected to effectively and efficiently promote the cross-linking reaction of hydrolyzable silanes.

[0116] A preferred example of a silane compound having an onium group in the molecule is represented by the formula (3).

[0117] [Chemical formula]

[0118] R 11 is a group bonded to the silicon atom and represents an onium group or an organic group having the same. R 12This group is bonded to a silicon atom and independently represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, or an organic group having a cyano group, or a combination of two or more of these. R 13 These are groups or atoms bonded to a silicon atom, and independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. f represents 1 or 2, g represents 0 or 1, and satisfies 1 ≤ f + g ≤ 2.

[0119] 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, and organic groups having epoxy groups, organic groups having acryloyl groups, organic groups having methacryloyl groups, organic groups having mercapto groups, organic groups having amino groups and organic groups having cyano groups, alkoxy groups, aralkyloxy groups, acyloxy groups, halogen atoms, and specific examples of substituents of 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 number of carbon atoms is R 12 Regarding R in equation (A-1), 2 Regarding the above, R 13 Regarding this, the previously mentioned values ​​for X in equation (A-1) can be listed.

[0120] 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. That is, preferred specific examples of the onium group or an organic group having the same include a cyclic ammonium group, a chain ammonium group, or an organic group having at least one of these, and a tertiary ammonium group, a quaternary ammonium group, or an organic group having at least one of these is preferred. When the onium group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as an atom constituting the ring. At this time, there are cases where the nitrogen atom and the silicon atom constituting the ring are bonded directly or via a divalent linking group, and cases where the carbon atom and the silicon atom constituting the ring are bonded directly or via a divalent linking group.

[0121] In one example of a preferred embodiment, R, which is a group bonded to the silicon atom 11 is a heteroaromatic cyclic ammonium group represented by the following formula (S1).

[0122]

Chemical formula

[0123]

Chemical formula

[0124] In formula (S1), R 14 Each independently represents 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, R 14 If there are two or more R 14 They may be bonded to each other to form a ring, and two R 14 The ring formed may be a bridging ring structure, in which case the cyclic ammonium group will have an adamantane ring, norbornene ring, spiro ring, etc. Specific examples of such alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, and alkenyl groups, and their preferred number of carbon atoms, are the same as those mentioned above.

[0125] In formula (S1), n 1 m is an integer from 1 to 8. 1 is 0 or 1, m 2 is a positive integer ranging from 0 or 1 to the maximum number that can be replaced by a monoring or polyring. m 1 If A is 0, 1 ~A 4 (4+n) 1 A member ring is formed. That is, n 1 When is 1, it is a 5-membered ring, n 1 When is 2, it is a 6-membered ring, n 1 When is 3, it is a 7-membered ring, n 1 When is 4, it is an 8-membered ring, n 1When is 5, it is a 9-membered ring, n 1 When n is 6, it is a 10-membered ring. 1 When is 7, it is an 11-membered ring, n 1 When the number is 8, a 12-membered ring is formed. m 1 If A is 1, 1 ~A 3 (4+n) 1 ) Member ring and A 4 A fused ring is formed by the fusion of a 6-membered ring containing the compound. A 1 ~A 4 Depending on which of formulas (J1) to (J3) it is, there may or may not be hydrogen atoms on the atoms constituting the ring, but A 1 ~A 4 However, if there is a hydrogen atom on the atom constituting the ring, that hydrogen atom is R 14 It may be replaced by A. 1 ~A 4 In the ring constituent atoms other than the ring constituent atoms inside, R 14 It may be substituted. For these reasons, as mentioned above, m 2 This is selected from integers ranging from 0 or 1 to the maximum number that can be replaced by a monoring or polyring.

[0126] The bonds of the heteroaromatic cyclic ammonium group represented by formula (S1) are located on any carbon or nitrogen atom present in such a monocyclic or fused ring, and either directly bond to a silicon atom or form an organic group with a cyclic ammonium group to which a linking group is attached, and this group then bonds to a silicon atom. Examples of such linking groups include, but are not limited to, alkylene groups, arylene groups, and alkenylene groups. Specific examples of alkylene groups and arylene groups, and their preferred number of carbon atoms, are the same as those mentioned above.

[0127] Furthermore, the alkenylene group is a divalent group derived by removing one more hydrogen atom from an alkenyl group, and specific examples of such alkenyl groups are the same as those mentioned 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. Specific examples include, but are not limited to, vinylene, 1-methylvinylene, propenylene, 1-butenylene, 2-butenylene, 1-pentenylene, and 2-pentenylene groups.

[0128] Specific examples of silane compounds represented by formula (3) having a heteroaromatic cyclic ammonium group represented by formula (S1) (hydrolyzable organosilanes) include, but are not limited to, the silanes represented by formulas (I-1) to (I-50) below.

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] In another example, the group R bonded to the silicon atom in formula (3) 11 This can be a heteroaliphatic cyclic ammonium group represented by the following formula (S2).

[0133] [ka]

[0134] In formula (S2), A 5 , A 6 , A 7 and A8 These represent a base that is independent of each other and can be expressed by any of the following formulas (J4) to (J6), but A 5 ~A 8 At least one of them is a group represented by the following formula (J5). The silicon atom in formula (3) is A 5 ~A 8 Depending on which of the following it bonds with, the resulting ring exhibits non-aromaticity, A 5 ~A 8 The bond between each atom and the adjacent atoms that form the ring together is determined to be either a single bond or a double bond. * represents a bond.

[0135] [ka]

[0136] In formulas (J4) to (J6), R 10 Each of these independently represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkyl halide, an aryl halide, an aralkyl halide, or an alkenyl group. Specific examples of alkyl groups, aryl groups, aralkyl groups, alkyl halides, aryl halides, aralkyl halides, and alkenyl groups, and their preferred number of carbon atoms, are the same as those mentioned above. * represents a bond.

[0137] In formula (S2), R 15 Each independently represents 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, R 15 If there are two or more R 15 They may be bonded to each other to form a ring, and two R 15 The ring formed may be a bridging ring structure, in which case the cyclic ammonium group will have an adamantane ring, norbornene ring, spiro ring, etc. Specific examples of alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, and alkenyl groups, and their preferred number of carbon atoms, are the same as those mentioned above.

[0138] In formula (S2), n 2 m is an integer from 1 to 8. 3 is 0 or 1, m 4 is a positive integer ranging from 0 or 1 to the maximum number that can be replaced by a monoring or polyring. m 3 If A is 0, 5 ~A 8 (4+n) 2 A member ring is formed. That is, n 2 When is 1, it is a 5-membered ring, n 2 When is 2, it is a 6-membered ring, n 2 When is 3, it is a 7-membered ring, n 2 When is 4, it is an 8-membered ring, n 2 When is 5, it is a 9-membered ring, n 2 When n is 6, it is a 10-membered ring. 2 When is 7, it is an 11-membered ring, n 2 When the number is 8, a 12-membered ring is formed. m 3 If A is 1, 5 ~A 7 (4+n) 2 ) Member ring and A 8 A fused ring is formed by the fusion of a 6-membered ring containing the compound. A 5 ~A 8 Depending on which of formulas (J4) to (J6) it is, there may or may not be hydrogen atoms on the atoms constituting the ring, but A 5 ~A 8 However, if there is a hydrogen atom on the atom constituting the ring, that hydrogen atom is R 15 It may be replaced by A. 5 ~A 8 In the ring constituent atoms other than the ring constituent atoms inside, R 15 It may be substituted. For these reasons, as mentioned above, m 4This is selected from integers ranging from 0 or 1 to the maximum number that can be replaced by a monoring or polyring.

[0139] The bonds of the heteroaliphatic cyclic ammonium group represented by formula (S2) are located on any carbon or nitrogen atom present in such a monocyclic or fused ring, and either directly bond to a silicon atom or form an organic group with a cyclic ammonium group by which a linking group is attached, and this organic group then bonds to a silicon atom. Examples of such linking groups include alkylene groups, arylene groups, or alkenylene groups. Specific examples of alkylene groups, arylene groups, and alkenylene groups, as well as their preferred number of carbon atoms, are the same as those mentioned above.

[0140] Specific examples of silane compounds represented by formula (3) having a heteroaliphatic cyclic ammonium group represented by formula (S2) (hydrolyzable organosilanes) include, but are not limited to, the silanes represented by formulas (II-1) to (II-30) below.

[0141] [ka]

[0142] [ka]

[0143] In yet another example, the group R bonded to the silicon atom in formula (3) 11 This can be a chain-like ammonium group represented by the following formula (S3).

[0144] [ka] In formula (S3), R 10Each of these independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, an alkyl halide, an aryl halide, an aralkyl halide, or an alkenyl group. Specific examples of alkyl groups, aryl groups, aralkyl groups, alkyl halides, aryl halides, aralkyl halides, and alkenyl groups, and their preferred number of carbon atoms, are the same as those mentioned above. * represents a bond.

[0145] The chain-like ammonium group represented by formula (S3) is either directly bonded to a silicon atom, or a linking group is attached to it to form an organic group having a chain-like ammonium group, which then bonds to a silicon atom. Examples of such linking groups include alkylene groups, arylene groups, or alkenylene groups, and specific examples of alkylene groups, arylene groups, and alkenylene groups are the same as those mentioned above.

[0146] Specific examples of silane compounds represented by formula (3) having a chain-like ammonium group represented by formula (S3) (hydrolyzable organosilanes) include, but are not limited to, the silanes represented by formulas (III-1) to (III-28) below.

[0147] [ka]

[0148] [ka]

[0149] <<Silane compounds containing a cyclic urea skeleton within the molecule (hydrolyzable organosilanes)>> Examples of hydrolyzable organosilanes having a cyclic urea skeleton in their molecule include hydrolyzable organosilanes represented by the following formula (4-1).

[0150] [ka] In formula (4-1), R401 These are groups that bond to silicon atoms and, independently of each other, represent groups represented by the following formula (4-2). R 402 This represents a group bonded to a silicon atom, and may represent an optionally substituted alkyl group, optionally substituted aryl group, optionally substituted aralkyl group, optionally substituted halogenated alkyl group, optionally substituted halogenated aryl group, optionally substituted halogenated aralkyl group, optionally substituted alkoxyalkyl group, optionally substituted alkoxyaryl group, optionally substituted alkoxyaralkyl group, or optionally substituted alkenyl group; or an organic group having an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, or an organic group having a cyano group, or a combination of two or more of these. R 403 These are groups or atoms bonded to a silicon atom, and independently represent an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. x is either 1 or 2, and y is either 0 or 1, satisfying x + y ≤ 2. R 402 Organic groups having alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, alkenyl groups, and epoxy groups, organic groups having acryloyl groups, organic groups having methacryloyl groups, organic groups having mercapto groups, and organic groups having cyano groups, as well as R 403 The alkoxy group, aralkyloxy group, acyloxy group, and halogen atom, as well as specific examples of their substituents, preferred number of carbon atoms, etc., are given by R in formula (A-1). 2 The same items as those mentioned above can be cited for X.

[0151] [ka] In formula (4-2), R 404Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an organic group having an epoxy group or a sulfonyl group, and R 405 These independently represent an alkylene group, a hydroxyalkylene group, a sulfide bond (-S-), an ether bond (-O-), or an ester bond (-CO-O- or -O-CO-). * represents a bond. Note, R 404 Specific examples of organic groups having an optionally substituted alkyl group, an optionally substituted alkenyl group, and an epoxy group, and preferred numbers of carbon atoms, etc., are given by R in formula (A-1). 2 The same things mentioned above can be cited regarding R, but in addition to these, 404 Preferably, the alkyl group that may be substituted is an alkyl group in which the terminal hydrogen atom is substituted with a vinyl group. Specific examples include the allyl group, 2-vinylethyl group, 3-vinylpropyl group, and 4-vinylbutyl group.

[0152] Organic groups having a sulfonyl group are not particularly limited as long as they contain a sulfonyl group, and include optionally substituted alkylsulfonyl groups, optionally substituted arylsulfonyl groups, optionally substituted aralkylsulfonyl groups, optionally substituted halogenated alkylsulfonyl groups, optionally substituted halogenated arylsulfonyl groups, optionally substituted halogenated aralkylsulfonyl groups, optionally substituted alkoxyalkylsulfonyl groups, optionally substituted alkoxyarylsulfonyl groups, optionally substituted alkoxyaralkylsulfonyl groups, optionally substituted alkenylsulfonyl groups, and the like. Specific examples of alkyl groups, aryl groups, aralkyl groups, halogenated alkyl groups, halogenated aryl groups, halogenated aralkyl groups, alkoxyalkyl groups, alkoxyaryl groups, alkoxyaralkyl groups, and alkenyl groups in these groups, as well as their substituents and preferred number of carbon atoms, are given by R in formula (A-1). 2 The same points mentioned above can be cited.

[0153] The alkylene group is a divalent group derived by removing one more hydrogen atom from an alkyl group, and can be linear, branched, or cyclic. Specific examples of such alkylene groups are the same as those mentioned 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 still more preferably 10 or less.

[0154] Also, R 405 The alkylene group may have one or more selected from sulfide bonds, ether bonds, and ester bonds at its terminal or in the middle, preferably in the middle. Specific examples of alkylene groups 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; and 1,2-cyclopropanediyl, 1,2-cyclobutanediyl, and 1,3-cyclobutanediyl. Examples of alkylene groups include cyclic alkylenes such as tandyl groups, 1,2-cyclohexanediyl groups, and 1,3-cyclohexanediyl groups, as well as alkylene groups containing ether groups such as -CH2OCH2-, -CH2CH2OCH2-, -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2OCH2CH2CH2-, -CH2SCH2-, -CH2CH2SCH2-, -CH2CH2SCH2CH2-, -CH2CH2SCH2CH2CH2-, -CH2CH2SCH2CH2CH2-, -CH2CH2CH2SCH2CH2CH2-, -CH2OCH2CH2SCH2-, etc., but are not limited to these.

[0155] A hydroxyalkylene group is an alkylene group in which at least one hydrogen atom is replaced by a hydroxyl group. Specific examples include, but are not limited to, 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.

[0156] In formula (4-2), X 401 Each of these independently represents one of the groups represented by formulas (4-3) to (4-5) below, and the carbon atoms of the ketone group in formulas (4-4) and (4-5) below are the same as R in formula (4-2). 405 It bonds with the nitrogen atom to which it is bonded. [ka]

[0157] In formulas (4-3) to (4-5), R 406 ~R 410 R independently represents an organic group having a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an epoxy or sulfonyl group. Specific examples and preferred number of carbon atoms of organic groups having optionally substituted alkyl groups, optionally substituted alkenyl groups, and epoxy or sulfonyl groups are given by R in formula (A-1). 2 The same examples mentioned above can be cited. Furthermore, specific examples of organic groups having a sulfonyl group and preferred carbon atom numbers are listed in R. 404 The same items mentioned above can be cited. * indicates a coupling. In particular, from the perspective of achieving excellent lithography characteristics with good reproducibility, X401 The base represented by formula (4-5) is preferred.

[0158] From the perspective of achieving excellent lithography characteristics with good reproducibility, R 404 and R 406 ~R 410 Preferably, at least one of the elements is an alkyl group in which the terminal hydrogen atom is substituted with a vinyl group.

[0159] The hydrolyzable organosilane represented by formula (4-1) may be a commercially available product, or it can be synthesized by known methods described in International Publication No. 2011 / 102470, etc.

[0160] Specific examples of hydrolyzable organosilanes represented by formula (4-1) include, but are not limited to, the silanes represented by formulas (4-1-1) to (4-1-29) below.

[0161] [ka]

[0162] [ka]

[0163] [ka]

[0164] [A]Polysiloxane and [A']Polysiloxane may be hydrolysis condensates or modified products thereof of hydrolyzable silanes containing other silane compounds other than those exemplified above, to the extent that the effects of the present invention are not impaired.

[0165] As mentioned above, modified products can be used as [A]polysiloxane and [A']polysiloxane, in which at least a portion of the silanol groups of the hydrolysis condensate are modified. For example, modified products in which a portion of the silanol groups are alcohol-modified or acetal-protected modified products can be used. Examples of the modified polysiloxane include reaction products obtained by the reaction of at least a portion of the silanol groups of the hydrolyzable silane hydrolysis condensate with the hydroxyl groups of an alcohol, dehydration reaction products of the condensate and an alcohol, and modified products obtained by protecting at least a portion of the silanol groups of the condensate with acetal groups.

[0166] Monohydric alcohols can be used as the alcohol, such as methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, and 1-hexanol. Examples include 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, and cyclohexanol. Additionally, 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.

[0167] The reaction between the silanol group of the hydrolysis condensate and the hydroxyl group of the alcohol is carried out by contacting the hydrolysis condensate with the alcohol and reacting 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 group is capped. In this case, the capping alcohol can be used as a solvent in a composition containing polysiloxane.

[0168] Furthermore, the dehydration reaction product of a hydrolyzable silane hydrolysis condensate and an alcohol can be produced by reacting the hydrolysis condensate with an alcohol in the presence of an acid catalyst, capping the silanol group with the alcohol, and removing the resulting water from the reaction system. The acid used can be an organic acid with an acid dissociation constant (pKa) of -1 to 5, preferably 4 to 5. For example, the acid can be trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, acetic acid, etc., with benzoic acid, isobutyric acid, and acetic acid being particularly noteworthy. Furthermore, the acid used can have a boiling point of 70 to 160°C, such as trifluoroacetic acid, isobutyric acid, acetic acid, and nitric acid. Thus, as an acid, it is preferable to use one that has either an acid dissociation constant (pKa) of 4 to 5 or a boiling point of 70 to 160°C. In other words, an acid with low acidity or an acid with high acidity but a low boiling point can be used. Furthermore, as an acid, it is possible to utilize either the acid dissociation constant or the boiling point properties.

[0169] The acetal protection of the silanol group in the hydrolysis condensate can be carried out using a vinyl ether, for example, a vinyl ether represented by the following formula (5), and through these reactions, the substructure represented by the following formula (6) can be introduced into the polysiloxane.

[0170] [ka] In formula (5), R 1a , R 2a , and R 3a Each of these represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, and R 4a R represents an alkyl group with 1 to 10 carbon atoms. 2a and R 4a These elements may be bonded to each other to form a ring. Examples of alkyl groups can be given above. [ka] In formula (6), R 1 ', R 2 ', and R 3 ' represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms, R 4 ' represents an alkyl group with 1 to 10 carbon atoms, R 2 'and R 4 The ' atoms may be bonded to each other to form a ring. In formula (6), * indicates a bond with an adjacent atom. The adjacent atom may be, for example, the oxygen atom of a siloxane bond, the oxygen atom of a silanol group, or the R in formula (1). 1 Examples of carbon atoms derived from this include the aforementioned examples of alkyl groups.

[0171] Examples of vinyl ethers represented by formula (5) include 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, as well as cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-pyran. In particular, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-pyran, or 2,3-dihydrofuran can be used.

[0172] The acetal protection of silanol groups can be carried out using a hydrolysis condensate, a vinyl ether, and an aprotic solvent such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, or 1,4-dioxane, with a catalyst such as pyridium p-toluenesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, or sulfuric acid.

[0173] Furthermore, the capping of these silanol groups with alcohol or acetal protection may be carried out simultaneously with the hydrolysis and condensation of the hydrolyzable silane, as described later.

[0174] The hydrolysis condensate or modified product of a hydrolyzable silane may have a weight-average molecular weight of, for example, 500 to 1,000,000. From the viewpoint of suppressing precipitation of the hydrolysis condensate or modified product in the composition, the weight-average molecular weight is preferably 500,000 or less, more preferably 250,000 or less, and even more preferably 100,000 or less. From the viewpoint of achieving both storage stability and applicability, it is preferably 700 or more, and more preferably 1,000 or more. The weight-average molecular weight is the molecular weight obtained by converting it to polystyrene using GPC analysis. GPC analysis can be performed, for example, using a GPC instrument (product name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (product name Shodex® KF803L, KF802, KF801, manufactured by Showa Denko K.K.), with a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate of 1.0 mL / min, and polystyrene (Shodex®, manufactured by Showa Denko K.K.) as the standard sample.

[0175] Hydrolyzable silane hydrolysis condensates are obtained by hydrolyzing and condensing the aforementioned silane compounds (hydrolyzable silanes). The aforementioned silane compounds (hydrolyzable silanes) contain 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 silyl halogenated group (hereinafter referred to as a hydrolyzable group). For the hydrolysis of these hydrolyzable groups, typically 0.1 to 100 moles of water, for example 0.5 to 100 moles, preferably 1 to 10 moles, are used per mole of hydrolyzable group. During hydrolysis and condensation, a hydrolysis catalyst may be used to accelerate the reaction, or it may be carried out without one. When a hydrolysis catalyst is used, typically 0.0001 to 10 moles, preferably 0.001 to 1 mole, of the hydrolysis catalyst can be used per mole of hydrolyzable group. The reaction temperature for hydrolysis and condensation is typically in the range of room temperature or higher, and below the reflux temperature at atmospheric pressure of the organic solvent that can be used for hydrolysis, for example, 20 to 110°C or 20 to 80°C. Hydrolysis may be complete, meaning all hydrolyzable groups may be converted to silanol groups, or it may be partial hydrolysis, meaning some hydrolyzable groups may remain unreacted. Examples of hydrolysis catalysts that can be used for hydrolysis and condensation include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0176] Examples of metal chelate compounds used as hydrolysis catalysts include triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-i-propoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, and di -i-propoxy bis(acetylacetonate) titanium, di-n-butoxy bis(acetylacetonate) titanium, di-sec-butoxy bis(acetylacetonate) titanium, di-t-butoxy bis(acetylacetonate) titanium, monoethoxy tris(acetylacetonate) titanium, mono-n-propoxy tris(acetylacetonate) titanium, mono-i-propoxy tris(acetylacetonate) titanium, mono-n-butoxy tris(acetylacetonate) titanium, mono-sec-butoxy tris(acetylacetonate) Titanium acetone, mono-t-butoxy tris(acetylacetonate) titanium, tetrakis(acetylacetonate) titanium, triethoxy mono(ethylacetoacetate) titanium, tri-n-propoxy mono(ethylacetoacetate) titanium, tri-i-propoxy mono(ethylacetoacetate) titanium, tri-n-butoxy mono(ethylacetoacetate) titanium, tri-sec-butoxy mono(ethylacetoacetate) titanium, tri-t-butoxy mono(ethylacetoacetate) titanium, diethoxy bis(ethylacetoacetate) titanium Titanium diacetate, di-n-propoxy-bis(ethylacetate) titanium, di-i-propoxy-bis(ethylacetate) titanium, di-n-butoxy-bis(ethylacetate) titanium, di-sec-butoxy-bis(ethylacetate) titanium, di-t-butoxy-bis(ethylacetate) titanium, monoethoxy-tris(ethylacetate) titanium, mono-n-propoxy-tris(ethylacetate) titanium, mono-i-propoxy-tris(ethylacetate) titanium,Titanium chelate compounds such as mono-n-butoxytris(ethylacetoacetate)titanium, mono-sec-butoxytris(ethylacetoacetate)titanium, mono-t-butoxytris(ethylacetoacetate)titanium, tetrakis(ethylacetoacetate)titanium, mono(acetylacetonate)tris(ethylacetoacetate)titanium, bis(acetylacetonate)bis(ethylacetoacetate)titanium, tris(acetylacetonate)mono(ethylacetoacetate)titanium; triethoxy-mono(acetylacetoacetate) Zirconium triacetate, tri-n-propoxy mono(acetylacetonate)zirconium, tri-i-propoxy mono(acetylacetonate)zirconium, tri-n-butoxy mono(acetylacetonate)zirconium, tri-sec-butoxy mono(acetylacetonate)zirconium, tri-t-butoxy mono(acetylacetonate)zirconium, diethoxy bis(acetylacetonate)zirconium, di-n-propoxy bis(acetylacetonate)zirconium, di-i-propoxy bis(A Cetylacetonate) zirconium, di-n-butoxy bis(acetylacetonate) zirconium, di-sec-butoxy bis(acetylacetonate) zirconium, di-t-butoxy bis(acetylacetonate) zirconium, monoethoxy tris(acetylacetonate) zirconium, mono-n-propoxy tris(acetylacetonate) zirconium, mono-i-propoxy tris(acetylacetonate) zirconium, mono-n-butoxy tris(acetylacetonate) zirconium, mono-sec- Butoxytris(acetylacetonate)zirconium, mono-t-butoxytris(acetylacetonate)zirconium, tetrakis(acetylacetonate)zirconium, triethoxymono(ethylacetoacetate)zirconium, tri-n-propoxymono(ethylacetoacetate)zirconium, tri-i-propoxymono(ethylacetoacetate)zirconium, tri-n-butoxymono(ethylacetoacetate)zirconium, tri-sec-butoxymono(ethylacetoacetate)zirconium,Tri-t-butoxy mono(ethyl acetate) zirconium, diethoxy bis(ethyl acetate) zirconium, di-n-propoxy bis(ethyl acetate) zirconium, di-i-propoxy bis(ethyl acetate) zirconium, di-n-butoxy bis(ethyl acetate) zirconium, di-sec-butoxy bis(ethyl acetate) zirconium, di-t-butoxy bis(ethyl acetate) zirconium, monoethoxy tris(ethyl acetate) zirconium, mono-n-propoxy tris(ethyl acetate) zirconium, mono-i-propoxy tris(ethyl acetate) zirconium, mono-n-butoxy Examples of zirconium chelate compounds include, but are not limited to, tris(ethylacetate)zirconium, mono-sec-butoxytris(ethylacetate)zirconium, mono-t-butoxytris(ethylacetate)zirconium, tetrakis(ethylacetate)zirconium, mono(acetylacetonate)tris(ethylacetate)zirconium, bis(acetylacetonate)bis(ethylacetate)zirconium, and tris(acetylacetonate)mono(ethylacetate)zirconium; and aluminum chelate compounds such as tris(acetylacetonate)aluminum and tris(ethylacetate)aluminum; etc.

[0177] Examples of organic acids used as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, meritic 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, tartaric acid, etc.

[0178] Examples of inorganic acids used as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0179] Examples of organic bases used as hydrolysis catalysts 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.

[0180] Examples of inorganic bases used as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

[0181] Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and these may be used individually or in combination of two or more.

[0182] In particular, nitric acid can be suitably used as a hydrolysis catalyst in this invention. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, and in particular, changes in the molecular weight of the hydrolysis condensate or its modified product can be suppressed. It is known that the stability of the hydrolysis condensate or its modified product in liquid depends on the pH of the solution. After diligent research, it was found that by using an appropriate amount of nitric acid, the pH of the solution can be brought into a stable range. Furthermore, as mentioned above, nitric acid can also be used when obtaining modified hydrolysis condensates, for example, when capping silanol groups with alcohol. Therefore, it is preferable from the viewpoint that it can contribute to both the hydrolysis and condensation of hydrolyzable silane and the alcohol capping of the hydrolysis condensate.

[0183] When hydrolysis and condensation occur, organic solvents may be used as solvents. Specific examples include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbencene, i-propylbencene, diethylbenzene, i- Aromatic hydrocarbon solvents such as butylbenzene, triethylbenzene, di-i-propylbencene, and n-amylnaphthalene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, and 2-ethylbutanol. n-heptanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, Monoalcohol solvents such as phenylmethylcarbinol, diacetone alcohol, and cresol; polyhydric alcohol solvents such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin;Ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and phenthion; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl Ethers, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and other ether-based solvents;Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol Examples of ester solvents include monomethyl ether, dipropylene glycol acetate monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents include 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 include dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propanesultone, but are not limited to these. These solvents can be used individually or in combination of two or more. ;

[0184] After the hydrolysis and condensation reactions are complete, the reaction solution can be neutralized, either as is or diluted or concentrated, and then treated with an ion exchange resin to remove the hydrolysis catalysts such as acids and bases used in the hydrolysis and condensation. Alternatively, before or after such treatment, by-products such as alcohol, water, and the hydrolysis catalysts used can be removed from the reaction solution by vacuum distillation or the like.

[0185] The hydrolysis condensate or its modified product (hereinafter also referred to as polysiloxane) obtained in this manner can be obtained in the form of a polysiloxane varnish dissolved in an organic solvent, and this can be used as is in the preparation of a composition for forming a silicon-containing resist underlayer film. That is, the reaction solution can be used as is (or diluted) in the preparation of a composition for forming a silicon-containing resist underlayer film, and in this case, the hydrolysis catalyst and by-products used for hydrolysis and condensation may remain in the reaction solution as long as they do not impair the effects of the present invention. For example, the hydrolysis catalyst and nitric acid used during alcohol capping of silanol groups may remain in the polymer varnish solution at a concentration of about 100 ppm to 5,000 ppm. The resulting polysiloxane varnish may be subjected to solvent substitution or diluted with an appropriate solvent. Furthermore, if its storage stability is not compromised, the organic solvent can be removed from the resulting polysiloxane varnish to obtain a 100% film-forming component concentration. The film-forming component refers to the components of the composition excluding the solvent component. The organic solvent used for solvent substitution or dilution of the polysiloxane varnish may be the same as or different from the organic solvent used in the hydrolysis and condensation reactions of the hydrolyzable silane. This dilution solvent is not particularly limited, and one or more types may be arbitrarily selected and used.

[0186] <[C] Component: Solvent> In the first embodiment, the solvent as component [C] can be any solvent that can dissolve and mix with component [A] and, if necessary, other components contained in the silicon-containing resist underlayer film forming composition, without any particular limitations. In the second embodiment, the solvent as component [C] can be any solvent that can dissolve and mix components [A'] and [B], as well as other components contained in the silicon-containing resist underlayer film forming composition as needed, without any particular limitations.

[0187] [C]The solvent is preferably an alcohol-based solvent, more preferably an alkylene glycol monoalkyl ether that is an alcohol-based solvent, and even more preferably a propylene glycol monoalkyl ether. Since these solvents also act as capping agents for the silanol groups of the hydrolysis condensate, a silicon-containing resist underlayer film forming composition can be prepared from a solution obtained by preparing [A]polysiloxane or [A']polysiloxane without the need for solvent substitution or the like. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutylcarbinol, and propylene glycol monobutyl ether.

[0188] Other specific examples of [C] solvents 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, and 2-hydroxy-2-methyl Ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 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 dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, acetic acid Methyl, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyethyl acetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, methyl 3-methoxypropionate,Examples of suitable solvents include ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. The solvent can be used individually or in combination of two or more.

[0189] Furthermore, the silicon-containing resist underlayer film forming composition of the present invention may contain water as a solvent. When water is included 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, based on the total mass of the solvents contained in the composition.

[0190] <[D]Component: Curing catalyst> The silicon-containing resist underlayer film formation composition may be a composition that does not contain a curing catalyst, but it is preferable that it contains a curing catalyst (component [D]).

[0191] As curing catalysts, ammonium salts, phosphines, phosphonium salts, sulfonium salts, etc., can be used. The salts listed below as examples of curing catalysts may be added in salt form, or they may form salts in the composition (added as separate compounds and forming salts in the system).

[0192] As an ammonium salt, formula (D-1): [ka] (In the formula, m a represents integers from 2 to 11, and n arepresents an integer between 2 and 3, R 21 Y represents an alkyl group, an aryl group, or an aralkyl group. - represents an anion. ) Quaternary ammonium salts having a structure represented by ),

[0193] Formula (D-2): [ka] (In the formula, R 22 , R 23 , R 24 and R 25 These independently represent an alkyl group, an aryl group, or an aralkyl group, Y - represents an anion, and R 22 , R 23 , R 24 , and R 25 Each of these is bonded to a nitrogen atom. ) A quaternary ammonium salt having a structure represented by ),

[0194] Formula (D-3): [ka] (In the formula, R 26 and R 27 These independently represent an alkyl group, an aryl group, or an aralkyl group, Y - represents an anion. ) Quaternary ammonium salts having a structure represented by ),

[0195] Formula (D-4): [ka] (In the formula, R 28 Y represents an alkyl group, an aryl group, or an aralkyl group. - represents an anion. ) Quaternary ammonium salts having a structure represented by ),

[0196] Formula (D-5): [ka] (In the formula, R 29and R 30 These independently represent an alkyl group, an aryl group, or an aralkyl group, Y - represents an anion. ) Quaternary ammonium salts having a structure represented by ),

[0197] Formula (D-6): [ka] (In the formula, m a represents integers from 2 to 11, and n a represents an integer between 2 and 3, Y - represents an anion. Examples of tertiary ammonium salts having the structure represented by ) are given.

[0198] Furthermore, as a phosphonium salt, formula (D-7): [ka] (In the formula, R 31 , R 32 , R 33 , and R 34 These independently represent an alkyl group, an aryl group, or an aralkyl group, Y - represents an anion, and R 31 , R 32 , R 33 , and R 34 Each of these is bonded to a phosphorus atom. Examples of quaternary phosphonium salts represented by ( ) can be given.

[0199] Furthermore, as a sulfonium salt, formula (D-8): [ka] (In the formula, R 35 , R 36 , and R 37 These independently represent an alkyl group, an aryl group, or an aralkyl group, Y - represents an anion, and R 35 , R 36 , and R 37Each of these is bonded to a sulfur atom. Examples of tertiary sulfonium salts represented by ( ) can be given.

[0200] The compound of formula (D-1) is a quaternary ammonium salt derived from an amine, and m a represents integers from 2 to 11, and n a R represents an integer between 2 and 3. 21 This represents, for example, an alkyl group having 1 to 18 carbon atoms, preferably 2 to 10, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms. Examples include linear alkyl groups such as ethyl, propyl, and butyl groups, as well as benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl groups. Also, an anion (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include those listed above.

[0201] The compound of formula (D-2) is R 22 R 23 R 24 R 25 N + Y - This is a quaternary ammonium salt represented by . The R of this quaternary ammonium salt 22 , R 23 , R 24 and R 25 These are, for example, alkyl groups with 1 to 18 carbon atoms such as ethyl group, propyl group, butyl group, cyclohexyl group, and cyclohexylmethyl group, aryl groups with 6 to 18 carbon atoms such as phenyl group, or aralkyl groups with 7 to 18 carbon atoms such as benzyl group. Anion (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO- ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include ) and others. These quaternary ammonium salts are commercially available, and examples include tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, and trimethylbenzylammonium chloride.

[0202] The compound of formula (D-3) is a quaternary ammonium salt derived from a 1-substituted imidazole, and R 26 and R 27 The number of carbon atoms is, for example, 1 to 18, and R 26 and R 27 It is preferable that the total number of carbon atoms is 7 or more. For example, R 26 Examples of R include alkyl groups such as methyl, ethyl, and propyl groups, aryl groups such as phenyl groups, and aralkyl groups such as benzyl groups. 27 Examples include aralkyl groups such as benzyl groups, octyl groups, and octadecyl groups. Anions (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include ). This compound can be obtained commercially, but it can also be produced by reacting imidazole compounds such as 1-methylimidazole and 1-benzylimidazole with aralkyl halides, alkyl halides, and aryl halides such as benzyl bromide, methyl bromide, and benzene bromide.

[0203] The compound of formula (D-4) is a quaternary ammonium salt derived from pyridine, and R 28This is, for example, 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 include a butyl group, an octyl group, a benzyl group, and a lauryl group. Anion (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include those such as ). This compound can be obtained commercially, but it can also be produced by reacting pyridine with an alkyl halide or aryl halide such as lauryl chloride, benzyl chloride, benzyl bromide, methyl bromide, or octyl bromide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0204] The compound of formula (D-5) is a quaternary ammonium salt derived from substituted pyridines such as picoline, and R 29 This is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 4 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 18 carbon atoms, and examples include a methyl group, an octyl group, a lauryl group, a benzyl group, etc. 30 For example, R 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, if the compound represented by formula (D-5) is a quaternary ammonium derived from picoline, then R 30 It is a methyl group. Anion (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O -Examples of acidic groups include those such as ). This compound can be obtained commercially, but it can also be produced by reacting a substituted pyridine such as picoline with an alkyl halide or aryl halide such as methyl bromide, octyl bromide, lauryl chloride, benzyl chloride, or benzyl bromide. Examples of this compound include N-benzylpicolinium chloride, N-benzylpicolinium bromide, and N-laurylpicolinium chloride.

[0205] The compound of formula (D-6) is a tertiary ammonium salt derived from an amine, and m a represents integers from 2 to 11, and n a This indicates 2 or 3. Also, the anion (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O - Examples of acidic groups include (Y). This compound can be produced by the reaction of an amine with a weak acid such as a carboxylic acid or phenol. Examples of carboxylic acids include formic acid and acetic acid, and when formic acid is used, an anion (Y - ) is (HCOO - ) and when acetic acid is used, the anion (Y - ) is (CH3COO - ) is also used. In addition, when phenol is used, the anion (Y - ) is (C6H5O - )

[0206] The compound of formula (D-7) is R 31 R 32 R 33 R 34 P + Y - It is a quaternary phosphonium salt having the structure R 31 , R 32 , R 33 , and R 34For example, R is an alkyl group having 1 to 18 carbon atoms such as an ethyl group, propyl group, butyl group, or cyclohexylmethyl group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, or an aralkyl group having 7 to 18 carbon atoms such as a benzyl group, preferably R 31 ~R 34 Three of the four substituents are unsubstituted or substituted phenyl groups, such as phenyl groups and tolyl groups, and the remaining one is an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. Also, the anion (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O -Examples of acidic groups include ) and others. This compound is available commercially, and examples include tetraalkylphosphonium halides such as tetra-n-butylphosphonium halide and tetra-n-propylphosphonium halide, trialkylbenzylphosphonium halides such as triethylbenzylphosphonium halide, triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, tritrilmonoarylphosphonium halide, or tritrilmonoalkylphosphonium halide (in all cases, the halogen atom is a chlorine atom or a bromine atom). Particularly preferred are triphenylmonoalkylphosphonium halides such as triphenylmethylphosphonium halide and triphenylethylphosphonium halide, triphenylmonoarylphosphonium halides such as triphenylbenzylphosphonium halide, tritrilmonoarylphosphonium halides such as tritrilmonophenylphosphonium halide, and tritrilmonoalkylphosphonium halides such as tritrilmonomethylphosphonium halide (the halogen atom is a chlorine atom or a bromine atom).

[0207] Furthermore, examples of phosphines include primary phosphines such as methylphosphine, ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0208] The compound of formula (D-8) is R 35 R 36 R 37 S + Y - It is a tertiary sulfonium salt having the structure R 35 , R36 , and R 37 For example, R is an alkyl group having 1 to 18 carbon atoms such as an ethyl group, propyl group, butyl group, or cyclohexylmethyl group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, or an aralkyl group having 7 to 18 carbon atoms such as a benzyl group, preferably R 35 ~R 37 Two of the three substituents are unsubstituted or substituted phenyl groups, such as phenyl or tolyl groups, and the remaining one is an alkyl group with 1 to 18 carbon atoms, an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. Also, the anion (Y - ) is a chloride ion (Cl - ), bromine ions (Br - ), iodide ion (I - Halide ions such as ) and carboxylates (-COO - ), sulfonate (-SO3 - ), Alcorato (-O -Examples of acid groups include maleate anions and nitrate anions. This compound is available commercially, and examples include trialkylsulfonium halides such as tri-n-butylsulfonium halide and tri-n-propylsulfonium halide, dialkylbenzylsulfonium halides such as diethylbenzylsulfonium halide, diphenylmonoalkylsulfonium halides such as diphenylmethylsulfonium halide and diphenylethylsulfonium halide, triphenylsulfonium halide (in all cases, the halogen atom is either a chlorine atom or a bromine atom), trialkylsulfonium carboxylates such as tri-n-butylsulfonium carboxylate and tri-n-propylsulfonium carboxylate, dialkylbenzylsulfonium carboxylates such as diethylbenzylsulfonium carboxylate, diphenylmonoalkylsulfonium carboxylates such as diphenylmethylsulfonium carboxylate and diphenylethylsulfonium carboxylate, and triphenylsulfonium carboxylate. In addition, triphenylsulfonium halide and triphenylsulfonium carboxylate can be preferably used.

[0209] Furthermore, a nitrogen-containing silane compound can be added as a curing catalyst. Examples of nitrogen-containing silane compounds include imidazole ring-containing silane compounds such as N-(3-triethoxysilipropyl)-4,5-dihydroimidazole.

[0210] In the silicon-containing resist underlayer film forming composition of the first embodiment, the content of the curing catalyst [D] 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, per 100 parts by mass of [A] polysiloxane, from the viewpoint of obtaining the effects of the present invention to the fullest extent. In the silicon-containing resist underlayer film forming composition of the second embodiment, the content of the curing catalyst [D] 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, per 100 parts by mass of [A']polysiloxane, from the viewpoint of obtaining the effects of the present invention to the fullest extent.

[0211] <[E] Ingredient: Nitrate> The silicon-containing resist underlayer film formation composition preferably contains [E] nitric acid. [E]Nitric acid may be added during the preparation of the silicon-containing resist underlayer film formation composition, but it can also be used as a hydrolysis catalyst or during alcohol capping of silanol groups in the production of the polysiloxane described above, and the residue remaining in the polysiloxane varnish can be treated as [E]nitric acid.

[0212] [E] The amount of nitric acid added (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.

[0213] <Other additives> Various additives can be incorporated into the silicon-containing resist underlayer film formation composition depending on the application of the composition. Examples of additives include known additives that are incorporated into materials (compositions) that form various films that can be used in the manufacture of semiconductor devices, such as resist underlayer films, anti-reflective films, and pattern reversal films. These additives include crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymers, acid generators, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, UV-curable surfactants, etc.). The following are examples of various additives, but they are not limited to these.

[0214] <<Stabilizer>> Stabilizers may be added for purposes such as stabilizing hydrolysis condensates of hydrolyzable silanes. Specific examples of such stabilizers include organic acids, water, alcohols, or combinations thereof. 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. Among these, oxalic acid and maleic acid are preferred. When adding organic acids, the amount added is 0.1 to 5.0% by mass relative to the hydrolysis condensate of the hydrolyzable silane. These organic acids can also act as pH adjusters. As the water used, pure water, ultrapure water, or deionized water can be used, and if used, the amount added can be 1 to 20 parts by mass per 100 parts by mass of the silicon-containing resist underlayer film forming composition. The alcohol used is preferably one that is easily dispersed by heating after application, such as methanol, ethanol, propanol, i-propanol, and butanol. When alcohol is added, the amount added can be 1 to 20 parts by mass per 100 parts by mass of the silicon-containing resist underlayer film forming composition.

[0215] <<Organic Polymers>> By adding organic polymers to a silicon-containing resist underlayer film formation composition, the dry etching rate (decrease in film thickness per unit time), as well as the damping coefficient and refractive index of the film (resist underlayer film) formed from the composition can be adjusted. There are no particular restrictions on the organic polymer used; various organic polymers (condensation polymers and addition polymers) can be appropriately selected depending on the purpose of their addition. Specific examples include addition polymerization polymers and condensation polymerization polymers such as polyester, polystyrene, polyimide, acrylic polymer, methacrylic polymer, polyvinyl ether, phenol novolac, naphthol novolac, polyether, polyamide, and polycarbonate. In the present invention, organic polymers containing aromatic rings or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoxaline rings that function as light-absorbing sites can also be suitably used when such functionality is required. Specific examples of such organic polymers include, but are not limited to, addition polymerization polymers containing addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthryl methacrylate, anthryl methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as structural units, and condensation polymerization polymers such as phenol novolac and naphthol novolac.

[0216] When an addition polymerization polymer is used as the organic polymer, the polymer may be either a homopolymer or a copolymer. Addition polymerizable monomers are used in the production of addition polymers. Specific examples of such addition polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, acrylic acid ester compounds, methacrylic acid ester compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, and acrylonitrile.

[0217] Specific examples of acrylic acid ester compounds include, but are not limited to, methyl acrylate, ethyl acrylate, n-hexyl acrylate, i-propyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthyl methyl acrylate, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trichloroethyl acrylate, 2-bromoethyl acrylate, 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-methyl-2-adamantyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-acryloxypropyltriethoxysilane, and glycidyl acrylate.

[0218] Specific examples of methacrylate ester compounds include, but are not limited to, methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, i-propyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthylmethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,2-trichloroethyl methacrylate, 2-bromoethyl methacrylate, 4-hydroxybutyl methacrylate, 2-methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methyl-2-adamantyl methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, and bromophenyl methacrylate.

[0219] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-antrylcrylamide.

[0220] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, and N-antlylmethacrylamide.

[0221] Specific examples of vinyl compounds include, but are not limited to, vinyl alcohol, 2-hydroxyethyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, benzyl vinyl ether, vinyl acetic acid, vinyl trimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl naphthalene, and vinyl anthracene.

[0222] Specific examples of styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, and acetylstyrene.

[0223] Specific examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0224] When a condensation polymer is used as the polymer, examples of such polymers include condensation polymers of glycol compounds and dicarboxylic acid compounds. Examples of glycol compounds include diethylene glycol, hexamethylene glycol, and butylene glycol. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, and maleic anhydride. Other examples include, but are not limited to, polyesters, polyamides, and polyimides such as polypyromellitrimide, poly(p-phenylene terephthalamide), polybutylene terephthalate, and polyethylene terephthalate. If an organic polymer contains hydroxyl groups, these hydroxyl groups can undergo crosslinking reactions with hydrolysis condensates and the like.

[0225] The weight-average molecular weight of organic polymers can typically be between 1,000 and 1,000,000. When incorporating organic polymers, in order to fully obtain the functional effects of the polymer while suppressing precipitation in the composition, the weight-average molecular weight can be set to, for example, 3,000 to 300,000, 5,000 to 300,000, or 10,000 to 200,000. Such organic polymers may be used individually or in combination of two or more types.

[0226] When a silicon-containing resist underlayer film forming composition contains an organic polymer, its content cannot be specified in general terms as it is determined appropriately considering the function of the organic polymer, etc. However, it can usually be in the range of 1 to 200% by mass relative to [A]polysiloxane or [A']polysiloxane. From the viewpoint of suppressing precipitation in the composition, for example, it can be 100% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less. From the viewpoint of obtaining the full effect, for example, it can be 5% by mass or more, preferably 10% by mass or more, and more preferably 30% by mass or more.

[0227] <<Acid Generator>> Examples of acid generators include thermal acid generators and photoacid generators, with photoacid generators being preferred. Examples of photoacid generators include, but are not limited to, onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds. Furthermore, depending on the type, some photoacid generators, such as carboxylates (nitrates, maleates, etc.) and hydrochlorides of onium salt compounds (described later), can also function as curing catalysts. Examples of thermal acid generators include, but are not limited to, tetramethylammonium nitrate.

[0228] Specific examples of iodonium salt compounds include, but are not limited to, iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-t-butylphenyl)iodonium camphorsulfonate, and bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nitrate, triphenylsulfonium trifluoroacetate, triphenylsulfonium maleate, and triphenylsulfonium chloride.

[0229] Specific examples of sulfonimide compounds include, but are not limited to, N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0230] Specific examples of disulfonyl diazomethane compounds 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.

[0231] When a silicon-containing resist underlayer film formation composition contains an acid generator, its content cannot be specified in general terms as it is determined appropriately considering the type of acid generator, etc. However, it is usually in the range of 0.01 to 5% by mass relative to [A]polysiloxane or [A']polysiloxane, preferably 3% by mass or less, more preferably 1% by mass or less, from the viewpoint of suppressing the precipitation of the acid generator in the composition, and preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of obtaining its effect sufficiently. The acid generator can be used alone or in combination of two or more types, and a photoacid generator and a thermoacid generator may be used in combination.

[0232] <<Surfactants>> Surfactants are effective in suppressing the occurrence of pinholes, striations, and other defects when silicon-containing resist underlayer formation compositions are applied to substrates or organic underlayer films. Examples of surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorine-based surfactants, and UV-curable surfactants. More specifically, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and polyoxyethylene sorbitan tristearate. Nonionic surfactants such as oleate, polyoxyethylene sorbitan tristearate, and other polyoxyethylene sorbitan fatty acid esters; trade names F-Top (registered trademark) EF301, EF303, EF352 (manufactured by 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); Florard F Examples of fluorinated surfactants include C430, FC431 (manufactured by 3M Japan Ltd.), the product name Asahi Guard (registered trademark) AG710 (manufactured by AGC Inc.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), and organosiloxane polymer-KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), but are not limited to these. Surfactants can be used individually or in combination of two or more types.

[0233] When a silicon-containing resist underlayer film forming composition contains a surfactant, its content is usually 0.0001 to 5% by mass, preferably 0.001 to 4% by mass, and more preferably 0.01 to 3% by mass, relative to [A]polysiloxane or [A']polysiloxane.

[0234] <<Rheology modifier>> Rheology modifiers are primarily added to improve the fluidity of compositions for forming silicon-containing resist underlayer films, particularly in the baking process, to improve the uniformity of the film thickness and enhance the filling of holes by the composition. Specific examples include phthalate derivatives such as dimethyl phthalate, diethyl phthalate, di-i-butyl phthalate, dihexyl phthalate, and butyl-i-decyl phthalate; adipic acid derivatives such as dinormal butyl adipate, di-i-butyl adipate, di-i-octyl adipate, and octyl decyl adipate; maleic acid derivatives such as dinormal butyl malate, diethyl malate, and dinonyl malate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; or stearic acid derivatives such as normal butyl stearate and glyceryl stearate. When these rheological modifiers are used, the amount added is usually less than 30% by mass of the total film-forming components of the silicon-containing resist underlayer film-forming composition.

[0235] <<Adhesion aid>> Next, the adhesion promoter is mainly added for the purpose of improving the adhesion between the substrate, the organic underlayer film or the resist, and the film (resist underlayer film) formed from the composition for forming a silicon-containing resist underlayer film, and particularly for suppressing and preventing the peeling of the resist during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, etc., alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, etc., silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, etc., other silanes such as γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc., heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, etc., ureas such as 1,1-dimethylurea, 1,3-dimethylurea, or thiourea compounds. When these adhesion promoters are used, the addition amount is usually less than 5% by mass, preferably less than 2% by mass, based on the film-forming components of the composition for forming a silicon-containing resist underlayer film.

[0236] <<pH Adjusting Agent>> In addition, as the pH adjusting agent, other than the acids having one or more carboxylic acid groups such as the organic acids mentioned as the stabilizers above can be mentioned. When the pH adjusting agent is used, the addition amount can be in a ratio of 0.01 to 20 parts by mass, or 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass, based on 100 parts by mass of [A] polysiloxane or [A'] polysiloxane.

[0237] <<Metal Oxide>> Furthermore, examples of metal oxides that can be added to silicon-containing resist underlayer film formation compositions 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 metalloids such as boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0238] The concentration of the film-forming component in the silicon-containing resist underlayer film-forming composition can be, for example, 0.1 to 50% by mass, 0.1 to 30% by mass, 0.1 to 25% by mass, or 0.5 to 20.0% by mass, relative to the total amount of the composition. The content of [A]polysiloxane or [A']polysiloxane in the film-forming component is usually 20% to 100% by mass, but from the viewpoint of obtaining the effects of the present invention with good reproducibility, the lower limit is preferably 50% by mass, more preferably 60% by mass, even more preferably 70% by mass, and still more preferably 80% by mass, and the upper limit is preferably 99% by mass, with the remainder being the additives described later. Furthermore, the silicon-containing resist underlayer film forming composition preferably has a pH of 2 to 5, and more preferably a pH of 3 to 4.

[0239] The silicon-containing resist underlayer film forming composition of the first embodiment can be manufactured 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 mixed with the [C]solvent and other components. The mixing order is not particularly limited. For example, the solution containing [A] polysiloxane may be mixed with [C] solvent, and the other components may be added to the mixture. Alternatively, the solution containing [A] polysiloxane, [C] solvent, and the other components may be mixed simultaneously. If necessary, additional [C] solvent may be added at the end, or some components that are relatively soluble in [C] solvent may be left out of the mixture and added at the end. However, from the viewpoint of suppressing aggregation and separation of constituent components and preparing a composition with excellent uniformity with good reproducibility, it is preferable to prepare a solution in which [A] polysiloxane is well dissolved in advance and use this to prepare the composition. Note that [A] polysiloxane may aggregate or precipitate when mixed with other components, depending on the type and amount of [C] solvent mixed with it, and the amount and properties of other components. Also, when preparing a composition using a solution in which [A] polysiloxane is dissolved, note that it is necessary to determine the concentration of the [A] polysiloxane solution and the amount used so that the amount of [A] polysiloxane in the final composition is the desired amount. During the preparation of the composition, heating may be used as appropriate, provided that the components do not decompose or deteriorate.

[0240] The silicon-containing resist underlayer film forming composition of the second embodiment can be produced by mixing [A']polysiloxane, [B]hydrolyzable silane (A) having a carbon-carbon triple bond, [C]solvent, and, if other components are included as desired, those other components. In this case, a solution containing [A']polysiloxane may be prepared in advance, and this solution may be mixed with [B]hydrolyzable silane (A) having a carbon-carbon triple bond, [C]solvent, and other components. The mixing order is not particularly limited. For example, a solution containing [A']polysiloxane may be mixed with [B]hydrolyzable silane (A) having a carbon-carbon triple bond and [C]solvent, and other components may be added to the mixture. Alternatively, the solution containing [A']polysiloxane, [B]hydrolyzable silane (A) having a carbon-carbon triple bond, [C]solvent, and other components may be mixed simultaneously. If necessary, additional [C] solvent may be added at the end, or some components that are relatively soluble in [C] solvent may be left out of the mixture and added at the end. However, from the viewpoint of suppressing aggregation and separation of constituent components and preparing a composition with excellent uniformity with good reproducibility, it is preferable to prepare a solution in which [A']polysiloxane is well dissolved in advance and use this to prepare the composition. Note that [A']polysiloxane may aggregate or precipitate when mixed with [B] hydrolyzable silane (A) having a carbon-carbon triple bond and [C] solvent, as well as the amount and properties of other components. Also, when preparing a composition using a solution in which [A']polysiloxane is dissolved, note that it is necessary to determine the concentration of the [A']polysiloxane solution and the amount used so that the amount of [A']polysiloxane in the final composition is the desired amount. During the preparation of the composition, heating may be used as appropriate, provided that the components do not decompose or deteriorate.

[0241] In the present invention, the silicon-containing resist underlayer film forming composition may be filtered using a sub-micrometer-order filter or the like during the manufacturing process or after all components have been mixed. The material of the filter used is not limited, but for example, a nylon filter or a fluororesin filter can be used.

[0242] The silicon-containing resist underlayer film formation composition of the present invention can be suitably used as a resist underlayer film formation composition for use in lithography processes.

[0243] (Resist underlayer film, semiconductor processing substrate, pattern formation method, and semiconductor device manufacturing method) 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.

[0244] The semiconductor processing substrate of the present invention comprises, for example, the silicon-containing resist underlayer film of the present invention.

[0245] The method for manufacturing a semiconductor device of the present invention is, for example, A process of forming an organic underlayer film on a substrate, A step of forming a resist underlayer on an organic underlayer using the silicon-containing resist underlayer forming composition of the present invention, A step of forming a resist film on top of the resist underlayer film, Includes.

[0246] The pattern forming method of the present invention is, for example, A process of forming an organic underlayer film on a semiconductor substrate, The process involves applying the silicon-containing resist underlayer film formation composition of the present invention onto an organic underlayer film, firing it, and forming a resist underlayer film. A step of applying a resist film-forming composition onto a resist underlayer film to form a resist film, The process involves exposing and developing a resist film to obtain a resist pattern, A process of etching the resist underlayer using a resist pattern as a mask, A process of etching an organic underlayer film using a patterned resist underlayer film as a mask, Includes.

[0247] Hereinafter, as an embodiment of the present invention, a semiconductor processing substrate, a pattern formation method, and a method for manufacturing a semiconductor device will be described, using the silicon-containing resist underlayer film of the present invention or the silicon-containing resist underlayer film forming composition of the present invention.

[0248] 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 [for example, semiconductor substrates such as silicon wafers coated with silicon oxide films, silicon nitride films, or silicon oxidizrin nitride films, silicon nitride substrates, quartz substrates, glass substrates (including alkali-free glass, low-alkali glass, and crystallized glass), glass substrates on which ITO (indium tin oxide) films or IZO (indium zinc oxide) films are formed, plastic (polyimide, PET, etc.) substrates, substrates coated with low-dielectric constant materials (low-k materials), flexible substrates, etc.] by an appropriate coating method such as a spinner or coater, and then the composition is cured by firing using a heating means such as a hot plate to form a resist underlayer film. Hereinafter, in this specification, "resist underlayer film" refers to the silicon-containing resist underlayer film of the present invention, or a film formed from the silicon-containing resist underlayer film forming composition of the present invention. The firing conditions are appropriately selected from among a firing temperature of 40°C to 400°C, or 80°C to 250°C, and a firing time of 0.3 minutes to 60 minutes. Preferably, the firing temperature is 150°C to 250°C and the firing time is 0.5 minutes to 2 minutes. The thickness of the resist underlayer film formed here can be, for example, 10 nm to 1,000 nm, or 20 nm to 500 nm, or 50 nm to 300 nm, or 100 nm to 200 nm, or 10 nm to 150 nm. Furthermore, as the silicon-containing resist underlayer formation composition used when forming the resist underlayer, a silicon-containing resist underlayer formation composition filtered with a nylon filter can be used. Here, a silicon-containing resist underlayer formation composition filtered with a nylon filter refers to a composition that has been filtered with a nylon filter either during the manufacturing process of the silicon-containing resist underlayer formation composition, or after all components have been mixed.

[0249] In one embodiment of the present invention, an organic underlayer film is formed on a substrate, and then a resist underlayer film is formed on top of it. However, in some cases, an embodiment may be made in which no organic underlayer film is provided. There are no particular restrictions on the organic underlayer film used here; any film that has been conventionally used in lithography processes can be arbitrarily selected and used. By providing an organic underlayer film, a resist underlayer film on top of that, and a resist film described later on top of that on the substrate, the pattern width of the photoresist film is narrowed. Even when the photoresist film is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas described later. For example, the resist underlayer film can be processed by using a fluorine-based gas with a sufficiently fast etching rate for the photoresist film as the etching gas, the organic underlayer film can be processed by using an oxygen-based gas with a sufficiently fast etching rate for the resist underlayer film as the etching gas, and the substrate can be processed by using a fluorine-based gas with a sufficiently fast etching rate for the organic underlayer film as the etching gas. The substrates and coating methods that can be used in this case are the same as those described above.

[0250] Next, a layer of, for example, a photoresist material (resist film) is formed on the resist underlayer. The resist film can be formed by a well-known method, that is, by coating a coating-type resist material (resist film forming composition) onto the resist underlayer and firing it. The thickness of the resist film is, for example, 10 nm to 10,000 nm, or 100 nm to 2,000 nm, or 200 nm to 1,000 nm, or 30 nm to 200 nm.

[0251] The photoresist material used for the resist film formed on the resist underlayer is not particularly limited as long as it is sensitive to the light used for exposure (e.g., KrF excimer laser, ArF excimer laser, etc.), and both negative-type and positive-type photoresist materials can be used. Examples include a positive-type photoresist material consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, a chemically amplified photoresist material consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, a chemically amplified photoresist material consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist material, an alkali-soluble binder and a photoacid generator, and a chemically amplified photoresist material consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate, a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist material and a photoacid generator. Specific examples of commercially available products include, but are not limited to, APEX-E (manufactured by Cypree), PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), AR2772JN (manufactured by JSR Corporation), and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.). Furthermore, examples of fluorine-containing polymer-based 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 cited.

[0252] Furthermore, instead of a photoresist film, an electron beam lithography resist film (also referred to as an electron beam resist film) or an EUV lithography resist film (also referred to as an EUV resist film) can be used as the resist film formed on the resist underlayer. In other words, the silicon-containing resist underlayer formation composition of the present invention can be used for forming a resist underlayer for electron beam lithography or for forming a resist underlayer for EUV lithography. It is particularly suitable as a resist underlayer formation composition for EUV lithography. For forming electron beam resist films, both negative and positive materials can be used as electron beam resist materials. Specific examples include: chemically amplified resist materials consisting of an acid generator and a binder having a group that decomposes with acid to change the alkali dissolution rate; chemically amplified resist materials consisting of an alkali-soluble binder, an acid generator, and a low-molecular-weight compound that decomposes with acid to change the alkali dissolution rate of the resist material; chemically amplified resist materials consisting of an acid generator, a binder having a group that decomposes with acid to change the alkali dissolution rate, and a low-molecular-weight compound that decomposes with acid to change the alkali dissolution rate of the resist material; non-chemically amplified resist materials consisting of a binder having a group that decomposes with electron beams to change the alkali dissolution rate; and non-chemically amplified resist materials consisting of a binder having a portion that is cut by an electron beam to change the alkali dissolution rate. When using these electron beam resist materials, a resist film pattern can be formed using an electron beam as the irradiation source, similar to when using a photoresist material. Furthermore, methacrylate resin-based resist materials and metal oxide resist materials can be used as EUV resist materials for forming EUV resist films. Examples of metal oxide resist materials include coating compositions containing a metal oxo-hydroxo network having organic ligands via metal-carbon bonds and / or metal-carboxylate bonds, as described in Japanese Patent Publication No. 2019-113855.

[0253] Next, the resist film formed on the upper layer of the resist underlayer is exposed through a predetermined mask (rectil). For exposure, a KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), EUV (wavelength 13.5 nm), electron beam, etc., can be used. After exposure, post-exposure baking can be performed if necessary. Post-exposure baking is carried out under conditions appropriately selected from a heating temperature of 70°C to 150°C and a heating time of 0.3 minutes to 10 minutes.

[0254] Next, development is performed using a developer (for example, an alkaline developer). This removes the photoresist film from the exposed areas, for example, if a positive-type photoresist film is used, and a pattern of the photoresist film is formed. Examples of developer 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 alkaline aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants can be added to these developers. Development conditions are appropriately selected from a temperature of 5 to 50°C and a time of 10 to 600 seconds.

[0255] Furthermore, in this invention, an organic solvent can be used as the developer, and development is performed with the developer (solvent) after exposure. As a result, for example, when a negative-type photoresist film is used, the photoresist film in the unexposed areas is removed, and a pattern of the photoresist film is formed. Examples of developers (organic solvents) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethyl 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-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, propyl lactate Examples include methyl propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc.Furthermore, surfactants and other substances can be added to these developing solutions. For development, the temperature should be between 5°C and 50°C, and the development time should be selected appropriately from 10 seconds to 600 seconds.

[0256] The pattern of the photoresist film (upper layer) formed in this manner is used as a protective layer to remove the resist underlayer film (intermediate layer). Then, the film consisting of the patterned photoresist film and the patterned resist underlayer film (intermediate layer) is used as a protective layer to remove the organic underlayer film (lower layer). Finally, the patterned resist underlayer film (intermediate layer) and the patterned organic underlayer film (lower layer) are used as protective layers to process the substrate.

[0257] The removal (patterning) of the resist underlayer (intermediate layer), which is performed using the pattern of the resist layer (upper layer) as a protective layer, is carried out 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. Furthermore, it is preferable to use halogen-based gases for dry etching of the resist underlayer. In dry etching with halogen-based gases, the resist film (photoresist film), which is basically made of organic material, is difficult to remove. In contrast, the resist underlayer containing many silicon atoms is quickly removed by halogen-based gases. Therefore, the reduction in the thickness of the photoresist film that occurs with dry etching of the resist underlayer can be suppressed. As a result, it becomes possible to use the photoresist film as a thin film. Accordingly, it is preferable to use fluorine-based gases for dry etching of the resist underlayer. Examples of fluorine-based gases include, but are not limited to, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0258] When an organic underlayer film is present between the substrate and the resist underlayer film, the removal (patterning) of the organic underlayer film (underlayer), which is then performed using a protective film consisting of a patterned resist film (upper layer) and a patterned resist underlayer film (intermediate layer), is preferably carried out by dry etching with an oxygen-based gas (oxygen gas, oxygen / carbonyl sulfide (COS) mixed gas, etc.). This is because the resist underlayer film of the present invention, which contains many silicon atoms, is difficult to remove by dry etching with an oxygen-based gas.

[0259] Subsequently, the processing (patterning) of the (semiconductor) substrate, which is carried out using a patterned resist underlayer film (intermediate layer) and optionally a patterned organic underlayer film (underlayer) as protective films, is preferably performed by dry etching with a fluorine-based gas. Examples of fluorinated gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0260] After the removal (patterning) of the organic underlayer film, or after the processing (patterning) of the substrate, the resist underlayer film may be removed. The resist underlayer film can be removed by dry etching or wet etching (wet method). Dry etching of the resist underlayer film is preferably performed using a fluorine-based gas, as mentioned in the patterning section. Examples include, but are not limited to, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2). Examples of chemicals used for wet etching of the resist underlayer include dilute hydrofluoric acid (hydrofluoric acid), 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), all of which are alkaline solutions. In addition to the aforementioned ammonia hydrochloride (SC-1 solution) obtained by mixing ammonia, hydrogen peroxide, and water, other examples of alkaline solutions include 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, mepicato hydroxide, trimethylsulfonium hydroxide, hydrazines, ethylenediamines, or guanidine. These solutions can also be used in combination.

[0261] Furthermore, an organic anti-reflective coating can be formed on top of the resist underlayer before the resist film is formed. There are no particular restrictions on the anti-reflective coating composition used; for example, any composition that has been conventionally used in lithography processes can be arbitrarily selected and used, and the anti-reflective coating can be formed by conventional methods, such as coating with a spinner or coater and firing.

[0262] Furthermore, the substrate on which the silicon-containing resist underlayer film formation composition is applied may have an organic or inorganic anti-reflective coating formed on its surface by CVD or the like, and the resist underlayer film can be formed on top of it. Even when an organic underlayer film is formed on the substrate and then the resist underlayer film of the present invention is formed on top of it, the substrate used may also have an organic or inorganic anti-reflective coating formed on its surface by CVD or the like.

[0263] The resist underlayer formed from the silicon-containing resist underlayer composition may also have absorption properties for certain wavelengths of light used in the lithography process. In such cases, it can function as an anti-reflective film that prevents reflected light from the substrate. Furthermore, the resist underlayer can also be used as a layer to prevent interaction between the substrate and the resist film (photoresist film, etc.), a layer that has the function of preventing adverse effects on the substrate by materials used in the resist film or substances generated during exposure to the resist film, a layer that has the function of preventing the diffusion of substances generated from the substrate into the resist film during heating and firing, and a barrier layer to reduce the poisoning effect of the resist film by the semiconductor substrate dielectric layer.

[0264] The resist underlayer film can be applied to substrates with via holes formed in the dual damascene process and can be used as a hole-filling material (filler) that can completely fill the holes. It can also be used as a planarizing material to flatten the surface of uneven semiconductor substrates. Furthermore, the resist underlayer film of the present invention, in addition to functioning as a hard mask under an EUV resist film, can prevent reflection of undesirable exposure light, such as UV (ultraviolet) light or DUV (deep ultraviolet) light (ArF light, KrF light), from the substrate or interface during EUV exposure (wavelength 13.5 nm), without intermixing with the EUV resist film. Therefore, the silicon-containing resist underlayer film forming composition of the present invention can be suitably used to form an anti-reflective underlayer film for EUV resist films. In other words, it can efficiently prevent reflection as an underlayer for EUV resist films. When used as an EUV resist underlayer film, the process can be carried out in the same way as for a photoresist underlayer film.

[0265] The semiconductor processing substrate comprising the resist underlayer film of the present invention described above and a semiconductor substrate can be suitably used to process a semiconductor substrate. Furthermore, according to a semiconductor device manufacturing method that includes the steps of forming an organic underlayer film, forming a resist underlayer film on the organic underlayer film using the silicon-containing resist underlayer film forming composition of the present invention, and forming a resist film on the silicon resist underlayer film, as described above, highly accurate semiconductor substrate processing can be achieved with good reproducibility, and therefore stable manufacturing of semiconductor devices can be expected. [Examples]

[0266] The present invention will be described in more detail below with reference to synthesis examples and embodiments, but the present invention is not limited to the embodiments described below.

[0267] The apparatus and conditions used for analyzing the physical properties of the sample in the examples are as follows. (1) Molecular weight measurement The molecular weight of the polysiloxane used in this invention is the molecular weight obtained in terms of polystyrene by GPC analysis. GPC measurement conditions can be followed, for example, using a GPC instrument (product name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (product name Shodex® KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, tetrahydrofuran as the eluent (elution solvent), a flow rate of 1.0 mL / min, and polystyrene (manufactured by Showa Denko K.K.) as the standard sample.

[0268] (2) 1 H-NMR The results were evaluated using a JEOL nuclear magnetic resonance spectrometer (1H-NMR, 400 MHz) with d6-acetone as the solvent.

[0269] (3) Residual nitric acid amount The amount of nitric acid remaining in the system was measured using ion chromatography evaluation.

[0270] [1] Synthesis of polymers (hydrolyzed condensates) (Synthesis Example 1) 16.66 g of tetraethoxysilane, 12.87 g of methyltriethoxysilane, 2.43 g of O-(propargyl)-N-(triethoxysilylpropyl)carbamate, and 47.89 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 20.18 g of 0.1 M aqueous nitric acid solution was added dropwise to the resulting mixture while stirring with a magnetic stirrer. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and reacted for 20 hours. Subsequently, the reaction by-products, ethanol and water, were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. The obtained solution was further diluted with propylene glycol monoethyl ether, and the concentration was adjusted so that the solid residue at 140°C was 20% by mass, assuming a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered through a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was 3,000 in polystyrene equivalents according to GPC. 1¹H-NMR revealed that the amount of propylene glycol monoethyl ether capping relative to the Si atoms was 3 mol%. The residual nitric acid content in the polymer solution was 0.07%. [ka]

[0271] (Synthesis Example 2) 15.87 g of tetraethoxysilane, 9.51 g of methyltriethoxysilane, 6.93 g of O-(propargyl)-N-(triethoxysilylpropyl)carbamate, and 48.47 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.22 g of 0.1 M aqueous nitric acid solution was added dropwise to the resulting mixture while stirring with a magnetic stirrer. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and reacted for 20 hours. Subsequently, the reaction by-products, ethanol and water, were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. The obtained solution was further diluted with propylene glycol monoethyl ether, and the concentration was adjusted so that the solid residue at 140°C was 20% by mass, assuming a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered through a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was 3,400 in polystyrene equivalents according to GPC. 1 ¹H-NMR revealed that the amount of propylene glycol monoethyl ether capping relative to the Si atoms was 3 mol%. The residual nitric acid content in the polymer solution was 0.08%. [ka]

[0272] (Synthesis Example 3) 15.9 g of tetraethoxysilane, 10.90 g of methyltriethoxysilane, 3.16 g of diallyl isocyanuratepropyltriethoxysilane, 2.32 g of O-(propargyl)-N-(triethoxysilylpropyl)carbamate, and 48.4 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.3 g of aqueous nitric acid solution (0.1 mol / L) was added dropwise to the resulting mixture while stirring with a magnetic stirrer. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Subsequently, the reaction by-products, ethanol and water, were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was added to the solution, and the concentration was adjusted so that the solvent ratio of propylene glycol monoethyl ether was 100%, resulting in a solid residue of 20% by mass at 140°C. The solution was then filtered through a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was Mw3,200 in polystyrene equivalents according to GPC. 1 ¹H-NMR revealed that the amount of propylene glycol monoethyl ether capping relative to the Si atoms was 2 mol%. The residual nitric acid content in the polymer solution was 0.08%. [ka]

[0273] (Synthesis Example 4) 16.39 g of tetraethoxysilane, 11.22 g of methyltriethoxysilane, 2.07 g of thiocyanate-propyltriethoxysilane, 2.39 g of O-(propargyl)-N-(triethoxysilylpropyl)carbamate, and 48.1 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.8 g of aqueous nitric acid solution (0.1 mol / L) was added dropwise to the resulting mixture while stirring with a magnetic stirrer. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Subsequently, the reaction by-products, ethanol and water, were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was added to the solution, and the concentration was adjusted so that the solvent ratio of propylene glycol monoethyl ether was 100%, resulting in a solid residue of 20% by mass at 140°C. The solution was then filtered through a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was Mw3,000 in polystyrene equivalents according to GPC. 1 ¹H-NMR revealed that the amount of propylene glycol monoethyl ether capping relative to the Si atoms was 3 mol%. The residual nitric acid content in the polymer solution was 0.09%. [ka]

[0274] (Synthesis Example 5) 16.13 g of tetraethoxysilane, 11.04 g of methyltriethoxysilane, 2.67 g of triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane, 2.35 g of O-(propargyl)-N-(triethoxysilylpropyl)carbamate, and 48.3 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.5 g of aqueous nitric acid solution (0.1 mol / L) was added dropwise to the resulting mixture while stirring with a magnetic stirrer. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Subsequently, the reaction by-products, ethanol and water, were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was added to the solution, and the concentration was adjusted so that the solvent ratio of propylene glycol monoethyl ether was 100%, resulting in a solid residue of 20% by mass at 140°C. The solution was then filtered through a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was Mw3,500 in polystyrene equivalents according to GPC. 1 ¹H-NMR revealed that the amount of propylene glycol monoethyl ether capping relative to the Si atoms was 4 mol%. The residual nitric acid content in the polymer solution was 0.08%. [ka]

[0275] (Synthesis Example 6) 16.4 g of tetraethoxysilane, 11.23 g of methyltriethoxysilane, 2.02 g of bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane, 2.39 g of O-(propargyl)-N-(triethoxysilylpropyl)carbamate, and 48.1 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 19.9 g of aqueous nitric acid solution (0.1 mol / L) was added dropwise to the resulting mixed solution while stirring with a magnetic stirrer. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Subsequently, the reaction by-products, ethanol and water, were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Furthermore, propylene glycol monoethyl ether was added, and the concentration was adjusted so that the solid residue at 140°C was 20% by mass, based on a solvent ratio of 100% propylene glycol monoethyl ether. The mixture was then filtered through a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was Mw2,800 in polystyrene equivalents according to GPC. 1 ¹H-NMR revealed that the amount of propylene glycol monoethyl ether capping relative to the Si atoms was 3 mol%. The residual nitric acid content in the polymer solution was 0.09%. [ka]

[0276] (Synthesis Example 7) 16.6 g of tetraethoxysilane, 12.53 g of methyltriethoxysilane, 2.42 g of O-(propargyl)-N-(triethoxysilylpropyl)carbamate, and 47.9 g of propylene glycol monoethyl ether were placed in a 300 mL flask. The resulting mixed solution was stirred with a magnetic stirrer, and 0.36 g of dimethylaminopropyltrimethoxysilane and 20.1 g of aqueous nitric acid solution (0.2 mol / L) were added dropwise. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Subsequently, the reaction by-products, ethanol, methanol, and water, were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was added to the solution, and the concentration was adjusted so that the solvent ratio of propylene glycol monoethyl ether was 100%, resulting in a solid residue of 20% by mass at 140°C. The solution was then filtered through a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was Mw3,100 in polystyrene equivalents according to GPC. 1 ¹H-NMR revealed that the amount of propylene glycol monoethyl ether capping relative to the Si atoms was 3 mol%. The residual nitric acid content in the polymer solution was 0.17%. [ka]

[0277] (Comparative Synthesis Example 1) 23.35 g of tetraethoxysilane, 8.57 g of methyltriethoxysilane, and 47.9 g of propylene glycol monoethyl ether were placed in a 300 mL flask, and 20.2 g of aqueous nitric acid solution (0.1 mol / L) was added dropwise to the resulting mixture while stirring with a magnetic stirrer. After dropwise addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Subsequently, the reaction by-products, ethanol and water, were removed by vacuum distillation, and the solution was concentrated to obtain a hydrolysis condensate (polymer) solution. Propylene glycol monoethyl ether was added to the solution, and the concentration was adjusted so that the solvent ratio of propylene glycol monoethyl ether was 100%, resulting in a solid residue of 20% by mass at 140°C. The solution was then filtered through a nylon filter (pore size 0.1 μm). The obtained polymer contained a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight was Mw3,500 in polystyrene equivalents according to GPC. 1 ¹H-NMR revealed that the amount of propylene glycol monoethyl ether capping relative to the Si atoms was 4 mol%. The residual nitric acid content in the polymer solution was 0.08%. [ka]

[0278] [2] Preparation of the composition to be applied to the resist pattern The polysiloxane (polymer), stabilizer (additive 1), curing catalyst (additive 2), and solvent obtained in the above synthesis example were mixed in the proportions shown in Table 1, and the mixtures were filtered through a 0.1 μm fluororesin filter to prepare compositions for coating the resist pattern. The amounts of each additive in Table 1 are shown in parts by mass. Note that while the hydrolysis condensate (polymer) was prepared as a solution containing the condensate obtained in the synthesis example, the polymer addition ratio in Table 1 indicates the amount of polymer itself added, not the amount of polymer solution added.

[0279] The abbreviations in Table 1 are as follows: <Solvent> ·DIW: Ultrapure water • PGEE: Propylene glycol monoethyl ether • PGME: Propylene glycol monomethyl ether <Additive 1> • MA: Maleic acid <Additive 2> TPSNO3: Triphenylsulfonium nitrate TPSML: Triphenylsulfonium maleate • TPSTfAc: Triphenylsulfonium trifluoroacetate • IMTEOS: Triethoxysilylpropyl-4,5-dihydroimidazole TPSAc: Triphenylsulfonium acetate BTEAC: Benzyltriethylammonium chloride salt

[0280] [Table 1] *Examples 1-7 and Comparative Example 1 further contain nitric acid, which is present in the polymer solutions prepared in Synthesis Examples 1-7 and Comparative Synthesis Example 1, respectively.

[0281] [3] Preparation of compositions for forming an organic resist underlayer film Under nitrogen, 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.) were added to a 100 ml four-necked flask. 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was then added and the mixture was stirred. The temperature was raised to 100°C to dissolve the mixture and begin polymerization. After 24 hours, the mixture was allowed to cool to 60°C. The cooled reaction mixture was diluted with chloroform (34 g, manufactured by Kanto Chemical Co., Ltd.), and the diluted mixture was added to methanol (168 g, manufactured by Kanto Chemical Co., Ltd.) to precipitate. The obtained precipitate was filtered and recovered, and the recovered solid was dried in a vacuum dryer at 80°C for 24 hours to obtain 9.37 g of the target polymer represented by formula (X) (hereinafter abbreviated as PCzFL). Note that PCzFL 1 The results of the 1H-NMR measurement were as follows: 1H-NMR(400MHz,DMSO-d6):δ7.03-7.55(br,12H),δ7.61-8.10(br,4H),δ11.18(br,1H) Furthermore, the weight-average molecular weight Mw of PCzFL was 2,800 when converted to polystyrene using GPC, and the polydispersity Mw / Mn was 1.77. [ka]

[0282] 20 g of PCzFL, 3.0 g of tetramethoxymethyl glycoluryl (manufactured by Nippon Scitec Industries Co., Ltd. (formerly Mitsui Scitec Co., Ltd.), trade name Powderlink 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 the mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10 μm, and then filtered again using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming an organic resist underlayer film for use in multilayer lithography processes.

[0283] [4] Solvent resistance and developer resistance tests The compositions prepared in Examples 1-7 and Comparative Example 1 were each coated onto a silicon wafer using a spinner. The wafers were heated on a hot plate at 215°C for 1 minute to form a Si-containing resist underlayer film, and the thickness of the resulting underlayer film was measured. Subsequently, a mixed solvent (7 / 3(V / V)) of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate was applied to each Si-containing resist underlayer film and spin-dried. The film thickness of the underlayer film after application was measured, and the percentage change in film thickness after application of the mixed solvent was calculated, with the film thickness before application of the mixed solvent set as the baseline (100%). Films with a film thickness change of 1% or less before and after application of the mixed solvent were evaluated as "good," and those with a film thickness change of more than 1% were evaluated as "not cured." Similarly, an alkaline developer (2.38% aqueous solution of tetramethylammonium hydroxide (TMAH)) was applied to each Si-containing resist underlayer film fabricated on a silicon wafer using the same method, and the film was spin-dried. The film thickness of the underlayer film after application was measured, and the percentage change in film thickness after application was calculated, with the film thickness before application of the developer set as the baseline (100%). Films with a film thickness change of 1% or less before and after application of the developer were classified as "good," and those with a film thickness change of more than 1% were classified as "not cured." The results obtained are shown in Table 2.

[0284] [Table 2]

[0285] [5] Formation of resist pattern by EUV exposure: Positive solvent development The above-mentioned organic resist underlayer film formation composition was applied onto a silicon wafer using a spinner and baked on a hot plate at 215°C for 60 seconds to obtain an organic underlayer film (layer A) with a thickness of 90 nm. The composition obtained in Example 1 was then spin-coated onto the resist, and the film was heated at 215°C for 1 minute to form a resist underlayer (layer B) (20 nm). Furthermore, an EUV resist solution (methacrylate resin-based resist) was spin-coated onto the surface and heated at 110°C for 1 minute to form an EUV resist film (C layer). Subsequently, the surface was exposed using an ASML EUV exposure system (NXE3400) under the conditions of NA=0.33, σ=0.63 / 0.84, and Quadropole. After exposure, post-exposure heating (PEB, 105°C for 1 minute) was performed, followed by cooling to room temperature on a cooling plate. Development was then carried out using TMAH 2.38% developer for 30 seconds, followed by rinsing to form a resist pattern. Using a similar procedure, resist patterns were formed using the compositions obtained in Examples 2-7 and Comparative Example 1. For each obtained pattern, the feasibility of forming a 28nm pitch, 12nm line pattern was evaluated by confirming the pattern shape through cross-sectional observation of the pattern. In observing the pattern shape, a state where the shape was between the footing and undercut, and where there was no significant residue in the space area, was evaluated as "good," while an undesirable state where the resist pattern was tilted was evaluated as "tilted." The results obtained are shown in Table 3.

[0286] [Table 3]

Claims

1. [A] Components: Carbon-carbon triple bond-containing polysiloxane, and [C] Component: Solvent It contains, The carbon-carbon triple bond-containing polysiloxane comprises structural units derived from hydrolyzable silane (A) having carbon-carbon triple bonds, The hydrolyzable silane (A) is a compound represented by the following formula (A-1), 【Chemistry 1】 (In equation (A-1), a represents an integer from 1 to 3.) b represents an integer between 0 and 2. a + b represents an integer between 1 and 3. R1 represents an organic group having a carbon-carbon triple bond and an oxygen atom and / or a nitrogen atom, and which may also have ionic bonds. R2 represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or 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. X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. If R1, R2, and X are multiple, these multiple R1, R2, and X may be the same or different. A silicon-containing resist underlayer film forming composition wherein R1 in formula (A-1) is represented by the following formula (A-2a). 【Chemistry 2】 (In formula (A-2a), R 11 represents a divalent organic group which may have an ionic bond.) R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have substituents, or an aryl group which may have substituents. * indicates a bonding operation.

2. [A'] Ingredients: Polysiloxane, [B] Component: Hydrolyzable silane (A) having a carbon-carbon triple bond, and [C] Component: Solvent It contains, The hydrolyzable silane (A) is a compound represented by the following formula (A-1), 【Transformation 3】 (In equation (A-1), a represents an integer from 1 to 3.) b represents an integer between 0 and 2. a + b represents an integer between 1 and 3. R1 represents an organic group having a carbon-carbon triple bond and an oxygen atom and / or a nitrogen atom, and which may also have ionic bonds. R2 represents an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted halogenated alkyl group, an optionally substituted halogenated aryl group, an optionally substituted halogenated aralkyl group, an optionally substituted alkoxyalkyl group, an optionally substituted alkoxyaryl group, an optionally substituted alkoxyaralkyl group, or an optionally substituted alkenyl group; or 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. X represents an alkoxy group, an aralkyloxy group, an acyloxy group, or a halogen atom. If R1, R2, and X are multiple, these multiple R1, R2, and X may be the same or different. A silicon-containing resist underlayer film forming composition wherein R1 in formula (A-1) is represented by the following formula (A-2a). 【Chemistry 4】 (In formula (A-2a), R 11 represents a divalent organic group which may have an ionic bond.) R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have substituents, or an aryl group which may have substituents. * indicates a bonding operation.

3. The silicon-containing resist underlayer film forming composition according to claim 1, wherein the carbon-carbon triple bond-containing polysiloxane, which is component [A], is a polysiloxane modified product in which a portion of the silanol groups are alcohol-modified or acetal-protected.

4. The silicon-containing resist underlayer film forming composition according to claim 2, wherein the polysiloxane, which is component [A'], is a polysiloxane modified product in which a portion of the silanol groups are alcohol-modified or acetal-protected.

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

6. The silicon-containing resist underlayer film forming composition according to claim 5, wherein the [C] component contains a propylene glycol monoalkyl ether.

7. [D] Component: The silicon-containing resist underlayer film forming composition according to claim 1 or 2, further comprising a curing catalyst.

8. [E] Component: The silicon-containing resist underlayer film forming composition according to claim 1 or 2, further comprising nitric acid.

9. The silicon-containing resist underlayer film forming composition according to claim 1 or 2, wherein the [C] component contains water.

10. A silicon-containing resist underlayer forming composition according to claim 1 or 2, for forming a resist underlayer for EUV lithography.

11. A silicon-containing resist underlayer film, which is a cured product of the silicon-containing resist underlayer film forming composition according to claim 1 or 2.

12. Semiconductor substrate and The silicon-containing resist underlayer film according to claim 11, A semiconductor processing substrate equipped with the following features.

13. A process of forming an organic underlayer film on a substrate, A step of forming a resist underlayer on the organic underlayer using the silicon-containing resist underlayer forming composition according to claim 1 or 2, The steps include forming a resist film on the aforementioned resist underlayer film, A method for manufacturing semiconductor devices, including

14. The resist film is formed from an EUV lithography resist. A method for manufacturing a semiconductor device according to claim 13.

15. In the process of forming the resist underlayer film, a silicon-containing resist underlayer film formation composition filtered through a nylon filter is used. A method for manufacturing a semiconductor device according to claim 13.

16. A process of forming an organic underlayer film on a semiconductor substrate, The steps include applying the silicon-containing resist underlayer film forming composition according to claim 1 or 2 onto the organic underlayer film and firing it to form a resist underlayer film, The steps include applying a resist film-forming composition onto the resist underlayer film to form a resist 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, A step of etching the organic underlayer film using the patterned resist underlayer film as a mask, A pattern formation method, including the following.

17. After the step of etching the organic underlayer film, a step of removing the resist underlayer film by a wet method using a chemical solution, The pattern forming method according to claim 16, further comprising:

18. The resist film is formed from an EUV lithography resist. The pattern forming method according to claim 16.

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