Composition for forming silicon-containing photoresist underlayer film, and silicon-containing photoresist underlayer film

Abstract

The present invention provides a composition for forming a silicon-containing photoresist underlayer film, which contains: [A] component: polysiloxane containing carbon-carbon triple bonds and [C] component: solvent.

Description

Technical Field

[0001] This invention relates to a composition for forming a silicon-containing photoresist underlayer film and a silicon-containing photoresist underlayer film. Prior Technology

[0002] Historically, in the manufacturing of semiconductor devices, microfabrication has been achieved using photoresist lithography. Microfabrication is a process in which a thin film of photoresist is formed on a semiconductor substrate such as a silicon wafer. An active light source, such as ultraviolet light, is then irradiated onto the film through a photomask pattern depicting a semiconductor element. The resulting photoresist pattern is then used as a protective film to etch the substrate, thereby forming fine irregularities on the substrate surface corresponding to the pattern. In recent years, the increasing density of semiconductor devices has led to a trend towards shorter wavelengths of active light, shifting from KrF excimer lasers (248nm) to ArF excimer lasers (193nm). With the shortening of active light wavelengths, the reflection of active light from the semiconductor substrate has become a major problem. Therefore, a method has been widely adopted that involves placing a bottom anti-reflective coating (BARC) between the photoresist and the substrate.

[0003] The underlying film between the semiconductor substrate and the photoresist is currently a film known as a hard mask, containing metallic elements such as silicon or titanium. In this case, because the photoresist and the hard mask differ greatly in their composition, the removal speed by dry etching depends primarily on the type of gas used in the dry etching process. Furthermore, by appropriately selecting the type of gas, the hard mask can be removed by dry etching without a significant reduction in the thickness of the photoresist film. As a result, in recent years, in the manufacture of semiconductor devices, to achieve various effects, primarily anti-reflection, the underlying photoresist film has increasingly been placed between the semiconductor substrate and the photoresist.

[0004] Although compositions for photoresist underlayers have been studied to date, the diverse range of required properties necessitates the development of novel materials for photoresist underlayers. For example, a composition for forming a coating-type BPSG (borophosphorus glass) film containing a structure based on a specific silicic acid framework has been disclosed, with the aim of forming a film capable of wet etching (Patent Document 1); and a composition for forming a silicon-containing photoresist underlayer containing a carbonyl structure has been disclosed, with the aim of removing masking residues after photolithography using a chemical solution (Patent Document 2). [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2016-74774 [Patent Document 2] International Publication No. 2018 / 181989 Summary of the Invention

[0006] [The technical problem that the invention aims to solve]

[0007] With the further miniaturization of photoresist patterns in cutting-edge semiconductor devices in recent years, there is a need for a photoresist underlayer film that can prevent the photoresist pattern from collapsing.

[0008] The present invention is made in view of the following circumstances, and its object is to provide a silicon-containing photoresist underlayer film that can prevent the collapse of fine photoresist patterns, thereby improving the resolution of the photoresist patterns; and a silicon-containing photoresist underlayer film forming composition capable of forming the silicon-containing photoresist underlayer film. [Technical means]

[0009] After conducting in-depth research to solve the aforementioned problems, the inventors discovered that the aforementioned problems could be solved, thus completing the present invention with the following key points.

[0010] That is, the present invention includes the following. [1] A composition for forming a silicon-containing photoresist underlayer film, comprising: [A] Ingredients: Polysiloxane containing carbon-carbon triple bonds, and... [C] Ingredients: Solvent. [2] The composition for forming a silicon-containing photoresist underlayer film as described in item [1], wherein the aforementioned polysiloxane containing carbon-carbon triple bonds contains structural units derived from hydrolyzable silane (A) having carbon-carbon triple bonds. [3] A composition for forming a silicon-containing photoresist underlayer film, comprising: [A'] Ingredients: Polysiloxane, [B] Components: Hydrolyzable silane with carbon-carbon triple bonds (A), and [C] Ingredients: Solvent. [4] The composition for forming a silicon-containing photoresist underlayer film as described in item [2] or [3], wherein the aforementioned hydrolyzable silane (A) is a compound represented by the following formula (A-1); [Chemistry 1] (In formula (A-1), a represents an integer from 1 to 3;) b represents an integer between 0 and 2; a+b represents an integer from 1 to 3; R 1 represents an organic group that has a carbon-carbon triple bond and may also have ionic bonds; R 2 represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted halogenated alkyl group, a substituted halogenated aryl group, a substituted halogenated aralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or represents an organogroup having an epoxy group, an organogroup having an acrylonitrile group, an organogroup having a methacrylonitrile group, an organogroup having a mercapto group, an organogroup having an amino group, an organogroup having an alkoxy group, an organogroup having a sulfonylurea group, or an organogroup having a cyano group, or a combination of two or more of these; X represents an alkoxy, arylalkoxy, acetoxy, or halogen atom; When there are multiple R1, R2, and X, the multiple R1, R2, and X can be the same or different. [5] The composition for forming a silicon-containing photoresist underlayer film as described in item [4], wherein R1 in the aforementioned formula (A-1) is represented by the following formula (A-2a); [Chemistry 2] (In formula (A-2a), R 11 represents a single bond or a divalent organic group that may have an ionic bond;) R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may have substituents, or an aryl group that may have substituents; * indicates a bond. [6] The silicon-containing photoresist underlayer composition as described in item [1] or [2], wherein the polysiloxane containing carbon-carbon triple bonds of the aforementioned component [A] is a polysiloxane modified by alcohol or protected by acetal, which is a part of the silanol group. [7] The composition for forming a silicon-containing photoresist underlayer film as described in item [3], wherein the polysiloxane of the aforementioned [A'] component is a polysiloxane modified by alcohol or protected by acetal, which is a part of the silanol group. [8] A composition for forming a silicon-containing photoresist underlayer as described in any of items [1] to [7], wherein the aforementioned component [C] contains an alcohol solvent. [9] The composition for forming a silicon-containing photoresist underlayer film as described in item [8], wherein the aforementioned component [C] contains a propylene glycol monoalkyl ether.

[10] The silicon-containing photoresist underlayer film forming composition as described in any of items [1] to [9], wherein the aforementioned silicon-containing photoresist underlayer film forming composition further contains component [D]: hardening catalyst.

[11] The silicon-containing composition for forming a photoresist underlayer as described in any of items [1] to

[10] , wherein the aforementioned silicon-containing composition for forming a photoresist underlayer further contains [E] component: nitric acid.

[12] The silicon-containing photoresist underlayer film forming composition as described in any of items [1] to

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

[13] The silicon-containing photoresist underlayer composition as described in any of items [1] to

[12] , wherein the aforementioned silicon-containing photoresist underlayer composition is used to form a photoresist underlayer for EUV lithography.

[14] A silicon-containing photoresist underlayer film, which is a cured form of the composition for forming a silicon-containing photoresist underlayer film as described in any one of items [1] to

[13] .

[15] A semiconductor processing substrate comprising: Semiconductor substrates, and Silicon-containing photoresist underlayer as described in item

[14] .

[16] A method for manufacturing a semiconductor device, comprising: The step of forming an organic lower layer film on a substrate; The step of forming a photoresist underlayer film on top of the aforementioned organic underlayer film using a silicon-containing photoresist underlayer film forming composition as described in any one of items [1] to

[13] ; and The step of forming a photoresist film on the aforementioned photoresist underlayer film.

[17] The method for manufacturing a semiconductor device as described in item

[16] , wherein, The aforementioned photoresist film is formed from EUV lithography photoresist.

[18] A method for manufacturing a semiconductor device as described in item

[16] or

[17] , wherein, In the aforementioned step of forming the photoresist underlayer film, a silicon-containing composition for forming the photoresist underlayer film, filtered through a nylon filter, is used.

[19] A pattern forming method, comprising: The step of forming an organic lower layer film on a semiconductor substrate; The step of coating a silicon-containing photoresist underlayer composition as described in any one of items [1] to

[13] onto the aforementioned organic underlayer film and then firing it to form a photoresist underlayer film; The step of forming a photoresist film by coating a composition for forming a photoresist film on the aforementioned photoresist lower layer film; The steps involve exposing and developing the aforementioned photoresist film to obtain a photoresist pattern. The steps of using the aforementioned photoresist pattern as a mask and etching the aforementioned photoresist underlayer film; and The steps involve using the patterned photoresist underlayer as a mask and etching the aforementioned organic underlayer.

[20] The pattern forming method as described in item

[19] , wherein the aforementioned pattern forming method further includes: After etching the aforementioned organic underlayer film, the aforementioned photoresist underlayer film is removed by a wet method using a chemical solution.

[21] The pattern forming method as described in item

[19] or

[20] , wherein the aforementioned photoresist film is formed from EUV lithography photoresist. [Effects of the Invention]

[0011] According to the present invention, a silicon-containing photoresist underlayer film is provided, which can prevent the collapse of fine photoresist patterns, thereby improving the resolution of the photoresist patterns; and a silicon-containing photoresist underlayer film forming composition capable of forming the silicon-containing photoresist underlayer film. Implementation

[0012] (Composition for forming silicon-containing photoresist underlayer film) <First Implementation Mode> The first embodiment of the composition for forming a silicon-containing photoresist underlayer film of the present invention contains a polysiloxane as component [A] and a solvent as component [C], and further contains other components as needed. Polysiloxane, as component [A], has carbon-carbon triple bonds.

[0013] The polysiloxane containing carbon-carbon triple bonds as component [A] (hereinafter sometimes referred to as "[A] polysiloxane") ideally contains structural units derived from hydrolyzable silane (A) with carbon-carbon triple bonds.

[0014] <Second Implementation Mode> The second embodiment of the composition for forming a silicon-containing photoresist underlayer film 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.

[0015] The inventors conducted the following research. The silicon-containing photoresist underlayer film formed by the composition for forming the silicon-containing photoresist underlayer film of the present invention has carbon-carbon triple bonds, thereby preventing the collapse of fine photoresist patterns and improving the resolution of the photoresist patterns. The carbon-carbon triple bonds react with polar functional groups in the photoresist under EUV or other light irradiation, resulting in cross-linking and increasing the cross-linking density of the silicon-containing photoresist underlayer film. This prevents the collapse of fine photoresist patterns and, consequently, improves the resolution of the photoresist patterns.

[0016] <Hydrolyzable silanes with carbon-carbon triple bonds (A)> Hydrolyzable silane (A) has carbon-carbon triple bonds. In other words, hydrolyzable silane (A) has a structure represented by the following formula (AA). Hydrolyzable silanes (A) with carbon-carbon triple bonds (hereinafter sometimes referred to as "hydrolyzable silanes (A)") may have more than two carbon-carbon triple bonds. In other words, hydrolyzable silanes (A) may have more than two structures represented by the following formula (AA). [Chemistry 3] (In structure (AA), * represents a bond. Also, the bond on one side can bond with a hydrogen atom.) In this case, two or more structures represented by formula (AA) can each be bonded to a linker that is bonded to a silicon atom, and two or more structures represented by formula (AA) can also be bonded to silicon atoms directly or through different linkers. Linking groups, such as organic groups. Linking groups can have ionic bonds. When linking groups have ionic bonds, they can have ionic bonds in the atomic rows connecting the structure represented by formula (AA) and silicon atoms, or they can have ionic bonds in the atomic rows branching from the atomic rows connecting the structure represented by formula (AA) and silicon atoms. There is no particular limitation on the number of carbon atoms in the linker group, but the ideal number of carbon atoms in the linker group is 1 to 30, and even more ideally it is 1 to 20. Linking groups typically contain hydrogen atoms. Linking groups can also contain oxygen or nitrogen atoms.

[0017] The ideal hydrolyzable silane (A) with carbon-carbon triple bonds is represented by the following formula (A-1).

[0018] [Chemistry 4] (In formula (A-1), a represents an integer from 1 to 3.) b represents an integer between 0 and 2. a+b represents an integer from 1 to 3. R 1 represents an organic group that has a carbon-carbon triple bond and may also have ionic bonds. R 2 represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted halogenated alkyl group, a substituted halogenated aryl group, a substituted halogenated aralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or an organogroup having an epoxy group, an organogroup having an acrylonitrile group, an organogroup having a methacrylonitrile group, an organogroup having a mercapto group, an organogroup having an amino group, an organogroup having an alkoxy group, an organogroup having a sulfonylurea group, or an organogroup having a cyano group, or a combination of two or more of these. X represents an alkoxy, arylalkoxy, acetoxy, or halogen atom. When there are multiple instances of R1, R2, and X, these multiple instances of R1, R2, and X can be the same or different.

[0019] <<R 1 in equation (A-1)>> R1 can have one or more carbon-carbon triple bonds. There is no particular limitation on the number of carbon atoms in R1, but the ideal number of carbon atoms in R1 is 2 to 30, and even more ideally it is 2 to 20. R1 typically contains a hydrogen atom. In addition to a carbon-carbon triple bond and a hydrogen atom, R1 can also contain an oxygen atom or a nitrogen atom. R1 can have ionic bonds. When R1 has ionic bonds, it can be in the atomic column connecting carbon-carbon triple bonds and silicon atoms, or in the atomic column branching from the atomic column connecting carbon-carbon triple bonds and silicon atoms.

[0020] The R1 ideal system of equation (A-1) is represented by the following equation (A-2a).

[0021] [Chemistry 5] In formula (A-2a), R 11 represents a single bond or a divalent organic group that may have an ionic bond. R 12 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may have substituents, or an aryl group that may have substituents. * indicates a bond.

[0022] When R11 is a divalent organic group that can have ionic bonds, there is no particular limitation on the number of carbon atoms in R11. Ideally, the number of carbon atoms in R11 is 1 to 25, and more ideally, it is 1 to 15.

[0023] R 12 may contain alkyl groups having 1 to 6 carbon atoms, for example, alkyl groups having 1 to 6 carbon atoms. Alkyl groups having 1 to 6 carbon atoms, examples of which include: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl- Cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl 1,1,2-trimethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl Methyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, etc. Alkyl groups having 1 to 6 carbon atoms can be included, for example: hydroxyl, halogen atom, carboxyl, nitro, cyano, methylenedioxy, acetoxy, methylthio, amino, alkoxy with 1 to 6 carbon atoms, etc. In this invention, halogen atoms may include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The number of such substituents may be one or more. Furthermore, in this specification, "iso" means "iso", "second level" means "sec", and "third level" means "tert".

[0024] The aryl group may be a substituent, such as any of the following: phenyl, a monovalent group derived from a condensed ring aromatic hydrocarbon compound by removing a hydrogen atom, and a monovalent group derived from a ring-linked aromatic hydrocarbon compound by removing a hydrogen atom; the number of carbon atoms is not particularly limited, but ideally is 40 or less, more ideally is 30 or less, and even more ideally is 20 or less. For example, aryl groups can be listed as having 6 to 20 carbon atoms, such as: phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-conjugated tetraphenyl, 2-conjugated tetraphenyl, 5-conjugated tetraphenyl, 2-chrysenyl group, 1-pyrene, 2-pyrene, conjugated pentaphenyl, benzo[a]pyrene, biphenyltriphenyl; biphenyl-2-yl (o-biphenyl), biphenyl-3-yl (meta-biphenyl), biphenyl-4-yl (p-biphenyl), p-triphenyl-4-yl, meta-triphenyl-4-yl, o-triphenyl-4-yl, 1,1'-binaphth-2-yl, 2,2'-binaphth-1-yl, etc., but are not limited to these. Substituents that may be aryl groups include, for example: hydroxyl, halogen atom, carboxyl, nitro, cyano, methylenedioxy, acetoxy, methylthio, amino, alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, etc. The number of such substituents may be one or more.

[0025] In addition to carbon-carbon triple bonds, R1 can have hydrogen atoms, oxygen atoms, or nitrogen atoms. R1 can have ionic bonds. When R1 has ionic bonds, it can have ionic bonds in the atomic column connecting carbon-carbon triple bonds and silicon atoms, or it can have nitro groups in the atomic column branching from the atomic column connecting carbon-carbon triple bonds and silicon atoms.

[0026] <<<R 11> >> R 11 is ideally a single bond, or any of the divalent organic groups represented by the following formulas (A-2-1) to (A-2-6). [Chemistry 6] [Chemistry 7] (In formula (A-2-1), R 21 represents an alkyl group with 1 to 6 carbon atoms.) In formula (A-2-2), R 31 represents an alkyl group having 1 to 6 carbon atoms. R 32 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 33 represents a single bond or an alkyl group having 1 to 6 carbon atoms. In formula (A-2-3), R 41 represents an alkyl group with 1 to 6 carbon atoms. R 42 represents a single bond or an alkyl group with 1 to 6 carbon atoms. In formula (A-2-4), R 51 represents an alkyl group with 1 to 6 carbon atoms. R 52 represents a single bond or an alkyl group with 1 to 6 carbon atoms. In formula (A-2-5), R 61 represents an alkyl group having 1 to 6 carbon atoms. R 62 and R 63 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 64 represents a single bond or an alkyl group having 1 to 6 carbon atoms. In formula (A-2-6), R 71 represents an alkyl group with 1 to 6 carbon atoms. R 72 represents a single bond or an alkyl group with 1 to 6 carbon atoms. In equations (A-2-1) to (A-2-6), *1 represents a bond bonded to Si. *2 represents a bond bonded to carbon atoms forming a carbon-carbon triple bond. *3 represents a bond bonded to the carbon atom shown in *4 or the carbon atom shown in *5.

[0027] Furthermore, in the composition for forming a silicon-containing photoresist underlayer film and in the photoresist underlayer film, the amine group (-N(R 32)-) in formula (A-2-2) can be cationized. For example, when nitric acid is added to the composition for forming a silicon-containing photoresist underlayer film, the amine group (-N(R 32)-) in formula (A-2-2) can be cationized to form a nitrate.

[0028] In R 21, R 31, R 33, R 41, R 42, R 51, R 52, R 61, R 64, R 71, and R 72, the alkyl groups having 1 to 6 carbon atoms can be linear or branched. Examples of linear alkyl groups having 1 to 6 carbon atoms include methylene, ethyl, trimethylene, tetramethylene, pentamethylene, and hexamethylene. Among these, methylene, ethyl, trimethylene, and tetramethylene are ideal.

[0029] In R 32, R 62, and R 63, the alkyl groups with 1 to 4 carbon atoms can be straight-chain or branched. Examples of alkyl groups with 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, and tertiary butyl. R 32, R 62, and R 63 are ideally represented by hydrogen atoms, methyl groups, and ethyl groups.

[0030] <<R 2 in equation (A-1)>> Alkyl groups can be straight-chain, branched, or cyclic, and there is no particular limitation on the number of carbon atoms, but ideally less than 40, more ideally less than 30, even more ideally less than 20, and still even more ideally less than 10. Specific examples of alkyl groups, whether straight-chain or branched, include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-... Pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, and 1-ethyl-2-methyl-n-propyl, etc.

[0031] Specific examples of cyclic alkyl groups include: cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl- Cycloalkyl groups such as cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl; and cross-linked cycloalkyl groups such as dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, and dicyclodecyl.

[0032] The aryl group can be any of the following: phenyl, a monovalent group derived from a condensed ring aromatic hydrocarbon compound by removing a hydrogen atom, and a monovalent group derived from a ring-linked aromatic hydrocarbon compound by removing a hydrogen atom; the number of carbon atoms is not particularly limited, but ideally it is 40 or less, more ideally 30 or less, and even more ideally 20 or less. For example, aryl groups can be listed as having 6 to 20 carbon atoms, such as: phenyl, 1-naphthyl, 2-naphthyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-conjugated tetraphenyl, 2-conjugated tetraphenyl, 5-conjugated tetraphenyl, 2-chrysenyl group, 1-pyrene, 2-pyrene, conjugated pentaphenyl, benzo[a]pyrene, biphenyltriphenyl; biphenyl-2-yl (o-biphenyl), biphenyl-3-yl (meta-biphenyl), biphenyl-4-yl (p-biphenyl), p-triphenyl-4-yl, meta-triphenyl-4-yl, o-triphenyl-4-yl, 1,1'-binaphth-2-yl, 2,2'-binaphth-1-yl, etc., but are not limited to these.

[0033] Aryl alkyl groups are alkyl groups substituted with aryl groups. Specific examples of such aryl and alkyl groups can be given as described above. There is no particular limitation on the number of carbon atoms in aryl alkyl groups, but ideally it is 40 or less, more ideally 30 or less, and even more ideally 20 or less. Specific examples of aralkyl groups include: phenylmethyl (benzyl), 2-phenylethyl, 3-phenyl-n-propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 6-phenyl-n-hexyl, 7-phenyl-n-heptyl, 8-phenyl-n-octyl, 9-phenyl-n-nonyl, 10-phenyl-n-decyl, etc., but are not limited to these.

[0034] Halogenated alkyl, halogenated aryl, and halogenated aralkyl are alkyl, aryl, and aralkyl groups respectively substituted with one or more halogen atoms, and specific examples of such alkyl, aryl, and aralkyl groups can be given as the examples described above. Halogen atoms can be listed as: fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0035] There is no particular limitation on the number of carbon atoms in alkyl halides, but ideally it is 40 or less, more ideally it is 30 or less, even more ideally it is 20 or less, and even more ideally it is 10 or less. Specific examples of alkyl halides include: monofluoromethyl, difluoromethyl, trifluoromethyl, bromodifluoromethyl, 2-chloroethyl, 2-bromoethyl, 1,1-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, pentafluoroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, 1,1,1,3,3,3-hexafluoropropyl-2-yl, 3-bromo-2-methylpropyl, 4-bromobutyl, perfluoropentyl, etc., but are not limited to these.

[0036] There is no particular limitation on the number of carbon atoms in aryl halogenated compounds, but ideally it is less than 40, more ideally less than 30, and even more ideally less than 20. Specific examples of halogenated aryl groups include: 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,4,5-tetrafluorophenyl, 2,3,4,6-tetrafluorophenyl, 2,3,5,6-tetrafluorophenyl, pentafluorophenyl, 2-fluoro-1-naphthyl, 3-fluoro-1-naphthyl 4-Fluoro-1-naphthyl, 6-Fluoro-1-naphthyl, 7-Fluoro-1-naphthyl, 8-Fluoro-1-naphthyl, 4,5-Difluoro-1-naphthyl, 5,7-Difluoro-1-naphthyl, 5,8-Difluoro-1-naphthyl, 5,6,7,8-Tetrafluoro-1-naphthyl, Heptafluoro-1-naphthyl, 1-Fluoro-2-naphthyl, 5-Fluoro-2-naphthyl, 6-Fluoro-2-naphthyl, 7-Fluoro-2-naphthyl, 5,7-Difluoro-2-naphthyl, Heptafluoro-2-naphthyl, etc.; in addition, groups in which the fluorine atom (fluorine group) is arbitrarily replaced by a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group) can be listed, but are not limited to these groups.

[0037] There is no particular limitation on the number of carbon atoms in aralkyl halides, but ideally it is 40 or less, more ideally it is 30 or less, and even more ideally it is 20 or less. Specific examples of aralkyl halides include: 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2,3-difluorobenzyl, 2,4-difluorobenzyl, 2,5-difluorobenzyl, 2,6-difluorobenzyl, 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2,3,4-trifluorobenzyl, 2,3,5-trifluorobenzyl, 2,3,6-trifluorobenzyl, 2,4,5-trifluorobenzyl, 2,4,6-trifluorobenzyl, 2,3,4,5-tetrafluorobenzyl, 2,3,4,6-tetrafluorobenzyl, 2,3,5,6-tetrafluorobenzyl, 2,3,4,5,6-pentafluorobenzyl, etc.; in addition, groups in which the fluorine atom (fluoro group) is arbitrarily replaced by a chlorine atom (chloro group), a bromine atom (bromo group), or an iodine atom (iodo group) can be listed, but are not limited to these.

[0038] Alkoxyalkyl, alkoxyaryl, and alkoxyaryl are alkyl, aryl, and aralkyl groups respectively substituted with one or more alkoxy groups, and specific examples of such alkyl, aryl, and aralkyl groups can be given as the examples described above.

[0039] Alkoxy groups that are substituents include, for example, alkoxy groups having at least one of the following: straight-chain, branched, and cyclic alkyl moieties having 1 to 20 carbon atoms. Examples of linear or branched alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, secondary butoxy, tertiary butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexoxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-propoxy, etc. Pentoxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, etc. In addition, examples of cyclic alkoxy groups include: cyclopropoxy, cyclobutoxy, 1-methyl-cyclopropoxy, 2-methyl-cyclopropoxy, cyclopentoxy, 1-methyl-cyclobutoxy, 2-methyl-cyclobutoxy, 3-methyl-cyclobutoxy, 1,2-dimethyl-cyclopropoxy, 2,3-dimethyl-cyclopropoxy, 1-ethyl-cyclopropoxy, 2-ethyl-cyclopropoxy, cyclohexyloxy, 1-methyl-cyclopentoxy, 2-methyl-cyclopentoxy, 3-methyl-cyclopentoxy, 1-ethyl-cyclobutoxy, 2-ethyl-cyclobutoxy, 3-ethyl-cyclobutoxy, 1,2-dimethyl-cyclobutoxy, 1,3-di... Methyl-cyclobutoxy, 2,2-dimethyl-cyclobutoxy, 2,3-dimethyl-cyclobutoxy, 2,4-dimethyl-cyclobutoxy, 3,3-dimethyl-cyclobutoxy, 1-n-propyl-cyclopropoxy, 2-n-propyl-cyclopropoxy, 1-isopropyl-cyclopropoxy, 2-isopropyl-cyclopropoxy, 1,2,2-trimethyl-cyclopropoxy, 1,2,3-trimethyl-cyclopropoxy, 2,2,3-trimethyl-cyclopropoxy, 1-ethyl-2-methyl-cyclopropoxy, 2-ethyl-1-methyl-cyclopropoxy, 2-ethyl-2-methyl-cyclopropoxy, and 2-ethyl-3-methyl-cyclopropoxy, etc.

[0040] Specific examples of alkoxyalkyl groups include: methoxymethyl, ethoxymethyl, 1-ethoxyethyl, 2-ethoxyethyl, ethoxymethyl, and other lower (less than 5 carbon atoms) alkoxyalkyl groups, but are not limited to these. Specific examples of alkoxyaryl groups include: 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-(1-ethoxy)phenyl, 3-(1-ethoxy)phenyl, 4-(1-ethoxy)phenyl, 2-(2-ethoxy)phenyl, 3-(2-ethoxy)phenyl, 4-(2-ethoxy)phenyl, 2-methoxynaphth-1-yl, 3-methoxynaphth-1-yl, 4-methoxynaphth-1-yl, 5-methoxynaphth-1-yl, 6-methoxynaphth-1-yl, 7-methoxynaphth-1-yl, etc., but are not limited to these. Specific examples of alkoxyaryl groups include 3-(methoxyphenyl)benzyl, 4-(methoxyphenyl)benzyl, etc., but are not limited to these.

[0041] The alkenyl group can be linear or branched, and there is no particular limitation on the number of carbon atoms. Ideally, it should be less than 40, more ideally less than 30, even more ideally less than 20, and still more ideally less than 10. Specific examples of alkenyl groups include: vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl... Alkenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4 -Pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-secondary butylvinyl, 1,3-dimethyl -1-Butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-Tributylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl, 2-Methyl-3-cyclopentenyl Examples of cycloalkenyl groups include: 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl; cross-linked cycloalkenyl groups such as dicycloheptenyl (norcamphenyl) can also be listed.

[0042] Furthermore, the substituents in the aforementioned alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, and alkenyl groups can be exemplified by, for example: alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, aryloxy, alkoxyaryl, alkenyl, alkoxyaralkyl, alkoxy, arylalkoxy, etc., and specific examples of these and their ideal carbon atom numbers can be listed as those described above or below. Furthermore, the aryloxy groups listed in the substituents are groups of aryl groups bonded by oxygen atoms (-O-); specific examples of such aryl groups can be given as the examples mentioned above. There is no particular limitation on the number of carbon atoms in the aryloxy group, but ideally it is 40 or less, more ideally 30 or less, and even more ideally 20 or less. Specific examples include phenoxy, naphth-2-yloxy, etc., but are not limited to these. Furthermore, when there are two or more substituents, the substituents can bond together to form a ring.

[0043] Organic groups containing epoxy groups include: glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, glycidoxycyclohexyl, etc. Organic groups containing an acrylamide group include: acrylamide methyl, acrylamide ethyl, acrylamide propyl, etc. Organic groups containing methacrylic acid can be listed as: methacrylic acid methyl, methacrylic acid ethyl, methacrylic acid propyl, etc. Organic groups containing a thiol group can be listed as: mercaptoethyl, mercaptobutyl, mercaptohexyl, mercaptooctyl, mercaptophenyl, etc. Organic groups containing an amino group include, but are not limited to, amino, aminomethyl, aminoethyl, aminophenyl, dimethylaminoethyl, and dimethylaminopropyl. Further details regarding organic groups containing an amino group will be discussed later. Organic groups containing alkoxy groups include, but are not limited to, methoxymethyl and methoxyethyl groups. However, groups in which the alkoxy group is directly bonded to a silicon atom are excluded. Organic groups having a sulfonyl group may include, for example, sulfonylalkyl and sulfonylaryl, but are not limited to these. Organic groups containing cyano groups include: cyanoethyl, cyanopropyl, cyanophenyl, cyanothio, etc.

[0044] Organic groups containing an amino group can be listed as those containing at least one of primary, secondary, and tertiary amino groups. Ideally, a hydrolysis condensate can be used, which is formed by hydrolyzing a hydrolyzable silane containing a tertiary amino group with a strong acid to create a relative cation containing a tertiary ammonium group. Furthermore, in addition to the nitrogen atom constituting the amino group, the organic group may also contain heteroatoms such as oxygen and sulfur atoms.

[0045] An ideal example of an organic group having an amine group can be a group represented by the following formula (A1).

[0046] [Chemistry 8] In formula (A1), R101 and R102 independently represent hydrogen atoms or hydrocarbon groups, and L independently represent substituted alkyl groups. * indicates a bond. Hydrocarbon groups may include alkyl, alkenyl, aryl, etc., but are not limited to these. Specific examples of such alkyl, alkenyl, and aryl groups can be given as those described in R 2 above. Furthermore, alkyl groups can be linear or branched, and their carbon number is typically 1 to 10, ideally 1 to 5. Examples include linear alkyl groups such as methylene, ethyl alkyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene. Organic groups containing an amino group can be listed as: amino, aminomethyl, aminoethyl, aminophenyl, dimethylaminoethyl, dimethylaminopropyl, etc., but are not limited to these.

[0047] <<X in formula (A-1)>> The alkoxy group in X can be exemplified by, for example, the alkoxy group listed in the description of R 2. The halogen atoms in X can be exemplified by, for example, the halogen atoms listed in the description of R 2.

[0048] Arylalkoxy groups are monovalent groups derived by removing a hydrogen atom from the hydroxyl group of an aryl alcohol. Specific examples of arylalkyl groups in arylalkoxy groups can be given as the examples mentioned above. There is no particular limitation on the number of carbon atoms in arylalkoxy groups; for example, it can be less than 40, ideally less than 30, and even more ideally less than 20. Specific examples of arylalkoxy groups include: phenylmethyloxy (benzyloxy), 2-phenylethyloxy, 3-phenyl-n-propyloxy, 4-phenyl-n-butyloxy, 5-phenyl-n-pentyloxy, 6-phenyl-n-hexyloxy, 7-phenyl-n-heptyloxy, 8-phenyl-n-octyloxy, 9-phenyl-n-nonyloxy, 10-phenyl-n-decyloxy, etc., but are not limited to these.

[0049] Acryloxy groups are monovalent groups derived by removing a hydrogen atom from the carboxyl group (-COOH) of a carboxylic acid compound. Typical examples include alkyl carbonyloxy, aryl carbonyloxy, or aralkyl carbonyloxy groups derived by removing a hydrogen atom from the carboxyl group of an alkyl carboxylic acid, aryl carboxylic acid, or aralkyl carboxylic acid, but are not limited to these. Specific examples of alkyl, aryl, and aralkyl groups in such alkyl carboxylic acids, aryl carboxylic acids, and aralkyl carboxylic acids can be given by examples similar to those described above. Specific examples of aceoxy groups include those with 2 to 20 carbon atoms, such as: methyl carbonyloxy, ethyl carbonyloxy, n-propyl carbonyloxy, isopropyl carbonyloxy, n-butyl carbonyloxy, isobutyl carbonyloxy, secondary butyl carbonyloxy, tertiary butyl carbonyloxy, n-pentyl carbonyloxy, 1-methyl-n-butyl carbonyloxy, 2-methyl-n-butyl carbonyloxy, 3-methyl-n-butyl carbonyloxy, 1,1-dimethyl-n-propyl carbonyloxy, 1,2-dimethyl-n-propyl carbonyloxy, 2,2-dimethyl-n-propyl carbonyloxy, 1-ethyl-n-propyl carbonyloxy, n-hexyl carbonyloxy, 1-methyl-n-pentyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-propyl carbonyloxy, 1-methyl-n-pentyl carbonyloxy, 2-methyl-n-pentyl carbonyloxy, 3-methyl-n-propyl carbonyloxy, 1-methyl-n-propyl ... The compounds include 4-methyl-n-pentylcarbonyloxy, 1,1-dimethyl-n-butylcarbonyloxy, 1,2-dimethyl-n-butylcarbonyloxy, 1,3-dimethyl-n-butylcarbonyloxy, 2,2-dimethyl-n-butylcarbonyloxy, 2,3-dimethyl-n-butylcarbonyloxy, 3,3-dimethyl-n-butylcarbonyloxy, 1-ethyl-n-butylcarbonyloxy, 2-ethyl-n-butylcarbonyloxy, 1,1,2-trimethyl-n-propylcarbonyloxy, 1,2,2-trimethyl-n-propylcarbonyloxy, 1-ethyl-1-methyl-n-propylcarbonyloxy, 1-ethyl-2-methyl-n-propylcarbonyloxy, phenylcarbonyloxy, and toluenesulfonylcarbonyloxy, etc.

[0050] Specific examples of hydrolyzable silanes (A) having carbon-carbon triple bonds include the following compounds, but hydrolyzable silanes (A) having carbon-carbon triple bonds are not limited to these compounds. [Chemistry 9] [Chemistry 10] [Chemistry 11] [Chemistry 12] [Chemistry 13] [Chemistry 14] [Chemistry 15] [Chemistry 16] [Chemistry 17] [Chemistry 18] [Chemistry 19] [Chemistry 20] [Chemistry 21] In the formula, R represents methyl or ethyl.

[0051] In the first embodiment, the amount of hydrolyzed silane (A) used in the synthesis of [A] containing a polysiloxane comprising a hydrolyzed silane (A) having a carbon-carbon triple bond is, from the viewpoint of more fully obtaining the effects of the present invention, ideally 0.01 to 100 parts by mass relative to 100 parts by mass of the total amount of hydrolyzed silane used in the synthesis of the polysiloxane, more ideally 0.05 to 50 parts by mass, even more ideally 0.1 to 30 parts by mass, and particularly ideally 1 to 20 parts by mass.

[0052] In the second embodiment, from the viewpoint of more fully obtaining the effects of the present invention, the content of hydrolyzable silane (A) having a carbon-carbon triple bond as component [B] in the composition for forming the silicon-containing photoresist lower layer film is ideally 0.01 to 100 parts by mass relative to 100 parts by mass of [A'] polysiloxane, more ideally 0.05 to 50 parts by mass, even more ideally 0.1 to 30 parts by mass, and particularly ideally 1 to 20 parts by mass.

[0053] <[A] component and [A'] component: polysiloxane> The polysiloxane used as component [A] is not particularly limited as long as it is a polymer having carbon-carbon triple bonds and siloxane bonds. The polysiloxane used as component [A'] is not particularly limited as long as it is a polymer containing siloxane bonds. The polysiloxane used as component [A'] can also be the polysiloxane used as component [A].

[0054] Polysiloxanes can be modified polysiloxanes in which a portion of the silanol group has been modified, such as polysiloxane modified by alcohol modification or acetal protection of a portion of the silanol group. Furthermore, an example of a polysiloxane may be a hydrolysis condensate of a hydrolyzable silane, or a modified product in which at least a portion of the silanol groups present in the hydrolysis condensate has been modified with alcohol or protected with acetal (hereinafter, sometimes referred to as "modified hydrolysis condensate"). The hydrolyzable silane associated with the hydrolysis condensate may comprise one or more hydrolyzable silanes. Furthermore, the polysiloxane used as component [A] or [A'] can have a main chain structure of any one of cage-like, ladder-like, linear, or branched types. Also, commercially available polysiloxanes can be used as component [A'].

[0055] Furthermore, in this invention, the "hydrolysis condensate" of hydrolyzable silane, i.e., the product of hydrolysis condensation, includes not only fully condensed organosiloxane polymers but also partially condensed organosiloxane polymers. These partially condensed polymers are similar to fully condensed polymers, both obtained through the hydrolysis and condensation of hydrolyzable silanes. However, since some hydrolysis stops without condensation, Si-OH groups may remain. In addition to hydrolysis condensates, the composition for forming the lower layer of silicon-containing photoresist may also contain uncondensed hydrolysates (fully hydrolyzed, partially hydrolyzed) and monomers (hydrolyzable silanes). Furthermore, in this specification, "hydrolyzable silane" is sometimes abbreviated as "silane compound".

[0056] Polysiloxanes that are components of [A] can be exemplified by, for example, hydrolytic condensates of hydrolytic silanes or their modifications containing hydrolytic silanes (A) having carbon-carbon triple bonds.

[0057] Polysiloxanes that are components of [A] include, for example, hydrolyzable silanes (A) containing a carbon-carbon triple bond and hydrolyzable silanes hydrolyzable condensates or modified forms thereof, which contain at least one hydrolyzable silane represented by the following formula (1). Polysiloxanes that are components of [A'] can be exemplified by, for example, hydrolytic condensates of hydrolytic silanes or their modifications containing at least one hydrolytic silane represented by the following formula (1).

[0058] <<Formula (1)>> [Chemistry 22]

[0059] In formula (1), R1 is a group bonded to a silicon atom, which independently represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted halogenated alkyl group, a substituted aralkyl halogenated alkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or independently represents an organogroup having an epoxy group, an organogroup having an acrylonitrile group, an organogroup having a methacrylonitrile group, an organogroup having a mercapto group, an organogroup having an amino group, an organogroup having an alkoxy group, an organogroup having a sulfonylurea group, or an organogroup having a cyano group, or a combination of two or more of these. In addition, R2 is a group or atom bonded to a silicon atom, which can independently represent an alkoxy, arylalkoxy, acetoxy, or halogen atom. a represents an integer from 0 to 3.

[0060] In formula (1), specific examples of each group and atom in R 1, and their ideal number of carbon atoms can be listed in formula (A-1) related to the aforementioned groups and carbon atoms in R 2. In formula (1), specific examples of each group and atom in R 2, as well as their ideal number of carbon atoms, can be listed in formula (A-1) related to the aforementioned groups and atoms and the number of carbon atoms.

[0061] <<<Specific examples of hydrolyzable silanes represented by formula (1)>>> Specific examples of hydrolyzable silanes represented by formula (1) include: tetramethoxysilane, tetrachlorosilane, tetraethoxysilane, tetraethoxysilane, tetran-propoxysilane, tetraisopropoxysilane, tetran-butoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriethoxysilane, methyltripropoxysilane, and methyltributoxysilane. Alkane, methyltripentoxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethoxysilane, epoxypropoxymethyltrimethoxysilane, epoxypropoxymethyltriethoxysilane, α-epoxypropoxyethyltrimethoxysilane, α-epoxypropoxyethyltriethoxysilane, β-epoxypropoxyethyltrimethoxysilane, β-epoxypropoxyethyltriethoxysilane α-Glycidoxypropyltrimethoxysilane, α-Glycidoxypropyltriethoxysilane, β-Glycidoxypropyltrimethoxysilane, β-Glycidoxypropyltriethoxysilane, γ-Glycidoxypropyltrimethoxysilane, γ-Glycidoxypropyltriethoxysilane, γ-Glycidoxypropyltripropoxysilane, γ-Glycidoxypropyltributoxysilane, γ-Glycidoxypropyltributoxysilane β-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexane) (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 γ-(3,4-epoxycyclohexyl)ethyltriphenoxysilane, γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ-(3,4-epoxycyclohexyl)butyltrimethoxysilane, δ-(3,4-epoxycyclohexyl)butyltriethoxysilane, epoxypropoxymethylmethyldimethoxysilane, epoxypropoxy Methylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylethyldimethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane,γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, methylvinyldichlorosilane, methylvinyldiethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, dimethylvinylchlorosilane, dimethylvinylethoxysilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldichlorosilane, divinyldiethoxysilane, γ- -Glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriethoxysilane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldichlorosilane, allylmethyldiethoxysilane, allylmethyldiethoxysilane, allyl Dimethylmethoxysilane, allyldimethylethoxysilane, allyldimethylchlorosilane, allyldimethylethoxysilane, diallyldimethoxysilane, diallyldiethoxysilane, diallyldichlorosilane, diallyldiethoxysilane, 3-allylaminopropyltrimethoxysilane, 3-allylaminopropyltriethoxysilane, p-styryltrimethyl oxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldiethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, phenyldimethylchlorosilane, phenyldimethylethoxysilane Alkane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, diphenylmethylchlorosilane, diphenylmethylacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, diphenyldiacetoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylacetoxysilane, triphenylchlorosilane, 3-aniline Propyltrimethoxysilane, 3-anilinepropyltriethoxysilane, dimethoxymethyl-3-(3-phenoxypropylthiopropyl)silane, triethoxy((2-methoxy-4-(methoxymethyl)phenoxy)methyl)silane, benzyltrimethoxysilane, benzyltriethoxysilane, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzyldimethyl Methoxysilane, benzyl dimethyl ethoxysilane, benzyl dimethyl chlorosilane, phenylethyl trimethoxysilane, phenylethyl triethoxysilane, phenylethyl trichlorosilane, phenylethyl triethoxysilane, phenylethyl methyl dimethoxysilane, phenylethyl methyl diethoxysilane, phenylethyl methyl dichlorosilane, phenylethyl methyl diethoxysilane, methoxyphenyl trimethoxysilane,Methoxyphenyltriethoxysilane, methoxyphenyltriethoxysilane, methoxyphenyltrichlorosilane, methoxybenzyltrimethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltriethoxysilane, methoxybenzyltrichlorosilane, methoxyphenylethyltrimethoxysilane, methoxyphenylethyltriethoxysilane, methoxyphenylethyltriethoxysilane, methoxyphenylethyltrichlorosilane, ethoxyphenyltrimethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltriethoxysilane, ethoxyphenyltrichlorosilane Alkane, ethoxybenzyltrimethoxysilane, ethoxybenzyltriethoxysilane, ethoxybenzyltriacetoxysilane, ethoxybenzyltrichlorosilane, isopropoxyphenyltrimethoxysilane, isopropoxyphenyltriethoxysilane, isopropoxyphenyltriacetoxysilane, isopropoxyphenyltrichlorosilane, isopropoxybenzyltrimethoxysilane, isopropoxybenzyltriethoxysilane, isopropoxybenzyltriacetoxysilane, isopropoxybenzyltrichlorosilane, tri-butoxyphenyltrimethoxysilane, tri-butoxyphenyltriethoxysilane Tri-butoxyphenyltriethoxysilane, tri-butoxyphenyltrichlorosilane, tri-butoxybenzyltrimethoxysilane, tri-butoxybenzyltriethoxysilane, tri-butoxybenzyltriethoxysilane, tri-butoxybenzyltriethoxysilane, methoxynaphthyltrimethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltriethoxysilane, methoxynaphthyltrichlorosilane, ethoxynaphthyltrimethoxysilane, ethoxynaphthyltriethoxysilane, ethoxynaphthyltriethoxysilane, γ- γ-Chloropropyltrimethoxysilane, γ-Chloropropyltriethoxysilane, γ-Chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methylpropyltrimethoxysilane, γ-methylpropyltriethoxysilane, β-cyanoethyltriethoxysilane, cyanothiopropyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, triethoxysilylpropyldiallyl isocyanurate (triethoxysilylpropyl diallyl) isocyanurate), bicyclic [2,2,1]heptenyltriethoxysilane, benzenesulfonylpropyltriethoxysilane, benzenesulfonylaminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropyl γ-methyldiethoxysilane, dimethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, and silanes represented by the following formulas (A-1) to (A-41),Silanes, etc., represented by formulas (1-1) to (1-225) and (1-246) to (1-290) below, but not limited to these.

[0062] [Chemistry 23]

[0063] [Chemistry 24]

[0064] [Chemistry 25]

[0065] [Chemistry 26]

[0066] [Chemistry 27]

[0067] [Chemistry 28]

[0068] [Chemistry 29]

[0069] [Chemistry 30]

[0070] [Chemistry 31]

[0071] [Chemistry 32]

[0072] [Chemistry 33]

[0073] [Chemistry 34]

[0074] [Chemistry 35]

[0075] [Chemistry 36]

[0076] [Chemistry 37]

[0077] [Chemistry 38]

[0078] [Chemistry 39]

[0079] [Chemistry 40]

[0080] [Chemistry 41]

[0081] [Chemistry 42]

[0082] [Chemistry 43]

[0083] [Chemistry 44]

[0084] [Chemistry 45]

[0085] [Chemistry 46]

[0086] [Chemistry 47]

[0087] [Chemistry 48]

[0088] [Chemistry 49]

[0089] [Chem. 50]

[0090] [Chemistry 51]

[0091] [Chemistry 52]

[0092] [Chemistry 53]

[0093] [Chemistry 54]

[0094] [Chemistry 55]

[0095] [Chemistry 56]

[0096] [Chemistry 57]

[0097] [Chem. 58]

[0098] [Chemistry 59]

[0099] [Chemistry 60]

[0100] [Chemistry 61]

[0101] [Chemistry 62]

[0102] [Chemistry 63]

[0103] [Chemistry 64]

[0104] [Chemistry 65]

[0105] [Chemistry 66]

[0106] [Chemistry 67]

[0107] [Chemistry 68]

[0108] [Chemistry 69]

[0109] In formulas (1-1) to (1-225) and (1-246) to (1-290), T independently represents an alkoxy, acetoxy, or halogen group, for example, ideally representing a methoxy or ethoxy group.

[0110] In addition, [A] polysiloxane may include hydrolyzable silane (A) containing a carbon-carbon triple bond and hydrolyzable silane hydrolysates or modified forms thereof represented by the following formula (2). In addition, [A] polysiloxane may include hydrolyzable silane (A) containing a carbon-carbon triple bond, hydrolyzable silane represented by formula (1), and hydrolyzable silane hydrolyzable condensate or modified thereof represented by formula (2). [A'] Polysiloxane, including hydrolyzed condensates of hydrolyzed silanes containing both hydrolyzed silanes represented by formula (1) and hydrolyzed silanes represented by formula (2) below, or hydrolyzed condensates of hydrolyzed silanes containing hydrolyzed silanes represented by formula (2) below instead of hydrolyzed silanes represented by formula (1), or hydrolyzed condensates of hydrolyzed silanes represented by formula (2) below, or hydrolyzed condensates of hydrolyzed silanes represented by formula (1).

[0111] <Formula (2)> [Chemistry 70]

[0112] In formula (2), R3 is a group bonded to a silicon atom, which independently represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted halogenated alkyl group, a substituted aralkyl group, a substituted aralkyl group, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or independently represents an organogroup having an epoxy group, an organogroup having an acrylonitrile group, an organogroup having a methacrylonitrile group, an organogroup having a mercapto group, an organogroup having an amino group, an organogroup having an alkoxy group, an organogroup having a sulfonylurea group, or an organogroup having a cyano group, or a combination of two or more of these. In addition, R4 represents a group or atom bonded to a silicon atom, which can independently represent an alkoxy, arylalkoxy, acetoxy, or halogen atom. R5 is a group bonded to a silicon atom, and each group can independently represent an alkyl or aryl group. b represents 0 or 1, c represents 0 or 1.

[0113] Specific examples of each group and atom in R3, and the ideal number of carbon atoms thereof, can be enumerated in formula (A-1) of the aforementioned groups and carbon atoms in R2. Specific examples of each group and atom in R 4, and the ideal number of carbon atoms thereof, can be enumerated in formula (A-1) with respect to the aforementioned groups and atoms and the number of carbon atoms. Specific examples of alkyl groups in R 5 include: straight-chain alkyl groups such as methylene, ethyl alkyl group, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched alkyl groups such as 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethyl alkyl group, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; and methyltriyl, ethyl-1,1,2-triyl, ethyl-1,2,2-triyl... Ethyl-2,2,2-triyl, prop-1,1,1-triyl, prop-1,1,2-triyl, prop-1,2,3-triyl, prop-1,2,2-triyl, prop-1,1,3-triyl, but-1,1,1-triyl, but-1,1,2-triyl, but-1,1,3-triyl, but-1,2,3-triyl, but-1,2,4-triyl, but-1,2,2-triyl, but-2,2,3-triyl, 2-methylprop-1,1,1-triyl, 2-methylprop-1,1,2-triyl, 2-methylprop-1,1,3-triyl alkyltriyl, etc., but not limited to these. Specific examples of aryl groups in R 5 include: 1,2-arylphenyl, 1,3-arylphenyl, 1,4-arylphenyl; 1,5-naphthodiyl, 1,8-naphthodiyl, 2,6-naphthodiyl, 2,7-naphthodiyl, 1,2-anthratriyl, 1,3-anthratriyl, 1,4-anthratriyl, 1,5-anthratriyl, 1,6-anthratriyl, 1,7-anthratriyl, 1,8-anthratriyl, 2,3-anthratriyl, 2,6-anthratriyl, 2,7-anthratriyl, 2,9-anthratriyl, 2,10-anthratriyl, 9,10-anthratriyl, etc., which are groups derived from the aromatic ring of a condensed-ring aromatic hydrocarbon compound by removing two hydrogen atoms; 4,4'-biphenyldiyl, 4,4”-p-triphenyldiyl, etc., which are groups derived from the aromatic ring of a ring-linked aromatic hydrocarbon compound by removing two hydrogen atoms, etc., but are not limited to these. The ideal value for b is 0. The ideal value of c is 1.

[0114] Specific examples of hydrolyzable silanes represented by formula (2) include: methylene bis(trimethoxy)silane, methylene bis(trichloro)silane, methylene bis(triethoxy)silane, ethyl bis(triethoxy)silane, ethyl bis(trichloro)silane, ethyl bis(triethoxy)silane, propyl bis(triethoxy)silane, butyl bis(trimethoxy)silane, phenyl bis(trimethoxy)silane, phenyl bis(triethoxy)silane, phenyl bis(methyl)ethoxysilane, phenyl bis(methyl)methoxysilane, naphthyl bis(trimethoxy)silane, bis(trimethoxy)silane, bis(triethoxy)silane, bis(ethyl)ethoxysilane, bis(methyl)methoxysilane, etc., but are not limited to these.

[0115] [A] Polysiloxane, including hydrolyzable silanes (A) containing carbon-carbon triple bonds, hydrolyzable silanes represented by formula (1) and / or hydrolyzable silanes represented by formula (2), and hydrolyzable silanes of other hydrolyzable silanes listed below, hydrolyzable condensates of hydrolyzable silanes or their modifications thereof. [A'] Polysiloxane, including hydrolytic condensates of hydrolytic silanes containing hydrolytic silanes represented by formula (1) and / or hydrolytic silanes represented by formula (2), as well as other hydrolytic silanes listed below, or their modifications. Other hydrolyzable silanes include, but are not limited to, silane compounds containing an ononium group in their molecules and silane compounds containing a cyclic urea skeleton in their molecules.

[0116] <<Silane compounds with intramolecular ononium groups (hydrolyzable organosilanes)>> Silane compounds with ononium groups in their molecules are expected to effectively and efficiently promote the cross-linking reaction of hydrolyzable silanes.

[0117] An ideal example of a silane compound having an intramolecular ononium group is represented by formula (3).

[0118] [Chemistry 71]

[0119] R 11 is a group bonded to silicon atoms, representing a tumene group or an organic group containing a tumene group. R 12 is a group bonded to a silicon atom, which independently represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted halogenated alkyl group, a substituted aralkyl halide, a substituted aralkyl halide, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or independently represents an organogroup having an epoxy group, an organogroup having an acrylonitrile group, an organogroup having a methacrylonitrile group, an organogroup having a mercapto group, an organogroup having an amino group, or an organogroup having a cyano group, or a combination of two or more of these. R 13 represents a group or atom bonded to a silicon atom, which can be independently represented as an alkoxy, arylalkoxy, acetoxy, or halogen atom. f represents 1 or 2, g represents 0 or 1, and satisfies 1≦f+g≦2.

[0120] Specific examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl, and organic groups having an epoxy group, organic groups having an acrylonitrile group, organic groups having a methacrylonitrile group, organic groups having a mercapto group, organic groups having an amino group and organic groups having a cyano group, alkoxy, arylalkoxy, acetoxy, halogen atoms; and specific examples of substituents of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaralkyl and alkenyl, and their ideal number of carbon atoms, respectively, for R 12, those described in R 2 of the preceding statement about formula (A-1) can be listed, and for R 13, those described in X of the preceding statement about formula (A-1) can be listed.

[0121] To elaborate further, specific examples of onnnage groups could be listed as cyclic ammonium groups or chain ammonium groups, ideally tertiary or quaternary ammonium groups. That is, ideal specific examples of onium groups or organic groups having onium groups can be listed as: cyclic ammonium groups or chain ammonium groups or organic groups having at least one of these, ideally tertiary ammonium groups or quaternary ammonium groups or organic groups having at least one of these. Furthermore, when the onnnage group is a cyclic ammonium group, the nitrogen atom constituting the ammonium group also serves as an atom constituting the ring. In this case, there may be cases where the nitrogen atom constituting the ring is directly bonded to the silicon atom or bonded through a divalent linker, and cases where the carbon atom constituting the ring is directly bonded to the silicon atom or bonded through a divalent linker.

[0122] In one example of an ideal state, R11 of the group bonded to the silicon atom is a heteroaromatic cyclic ammonium group represented by the following formula (S1).

[0123] [Chemistry 72] In formula (S1), A1, A2, A3, and A4 independently represent groups represented by any of the formulas (J1) to (J3) below, except that at least one of A1 to A4 is a group represented by formula (J2) below. Furthermore, depending on which of A1 to A4 the silicon atom in formula (3) bonds with, it is determined whether the bond between each A1 to A4 and its respective adjacent atoms forming the ring is a single bond or a double bond, so that the formed ring exhibits aromaticity. * indicates a bond.

[0124] [Chemistry 73] In formulas (J1) to (J3), R10 independently represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a haloalkyl group, a haloaryl group, a haloaralkyl group, or an alkenyl group, and specific examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, and alkenyl groups, as well as their ideal number of carbon atoms, can be listed as the same as those mentioned above. * indicates a bond.

[0125] In formula (S1), R14 independently represents alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkenyl or hydroxyl. When there are two or more R14, the two R14 can bond together to form a ring. The ring formed by the two R14 can be a cross-linked ring structure. In this case, the cyclic ammonium group will have adamantane ring, norcamphene ring, spiro ring, etc. Specific examples of such alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl and alkenyl groups, and their ideal carbon number, are the same as those mentioned above.

[0126] In formula (S1), n1 is an integer from 1 to 8, m1 is 0 or 1, and m2 is 0 or a positive integer from 1 to the largest number that can be substituted on a single ring or multiple rings. When m1 is 0, a (4+n1)-element ring is formed containing A1 to A4. That is, a quinary ring is formed when n1 is 1, a hexagram when n1 is 2, a septem ring when n1 is 3, an octem ring when n1 is 4, a quintuple ring when n1 is 5, a decagram when n1 is 6, an eleven-eighths ring when n1 is 7, and a twelfths ring when n1 is 8. When m1 is 1, a condensed ring is formed by the condensation of a (4+n1)-membered ring containing A1~A3 and a six-membered ring containing A4. Depending on whether A1 to A4 are formulas (J1) to (J3), there may be cases where the atoms constituting the ring have hydrogen atoms or cases where they do not. When A1 to A4 have hydrogen atoms on the atoms constituting the ring, the hydrogen atoms can be substituted with R14. In addition, R14 can also be substituted on ring-constituting atoms other than those in A1 to A4. In view of this, as mentioned above, m2 is an integer selected from 0 or from 1 up to the largest number that can be substituted on a single ring or multiple rings.

[0127] The bonds of the heteroaromatic cyclic ammonium group represented by formula (S1) are any carbon or nitrogen atom present in such a monocyclic or condensed ring, and are directly bonded to silicon atoms, or are bonded to linking groups to form an organic group with cyclic ammonium, which is then bonded to silicon atoms. Examples of such linking groups include: alkyl, aryl, alkenyl, etc., but are not limited to these. Specific examples of alkyl and aryl groups, and their ideal carbon number, are the same as those mentioned above.

[0128] Furthermore, the alkenyl group is a divalent group derived by further removing a hydrogen atom from the alkenyl group. Specific examples of such alkenyl groups can be given as described above. The number of carbon atoms in the alkenyl group is not particularly limited, but ideally it is 40 or less, more ideally 30 or less, and even more ideally 20 or less. Specific examples include: vinyl, 1-methylvinyl, vinyl propenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, etc., but are not limited to these.

[0129] Specific examples of silane compounds (hydrolyzable organosilanes) having a heteroaromatic cyclic ammonium group represented by formula (S1) and represented by formula (3) can be listed, but are not limited to these, silanes represented by formulas (I-1) to (I-50) below.

[0130] [Chemistry 74]

[0131] [Chemistry 75]

[0132] [Chemistry 76]

[0133] In another example, R11 of the group bonded to silicon atoms in formula (3) can be a heteroaliphatic cyclic ammonium group represented by the following formula (S2).

[0134] [Chemistry 77]

[0135] In formula (S2), A5, A6, A7, and A8 independently represent groups represented by any of the formulas (J4) to (J6) below, except that at least one of A5 to A8 is a group represented by formula (J5) below. Based on which of A5 to A8 the silicon atom in formula (3) bonds with, it is determined whether the bond between each A5 to A8 and its adjacent atoms forming the ring is a single bond or a double bond, thus making the formed ring non-aromatic. * indicates a bond.

[0136] [Chemistry 78]

[0137] In formulas (J4) to (J6), R10 independently represents a single bond, a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a haloalkyl group, a haloaryl group, a haloaralkyl group, or an alkenyl group, and specific examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, and alkenyl groups, as well as their ideal number of carbon atoms, can be listed as the same as those mentioned above. * indicates a bond.

[0138] In formula (S2), R15 can independently represent alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkenyl or hydroxyl. When there are two or more R15, the two R15 can bond together to form a ring. The ring formed by the two R15 can be a cross-linked ring structure. In this case, the cyclic ammonium group will have adamantane ring, norcamphene ring, spiro ring, etc. Specific examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl and alkenyl groups, and their ideal carbon number, are the same as those mentioned above.

[0139] In formula (S2), n2 is an integer from 1 to 8, m3 is 0 or 1, and m4 is 0 or a positive integer from 1 to the largest number that can be substituted on a single ring or multiple rings. When m3 is 0, a (4+n2)-element ring is formed containing A5 to A8. That is, a quinary ring is formed when n2 is 1, a hexagram when n2 is 2, a septem ring when n2 is 3, an octem ring when n2 is 4, a quintuple ring when n2 is 5, a decagram when n2 is 6, an eleven-eighths ring when n2 is 7, and a twelfths ring when n2 is 8. When m3 is 1, a condensed ring is formed by the condensation of a (4+n2)-membered ring containing A5~A7 and a six-membered ring containing A8. Depending on whether A5 to A8 are formulas (J4) to (J6), there may be cases where the atoms constituting the ring have hydrogen atoms or cases where they do not. When A5 to A8 have hydrogen atoms on the atoms constituting the ring, the hydrogen atoms can be substituted with R15. In addition, R15 can also be substituted on the ring-constituting atoms other than the ring-constituting atoms in A5 to A8. In view of this situation, as mentioned above, m4 is an integer selected from 0 or from 1 up to the largest number that can be substituted on a single ring or multiple rings.

[0140] The bond of the heteroaliphatic cyclic ammonium group represented by formula (S2) is any carbon or nitrogen atom present in such a monocyclic or condensed ring, and is directly bonded to a silicon atom, or is bonded to a linker group to form an organic group with cyclic ammonium, which is then bonded to a silicon atom. Such linking groups can be listed as: alkyl, aryl, or alkenyl, and specific examples of alkyl, aryl, and alkenyl groups, as well as their ideal carbon number, can be listed as those mentioned above.

[0141] Specific examples of silane compounds (hydrolyzable organosilanes) having a heteroaliphatic cyclic ammonium group represented by formula (S2) and represented by formula (3) can be listed, but are not limited to these.

[0142] [Chemistry 79]

[0143] [Chemistry 80]

[0144] In another example, R11 of the group bonded to silicon atoms in formula (3) can be a chain-like ammonium group represented by the following formula (S3).

[0145] [Chemistry 81] In formula (S3), R 10 independently represent hydrogen atoms, alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, or alkenyl, and specific examples of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, and alkenyl, as well as their ideal number of carbon atoms, can be listed as above. * indicates a bond.

[0146] The chain-like ammonium group represented by formula (S3) is directly bonded to silicon atoms, or it is bonded to a linker group to form an organic group with chain-like ammonium groups, which is then bonded to silicon atoms. Such linking groups can be listed as: alkyl, aryl, or alkenyl, and specific examples of alkyl, aryl, and alkenyl groups can be listed as the same examples as those mentioned above.

[0147] Specific examples of silane compounds (hydrolyzable organosilanes) having a chain-like ammonium group represented by formula (S3) can be listed as silanes represented by formulas (III-1) to (III-28) below, but are not limited to these.

[0148] [Chemistry 82]

[0149] [Chemistry 83]

[0150] <<Silicone compounds with an intramolecular cyclic urea skeleton (hydrolyzable organosilicones)>> Hydrolyzable organosilicones with an intramolecular cyclic urea skeleton can be exemplified by hydrolyzable organosilicones represented by the following formula (4-1).

[0151] [Chemistry 84] In formula (4-1), R 401 is a group bonded to silicon atoms, and each group is independently represented by the group represented by the following formula (4-2). R 402 is a group bonded to a silicon atom, representing a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted halogenated alkyl group, a substituted aralkyl halide, a substituted aralkyl halide, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or representing an organogroup having an epoxy group, an organogroup having an acrylonitrile group, an organogroup having a methacrylonitrile group, an organogroup having a mercapto group, or an organogroup having a cyano group, or a combination of two or more of these. R 403 represents a group or atom bonded to a silicon atom, which can be independently represented as an alkoxy, arylalkoxy, acetoxy, or halogen atom. x is 1 or 2, y is 0 or 1, and x + y ≦ 2. R 402 includes alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, alkenyl, and organic groups having epoxy groups, organic groups having acrylonitrile groups, organic groups having methacrylonitrile groups, organic groups having mercapto groups, and organic groups having cyano groups; and R 403 includes alkoxy, arylalkoxy, acetoxy, and halogen atoms; and specific examples of such substituents, the ideal number of carbon atoms, etc., can be listed as the same as those described in R 2 and X in the previous statement concerning formula (A-1).

[0152] [Chemistry 85] In formula (4-2), R 404 independently represents a hydrogen atom, a substituted alkyl group, a substituted alkenyl group, or an organogroup with an epoxy group or an organogroup with a sulfonylurea group; R 405 independently represents an alkyl group, a hydroxyalkyl group, a sulfur bond (-S-), an ether bond (-O-), or an ester bond (-CO-O- or -O-CO-). * indicates a bond. Furthermore, specific examples of substituted alkyl groups, substituted alkenyl groups, and organic groups having epoxy groups in R 404, as well as the ideal number of carbon atoms, can be listed as those identical to those described in R 2 of the previous formula (A-1). In addition, the substituted alkyl groups in R 404 are ideally alkyl groups in which the terminal hydrogen atom is replaced by a vinyl group, and specific examples can be listed as: allyl, 2-vinylethyl, 3-vinylpropyl, 4-vinylbutyl, etc.

[0153] Organic groups containing a sulfonylurea group are not particularly limited as long as they contain a sulfonylurea group. Examples include: substituted alkyl sulfonylureas, substituted aryl sulfonylureas, substituted aralkyl sulfonylureas, substituted alkyl halogenated alkyl sulfonylureas, substituted aryl halogenated aryl sulfonylureas, substituted alkoxyalkyl sulfonylureas, substituted alkoxyaryl sulfonylureas, substituted alkoxyaryl sulfonylureas, and substituted alkenyl sulfonylureas, etc. Specific examples and ideal carbon number of alkyl, aryl, aralkyl, haloalkyl, haloaryl, haloaralkyl, alkoxyalkyl, alkoxyaryl, alkoxyaralkyl, and alkenyl, and their substituents, can be listed as the same as those described in R 2 of formula (A-1) above.

[0154] An alkyl group is a divalent group derived by further removing a hydrogen atom from an alkyl group. It can be linear, branched, or cyclic. Specific examples of such alkyl groups can be given as described above. There is no particular limitation on the number of carbon atoms in an alkyl group, but ideally it is 40 or less, more ideally 30 or less, even more ideally 20 or less, and even more ideally 10 or less.

[0155] In addition, the alkyl group of R 405 may have one or more of the following: a sulfur bond, an ether bond, and an ester bond, either at its end or in the middle, ideally in the middle. Specific examples of alkyl groups include: straight-chain alkyl groups such as methylene, ethyl alkyl group, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene; branched-chain alkyl groups such as methyl ethyl alkyl group, 1-methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethyl alkyl group, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, and 1-ethyltrimethylene; cyclic alkyl groups such as 1,2-cyclopropyldiyl, 1,2-cyclobutyldiyl, 1,3-cyclobutyldiyl, 1,2-cyclohexanediyl, and 1,3-cyclohexanediyl; and cyclic alkyl groups such as -CH 2OCH 2-, -CH 2CH 2OCH 2-, -CH 2CH 2OCH 2CH 2-, and -CH 2CH 2CH 2OCH 2CH. 2-, -CH 2CH 2OCH 2CH 2CH 2-, -CH 2CH 2CH 2OCH 2CH 2CH 2-, -CH 2SCH 2-, -CH 2CH 2SCH 2-, -CH 2CH 2SCH 2CH 2-, -CH 2CH 2CH 2SCH 2CH 2-, -CH 2CH 2SCH 2CH 2CH 2-, -CH 2CH 2SCH 2CH 2CH 2-, -CH 2CH 2CH 2SCH 2CH 2CH 2-, -CH 2OCH 2CH 2SCH 2-, etc., containing alkyl groups such as ether groups, but not limited to these.

[0156] Hydroxyalkylene refers to an alkylene group in which at least one hydrogen atom is replaced by a hydroxyl group. Specific examples include: hydroxymethylene, 1-hydroxyethylalkylene, 2-hydroxyethylalkylene, 1,2-dihydroxyethylalkylene, 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, 4,4-dihydroxytetramethylene, etc., but not limited to these.

[0157] In formula (4-2), X 401 independently represents any of the groups represented by formulas (4-3) to (4-5) below, and the carbon atoms of the ketone groups in formulas (4-4) and (4-5) below are bonded to the nitrogen atoms bonded to R 405 in formula (4-2). [Chemistry 86]

[0158] In formulas (4-3) to (4-5), R 406 to R 410 independently represent hydrogen atoms, substituted alkyl groups, substituted alkenyl groups, or organogroups having epoxy or sulfonyl groups. Specific examples of substituted alkyl groups, substituted alkenyl groups, and organogroups having epoxy or sulfonyl groups, as well as the ideal number of carbon atoms, are the same as those described above regarding R 2 in formula (A-1). Furthermore, specific examples of organogroups having sulfonyl groups, as well as the ideal number of carbon atoms, are the same as those described above regarding R 404. * indicates a bond. From the viewpoint of achieving excellent lithography properties with good reproducibility, X 401 is ideally represented by the group represented by formula (4-5).

[0159] From the viewpoint of achieving excellent lithography properties with good reproducibility, the ideal system is an alkyl group in which at least one of R 404 and R 406 to R 410 is a vinyl group in which the terminal hydrogen atom is replaced by a vinyl group.

[0160] Hydrolyzable organosilanes represented by formula (4-1) can be commercially available or synthesized using conventional methods as described in International Publication No. 2011 / 102470, etc.

[0161] The following are specific examples of hydrolyzable organosilicones represented by formula (4-1), including silanes represented by formulas (4-1-1) to (4-1-29), but not limited to these.

[0162] [Chemistry 87]

[0163] [Chemistry 88]

[0164] [Chemistry 89]

[0165] Without impairing the effects of the present invention, [A]polysiloxane and [A']polysiloxane may be hydrolytic condensates of hydrolyzable silanes containing other silane compounds not exemplified above, or modified thereof.

[0166] As previously stated, [A]polysiloxane and [A']polysiloxane may be modified with at least a portion of the silanol group of the hydrolysis condensate. For example, a modified product with a portion of the silanol group modified with alcohol or a modified product protected with acetal may be used. Examples of the modified polysiloxanes include: reaction products obtained by reacting at least a portion of the silanol groups in the aforementioned hydrolyzable silane hydrolysis condensate with the hydroxyl groups of an alcohol; dehydration products of the condensate and an alcohol; and modified products in which at least a portion of the silanol groups in the condensate are protected by acetal groups.

[0167] Alcohols can be monohydric alcohols, such as: methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tributanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-heptanol, 2-heptanol, tripentanol, neopentanol, 2-methyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-prop ... -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. In addition, alcohols containing alkoxy groups, 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.

[0168] The reaction between the silyl group of the hydrolysis condensate and the hydroxyl group of the alcohol is achieved by contacting the hydrolysis condensate with the alcohol and reacting at a temperature of 40–160°C (e.g., 60°C) for 0.1–48 hours (e.g., 24 hours) to obtain a silyl-terminated modified product. In this case, the alcohol of the terminator can be used as a solvent in compositions containing polysiloxanes.

[0169] Furthermore, the dehydration reaction product of hydrolyzable silane hydrolysis condensate and alcohol can be produced by reacting the hydrolysis condensate with alcohol in the presence of an acid as a catalyst, thereby capping the silyl group with alcohol and removing the water generated during dehydration from the reaction system. Acids can be organic acids with an acid dissociation constant (pKa) of -1 to 5, ideally 4 to 5. Examples of acids include trifluoroacetic acid, maleic acid, benzoic acid, isobutyric acid, and acetic acid, among which benzoic acid, isobutyric acid, and acetic acid are examples. In addition, acids with boiling points of 70~160℃ can be used, such as trifluoroacetic acid, isobutyric acid, acetic acid, nitric acid, etc. In this way, an ideal acid system possesses any of the following properties: an acid dissociation constant (pKa) of 4 to 5, or a boiling point of 70 to 160 °C. That is, weaker acids or acids with strong acidity but low boiling points can be used. Furthermore, acids can also utilize any of the properties of acid dissociation constant and boiling point.

[0170] The acetal protection of the silanol group in the hydrolysis condensate is achieved by using a vinyl ether, such as the vinyl ether represented by formula (5) below, through which a partial structure represented by formula (6) below can be introduced into the polysiloxane.

[0171] [Chemistry 90] In formula (5), R1a, R2a, and R3a each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R4a represents an alkyl group having 1 to 10 carbon atoms; R2a and R4a may bond together to form a ring. Alkyl groups can be exemplified by the foregoing examples. [Chemistry 91] In formula (6), R1', R2', and R3' each represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R4' represents an alkyl group having 1 to 10 carbon atoms; R2' and R4' can bond to each other to form a ring. In formula (6), * indicates a bond with an adjacent atom. Adjacent atoms can be, for example, the oxygen atom of a siloxane bond, the oxygen atom of a silyl group, or the carbon atom derived from R1 in formula (1). Alkyl groups can be exemplified by the foregoing examples.

[0172] Vinyl ethers represented by formula (5) may include, for example, aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether, tributyl vinyl ether, and cyclohexyl vinyl ether; or cyclic vinyl ether compounds such as 2,3-dihydrofuran, 4-methyl-2,3-dihydrofuran, and 3,4-dihydro-2H-piperan. In particular, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, ethylhexyl vinyl ether, cyclohexyl vinyl ether, 3,4-dihydro-2H-piperan, or 2,3-dihydrofuran may be used.

[0173] The protection of silyl groups with acetals can be achieved using hydrolytic condensates, vinyl ethers, and nonprotic solvents such as propylene glycol monomethyl ether acetate, ethyl acetate, dimethylformamide, tetrahydrofuran, and 1,4-dioxane, and catalysts such as pyridium p-toluenesulfonate, trifluoromethanesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, and sulfuric acid.

[0174] Furthermore, these silyl groups, through alcohol end-capping and acetal protection, can also be subjected to hydrolysis and condensation simultaneously with the hydrolytic silanes described later.

[0175] The weight-average molecular weight of the hydrolyzable silane hydrolysis condensate or its modified form can be, for example, 500 to 1,000,000. From the viewpoint of inhibiting the precipitation of the hydrolyzable condensate or its modified form from the composition, the weight-average molecular weight is ideally 500,000 or less, more ideally 250,000 or less, and even more ideally 100,000 or less; from the viewpoint of balancing storage stability and coatability, it is ideally 700 or more, and even more ideally 1,000 or more. Furthermore, the weight-average molecular weight was obtained by converting the molecular weight to polystyrene using gel permeation chromatography (GPC). GPC analysis can be performed as follows: GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), GPC column (trade name Shodex KF803L, KF802, KF801, manufactured by Showa Denko Corporation), column temperature set to 40°C, tetrahydrofuran used as the dissolution solvent, flow rate set to 1.0 mL / min, and polystyrene (Shodex manufactured by Showa Denko Corporation, a registered trademark) used as the standard sample.

[0176] Hydrolyzable silane hydrolysis condensates can be obtained by hydrolyzing and condensing the aforementioned silane compounds (hydrolyzable silanes). The aforementioned silane compounds (hydrolyzable silanes) contain: alkoxy, arylalkoxy, acetoxy, or halogen atoms directly bonded to silicon atoms, that is, they contain: alkoxysilyl, arylalkoxysilyl, acetoxysilyl, or halide silyl (hereinafter referred to as hydrolyzable groups). In the hydrolysis of these hydrolyzable groups, 0.1 to 100 mol of water is typically used for every 1 mol of hydrolyzable group, for example, 0.5 to 100 mol of water, and ideally 1 to 10 mol of water. Hydrolysis and condensation can be carried out with or without a hydrolysis catalyst, depending on the purpose of promoting the reaction. When a hydrolysis catalyst is used, 0.0001 to 10 mol of hydrolysis catalyst can usually be used for every 1 mol of hydrolyzable group, and ideally 0.001 to 1 mol of hydrolysis catalyst can be used. The reaction temperature for hydrolysis and condensation is usually above room temperature and below the reflux temperature of the organic solvent that can be used for hydrolysis at normal pressure, for example, 20~110℃, or 20~80℃. Hydrolysis can occur completely, where all hydrolyzable groups are converted into silanol groups; or it can occur partially, where unreacted hydrolyzable groups remain. Hydrolysis catalysts that can be used during hydrolysis and condensation include: metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0177] Examples of metal chelating compounds that serve as hydrolysis catalysts include: triethoxymono(acetylene)titanium, tri-n-propoxymono(acetylene)titanium, triisopropoxymono(acetylene)titanium, tri-n-butoxymono(acetylene)titanium, tri-secondary butoxymono(acetylene)titanium, tri-tertiary butoxymono(acetylene)titanium, diethoxybis(acetylene)titanium, di-n-propoxybis(acetylene)titanium, diisopropoxybis(acetylene)titanium, and di-n-butoxybis(acetylene)titanium. Di- and tertiary butoxy-bis(acetyl ketone) titanium, monoethoxy-triacetyl ketone (acetyl ketone) titanium, mono-n-propoxy-triacetyl ketone (acetyl ketone) titanium, monoisopropoxy-triacetyl ketone (acetyl ketone) titanium, mono-n-butoxy-triacetyl ketone (acetyl ketone) titanium, mono-di-butoxy-triacetyl ketone (acetyl ketone) titanium, mono-tertiary butoxy-triacetyl ketone (acetyl ketone) titanium, tetraacetyl ketone (acetyl ketone) titanium, triethoxy-monoacetyl ketone (acetyl ethyl ketone) titanium, tri-n-propoxy-monoacetyl ketone (acetyl ethyl ketone) titanium, triisopropoxy-triacetyl ketone (acetyl ... Mono(ethyl acetate) titanium, tri-n-butoxy-mono(ethyl acetate) titanium, tri-secondary butoxy-mono(ethyl acetate) titanium, tri-tertiary butoxy-mono(ethyl acetate) titanium, diethoxy-bis(ethyl acetate) titanium, di-n-propoxy-bis(ethyl acetate) titanium, diisopropoxy-bis(ethyl acetate) titanium, di-n-butoxy-bis(ethyl acetate) titanium, di-secondary butoxy-bis(ethyl acetate) titanium, di-tertiary butoxy-bis(ethyl acetate) titanium, monoethoxy Titanium chelate compounds include: · Titanium trioxide (ethyl acetate) , ...Triethoxymono(acetylene)zirconium, Tri-n-propoxymono(acetylene)zirconium, Triisopropoxymono(acetylene)zirconium, Tri-n-butoxymono(acetylene)zirconium, Tri-di-butoxymono(acetylene)zirconium, Tri-tert-butoxymono(acetylene)zirconium, Diethoxybis(acetylene)zirconium, Di-n-propoxybis(acetylene)zirconium, Diisopropoxybis(acetylene)zirconium, Di-n-butoxybis(acetylene)zirconium, Di-di-di-butoxybis(acetylene)zirconium, Di-di-di-butoxybis(acetylene)zirconium, Di-di-di-butoxybis(acetylene)zirconium, Di-di-di-butoxybis(acetylene)zirconium, Di-di-di-butoxybis(acetylene)zirconium, Di-di-di-butoxybis(acetylene)zirconium Zirconium (acetyl acetone), monoethoxy-trimethoxy-zirconium (acetyl acetone), mono-n-propoxy-trimethoxy-zirconium (acetyl acetone), monoisopropoxy-trimethoxy-zirconium (acetyl acetone), mono-n-butoxy-trimethoxy-zirconium (acetyl acetone), mono-secondary butoxy-trimethoxy-trimethoxy-zirconium (acetyl acetone), mono-tertiary butoxy-trimethoxy-zirconium (acetyl acetone), zirconium (acetyl acetone), triethoxy-mono(acetyl ethyl acetate) zirconium, tri-n-propoxy-mono(acetyl ethyl acetate) zirconium, triisopropoxy-mono(acetyl ethyl acetate) zirconium, tri-n-butoxy-mono(acetyl ethyl acetate) zirconium, Zirconium tri- and di-butoxy-mono(ethyl acetate) , Zirconium tri- and di-butoxy-mono(ethyl acetate) , Zirconium diethoxy-bis(ethyl acetate) , Zirconium di-n-propoxy-bis(ethyl acetate) , Zirconium diisopropoxy-bis(ethyl acetate) , Zirconium di-n-butoxy-bis(ethyl acetate) , Zirconium di- and di ... Zirconium chelates include propoxy-triethyl(ethyl acetate)zirconium, mono-n-butoxy-triethyl(ethyl acetate)zirconium, mono-secondary-butoxy-triethyl(ethyl acetate)zirconium, mono-tertiary-butoxy-triethyl(ethyl acetate)zirconium, tetra(ethyl acetate)zirconium, mono(ethyl acetone)triethyl(ethyl acetate)zirconium, bis(ethyl acetone)bis(ethyl acetate)zirconium, triethyl(ethyl acetone)mono(ethyl acetate)zirconium, etc.; aluminum chelates include triethyl(ethyl acetone)aluminum, triethyl(ethyl acetate)aluminum, etc., but are not limited to these.

[0178] Organic acids that can serve as hydrolysis catalysts include, but are not limited to, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, benzoic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linolenic acid, alpha-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.

[0179] Inorganic acids that can act as hydrolysis catalysts include, but are not limited to, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0180] Organic bases that can serve as hydrolysis catalysts include, but are not limited to, pyridine, pyrrole, piperazine, pyrrolidine, piperidine, methylpyridine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethyl monoethanolamine, monomethyl diethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylphenylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, etc.

[0181] Inorganic bases that can serve as hydrolysis catalysts include, but are not limited to, ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

[0182] Ideally, these catalysts are metal chelates, organic acids, or inorganic acids. One of these can be used alone, or two or more can be used in combination.

[0183] In this invention, nitric acid can be appropriately used as a hydrolysis catalyst. By using nitric acid, the storage stability of the reaction solution after hydrolysis and condensation can be improved, especially the molecular weight change of the hydrolyzed condensate or its modified form can be suppressed. It is known that the stability of the hydrolyzed condensate or its modified form in liquid depends on the pH of the solution. After in-depth research, it was found that by using an appropriate amount of nitric acid, the pH of the solution can be kept within a stable range. Furthermore, as mentioned above, nitric acid can also be used when obtaining modified hydrolysis condensates, for example, when performing alcohol-terminated hydrolysis of silanol groups. Therefore, it is ideal from the viewpoint that it can simultaneously facilitate both the hydrolysis and condensation of hydrolyzable silanes and the alcohol-terminated hydrolysis condensates.

[0184] Organic solvents can also be used as solvents during hydrolysis and condensation. Specific examples include: aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, diisopropylbenzene, and n-pentanenaphthalene; and methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, isopentanol, 2-methylbutanol, secondary pentanol, tertiary pentanol, 3-methoxybutanol, n-hexanol, and 2-methylpentanol. Monool solvents including 2-hexanol, 2-ethylbutanol, n-heptanol, 2-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, 2-octanol, n-nonanol, 2,6-dimethyl-4-heptanol, n-decanol, 2-undecanol, trimethylnonanol, 2-tetradecanool, 2-heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethyl methanol, diacetone alcohol, cresol, etc.; polyols including ethylene glycol, propylene glycol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, etc. Ketone solvents: acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone, cyclohexanone, methyl cyclohexanone, 2,4-pentanedione, acetone-based acetone, diacetone alcohol, acetophenone, ketone, etc.; diethyl ether, isopropyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-epoxypropane, dioxolane, 4-methyldioxolane, dioxane, dimethyl dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, etc. Ether solvents including diethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriethylene glycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, etc.Diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, butyl acetate 2, n-pentyl acetate, pentyl acetate 2, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriethylene glycol acetate Ester solvents such as acetate, ethylene glycol diacetate, triethylene glycol methyl ether acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methyl-2-pyrrolidone; and sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfide, cyclobutane, and 1,3-propane sulpholone, etc., but not limited to these. These solvents can be used in one or in combination of two or more.

[0185] After the hydrolysis and condensation reactions are completed, the reaction solution can be neutralized by directly or by diluting or concentrating it, and then treated with an ion exchange resin to remove the hydrolysis catalysts such as acids or bases used in the hydrolysis and condensation. Furthermore, before or after this treatment, byproducts such as alcohols and water, as well as the hydrolysis catalysts used, can be removed from the reaction solution by means such as vacuum distillation.

[0186] The resulting hydrolysis condensate or its modified form (hereinafter also referred to as polysiloxane) is obtained in the form of a polysiloxane varnish dissolved in an organic solvent and can be directly used in the preparation of compositions for forming silicon-containing photoresist underlayer films. That is, the reaction solution can be used directly (or after dilution) in the preparation of compositions for forming silicon-containing photoresist underlayer films. In this case, hydrolysis catalysts or byproducts used for hydrolysis and condensation can remain in the reaction solution as long as they do not impair the effects of the present invention. For example, nitric acid used in hydrolysis catalysts or silanol-based alcohol end-capping can remain in the polymer varnish solution at a concentration of approximately 100 ppm to 5,000 ppm. The obtained polysiloxane varnish can be solvent-substituted, and can also be diluted with a suitable solvent. Furthermore, provided its storage stability is not poor, the obtained polysiloxane varnish can also have its organic solvent removed by distillation to achieve a film-forming component concentration of 100%. The film-forming component refers to the component remaining after removing the solvent component from all components of the composition. The organic solvent used for solvent substitution or dilution in polysiloxane varnishes may be the same as or different from the organic solvent used in the hydrolysis and condensation reactions of hydrolyzable silanes. There are no particular limitations on the diluent; one or more solvents may be used.

[0187] <[C]Ingredients: Solvent> In the first embodiment, the solvent for component [C] can be any solvent that can dissolve and mix component [A] and other components contained in the composition for forming a silicon-containing photoresist underlayer film, as needed, without any particular restrictions. In the second embodiment, the solvent for component [C] can be any solvent that can dissolve and mix components [A'], [B], and other components contained in the composition for forming a silicon-containing photoresist underlayer film as needed, without any particular restrictions.

[0188] [C] Solvent, ideally an alcohol solvent, more ideally an alkylene glycol monoalkyl ether of an alcohol solvent, and even more ideally a propylene glycol monoalkyl ether. These solvents are also end-capping agents for the silanol group of the hydrolysis condensate, so there is no need for solvent substitution, and the composition for forming the silicon-containing photoresist underlayer can be prepared from a solution obtained by preparing [A]polysiloxane or [A']polysiloxane. Alkyl glycol monoalkyl ethers include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), methyl isobutyl methanol, propylene glycol monobutyl ether, etc.

[0189] Other specific examples of [C] solvents include: methyl cellulose acetate, ethyl cellulose acetate, propylene glycol monomethyl ether acetate (1-methoxy-2-propanol monoacetate), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3 - Ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol 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, methyl Isoamyl acetate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl 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, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethyl acetate 3-Methoxybutyl ester, 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, γ-butyrolactone, etc., and the solvent can be used alone or in combination of two or more.

[0190] Furthermore, the silicon-containing photoresist underlayer film formation composition of the present invention may also contain water as a solvent. When water is contained as a solvent, its content relative to the total mass of the solvent contained in the composition may, for example, be 30% by mass or less, ideally 20% by mass or less, and more ideally 15% by mass or less.

[0191] <[D] Ingredients: Hardening catalyst> While the composition for forming the silicon-containing photoresist underlayer film can be a composition without a curing catalyst, it is ideal to contain a curing catalyst ([D] component).

[0192] Hardening catalysts may use ammonium salts, phosphine salts, phosphonium salts, strontium salts, etc. Furthermore, the following salts described as examples of hardening catalysts may be any of the following: substances that can be added in the form of a salt, or substances that can form a salt in the composition (substances added as another compound and forming a salt within the system).

[0193] Ammonium salts can be listed as follows: Quaternary ammonium salts having a structure represented by formula (D-1): [Chemistry 92] (In the formula, ma represents an integer from 2 to 11, na represents an integer from 2 to 3, R 21 represents alkyl, aryl, or aralkyl, and Y - represents an anion.)

[0194] Quaternary ammonium salts having a structure represented by formula (D-2): [Chemistry 93] (In the formula, R22, R23, R24, and R25 independently represent alkyl, aryl, or aralkyl groups, and Y- represents an anion; and R22, R23, R24, and R25 are each bonded to a nitrogen atom.)

[0195] Quaternary ammonium salts having a structure represented by formula (D-3): [Chemistry 94] (In the formula, R26 and R27 independently represent alkyl, aryl, or aralkyl groups, and Y- represents an anion.)

[0196] Quaternary ammonium salts having a structure represented by formula (D-4): [Chem. 95] (In the formula, R 28 represents alkyl, aryl, or aralkyl, and Y - represents an anion.)

[0197] Quaternary ammonium salts having a structure represented by formula (D-5): [Chem. 96] (In the formula, R29 and R30 independently represent alkyl, aryl, or aralkyl groups, and Y- represents an anion.)

[0198] Tertiary ammonium salts having a structure represented by formula (D-6): [Chem. 97] (In the formula, ma represents an integer from 2 to 11, na represents an integer from 2 to 3, and Y- represents an anion.)

[0199] Furthermore, phosphonium salts can be listed as fourth-order phosphonium salts represented by formula (D-7): [Chem. 98] (In the formula, R31, R32, R33, and R34 independently represent alkyl, aryl, or aralkyl groups, and Y- represents an anion; and R31, R32, R33, and R34 are each bonded to a phosphorus atom.)

[0200] In addition, strontium salts can be listed as three grades of strontium salts represented by formula (D-8): [Chem.99] (In the formula, R35, R36, and R37 independently represent alkyl, aryl, or aralkyl groups, and Y- represents an anion; and R35, R36, and R37 are each bonded to a sulfur atom.)

[0201] The compound of formula (D-1) is a quaternary ammonium salt derived from an amine, where ma represents an integer from 2 to 11 and na represents an integer from 2 to 3. R21 of this quaternary ammonium salt, for example, represents an alkyl group with 1 to 18 carbon atoms, ideally an alkyl group with 2 to 10 carbon atoms, or an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. Examples include linear alkyl groups such as ethyl, propyl, and butyl; or benzyl, cyclohexyl, cyclohexylmethyl, and dicyclopentadienyl. Furthermore, the anion (Y-) can include halide ions such as chloride (Cl-), bromide (Br-), and iodide (I-), or acid groups such as carboxylate (-COO-), sulfonic acid (-SO3-), and alkoxide (-O-).

[0202] The compound of formula (D-2) is a quaternary ammonium salt represented by R 22R 23R 24R 25N +Y -. R 22, R 23, R 24, and R 25 of this quaternary ammonium salt are, for example, alkyl groups with 1 to 18 carbon atoms such as ethyl, propyl, butyl, cyclohexyl, and cyclohexylmethyl; aryl groups with 6 to 18 carbon atoms such as phenyl; or aralkyl groups with 7 to 18 carbon atoms such as benzyl. The anion (Y -) can be listed as: halide ions such as chloride ions (Cl -), bromide ions (Br -), and iodide ions (I -); or acid groups such as carboxylic acid groups (-COO -), sulfonic acid groups (-SO 3 -), and alkoxide groups (-O -). These quaternary ammonium salts are available from commercially available products, such as: tetramethylammonium acetate, tetrabutylammonium acetate, triethylbenzylammonium chloride, triethylbenzylammonium bromide, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, etc.

[0203] The compound of formula (D-3) is a quaternary ammonium salt derived from a 1-substituted imidazole. The number of carbon atoms in R26 and R27 is, for example, 1 to 18, and the total number of carbon atoms in R26 and R27 is ideally 7 or more. For example, R26 can be exemplified as alkyl groups such as methyl, ethyl, and propyl; aryl groups such as phenyl; and aralkyl groups such as benzyl. R27 can be exemplified as aralkyl groups such as benzyl; and alkyl groups such as octyl and octadecyl. The anion (Y-) can be listed as halide ions such as chloride (Cl-), bromide (Br-), and iodide (I-), or acid groups such as carboxylic acid groups (-COO-), sulfonic acid groups (-SO3-), and alkoxides (-O-). Although this compound can also be obtained from commercially available products, it can be manufactured, for example, 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.

[0204] The compound of formula (D-4) is a quaternary ammonium salt derived from pyridine. R 28 is, for example, an alkyl group with 1 to 18 carbon atoms, ideally an alkyl group with 4 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms or an aralkyl group with 7 to 18 carbon atoms, such as butyl, octyl, benzyl, and lauryl. The anion (Y-) can be a halide ion such as chloride (Cl-), bromide (Br-), or iodide (I-), or an acid group such as a carboxylic acid group (-COO-), a sulfonic acid group (-SO3-), or an alkoxide group (-O-). Although this compound can also be obtained commercially, it can be prepared by reacting pyridine with alkyl halides or aryl halides such as lauryl chloride, benzyl chloride, benzyl bromide, methane bromide, and octane bromide. Examples of this compound include N-laurylpyridinium chloride and N-benzylpyridinium bromide.

[0205] Compounds of formula (D-5) are quaternary ammonium salts derived from substituted pyridines, such as methylpyridine. R 29 is, for example, an alkyl group with 1 to 18 carbon atoms, ideally an alkyl group with 4 to 18 carbon atoms, or an aryl group with 6 to 18 carbon atoms, or an aralkyl group with 7 to 18 carbon atoms. Examples include methyl, octyl, lauryl, benzyl, etc. R 30 is, for example, 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. For example, in the case where the compound represented by formula (D-5) is a quaternary ammonium salt derived from methylpyridine, R 30 is methyl. Anions (Y-) can be listed as: halide ions such as chloride ions (Cl-), bromide ions (Br-), iodide ions (I-), or acid groups such as carboxylic acid groups (-COO-), sulfonic acid groups (-SO3-), alkoxides (-O-). While this compound is also available commercially, it can be produced by reacting substituted pyridines, such as methylpyridine, with alkyl halides or aryl halides, such as methane bromide, octane bromide, lauryl chloride, benzyl chloride, and benzyl bromide. Examples of this compound include N-benzylmethylpyridinium chloride, N-benzylmethylpyridinium bromide, and N-laurylmethylpyridinium chloride.

[0206] The compound of formula (D-6) is a tertiary ammonium salt derived from an amine, where ma represents an integer from 2 to 11, and na represents 2 or 3. Furthermore, the anion (Y-) can be listed as: halide ions such as chloride (Cl-), bromide (Br-), and iodide (I-), or acid groups such as carboxylic acid groups (-COO-), sulfonic acid groups (-SO3-), and alkoxides (-O-). This compound can be prepared by reacting an amine with a carboxylic acid or a weak acid such as phenol. Carboxylic acids include formic acid and acetic acid. When formic acid is used, the anion (Y-) is (HCOO-); when acetic acid is used, the anion (Y-) is (CH3COO-). Furthermore, when phenol is used, the anion (Y-) is (C6H5O-).

[0207] The compound of formula (D-7) is a quaternary phosphonium salt having the structure R 31R 32R 33R 34P +Y -. R 31, R 32, R 33, and R 34 are, for example, alkyl groups with 1 to 18 carbon atoms such as ethyl, propyl, butyl, and cyclohexylmethyl, aryl groups with 6 to 18 carbon atoms such as phenyl, or aralkyl groups with 7 to 18 carbon atoms such as benzyl. Ideally, three of the four substituents in R 31 to R 34 are unsubstituted or substituted phenyl groups, such as phenyl or tolyl, 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. In addition, anions (Y-) can include: chloride ions (Cl-), bromide ions (Br-), iodide ions (I-), and other halide ions, or acid groups such as carboxylic acid groups (-COO-), sulfonic acid groups (-SO3-), and alkoxides (-O-). These compounds are available commercially, and examples include: tetrabutylphosphonium halide, tetrapropylphosphonium halide, and other tetraalkylphosphonium halide; triethylbenzylphosphonium halide, and other trialkylbenzylphosphonium halide; triphenylmethylphosphonium halide, triphenylethylphosphonium halide, and other triphenylmonoalkylphosphonium halide; triphenylbenzylphosphonium halide, tetraphenylphosphonium halide, trimethylmethylmonoarylphosphonium halide, or trimethylmethylmonoalkylphosphonium halide (where the halogen atom is a chlorine or bromine atom). In particular, ideally: triphenylmethylphosphonium halide, triphenylethylphosphonium halide, and other triphenylmonoalkylphosphonium halide; triphenylbenzylphosphonium halide, and other triphenylmonoarylphosphonium halide; trimethylmethylphosphonium halide, and other trimethylmethylphosphonium halide; or trimethylmethylphosphonium halide, and other trimethylmethylphosphonium halide (the halogen atom is a chlorine atom or a bromine atom).

[0208] In addition, phosphine derivatives include: primary phosphine such as methylphosphine, ethylphosphine, propionylphosphine, isopropylphosphine, isobutylphosphine, and phenylphosphine; secondary phosphine such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisopentylphosphine, and diphenylphosphine; and tertiary phosphine such as trimethylphosphine, triethylphosphine, triphenylphosphine, methyldiphenylphosphine, and dimethylphenylphosphine.

[0209] The compound of formula (D-8) is a tertiary strontium salt having the structure R 35R 36R 37S +Y -. R 35, R 36, and R 37 are, for example, alkyl groups with 1 to 18 carbon atoms such as ethyl, propyl, butyl, and cyclohexylmethyl, aryl groups with 6 to 18 carbon atoms such as phenyl, or aralkyl groups with 7 to 18 carbon atoms such as benzyl. Ideally, two of the three substituents in R 35 to R 37 are unsubstituted or substituted phenyl groups, such as phenyl or tolyl, 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. In addition, anions (Y-) can be listed as: halide ions such as chloride ion (Cl-), bromide ion (Br-), iodide ion (I-), or acid groups such as carboxylic acid group (-COO-), sulfonic acid group (-SO 3-), alkoxide (-O-), maleic acid anion, nitrate anion, etc. This compound is available in commercially available forms, including, for example: tri-n-butyl strontium halide, tri-n-propyl strontium halide, and other trialkyl strontium halides; dialkyl benzyl strontium halide, diethylbenzyl strontium halide, and other dialkyl benzyl strontium halides; diphenylmethyl strontium halide, diphenylethyl strontium halide, and other dialkyl monoalkyl strontium halides; triphenyl strontium halide (all of which have chlorine or bromine atoms); tri-n-butyl strontium carboxylate, tri-propyl strontium carboxylate, and other trialkyl strontium carboxylates; diethyl benzyl strontium carboxylate, dialkyl benzyl strontium carboxylate, diphenylmethyl strontium carboxylate, diphenylethyl strontium carboxylate, and other dialkyl monoalkyl strontium carboxylates; and triphenyl strontium carboxylate. Furthermore, triphenyl strontium halide and triphenyl strontium carboxylate are particularly desirable.

[0210] In addition, nitrogen-containing silane compounds can be added as curing catalysts. Examples of nitrogen-containing silane compounds include imidazole ring-containing silane compounds such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.

[0211] From the viewpoint of more fully obtaining the effects of the present invention, the content of the [D] curing catalyst in the composition for forming the silicon-containing photoresist lower layer film of the first embodiment is ideally 0.1 to 30 parts by mass relative to 100 parts by mass of [A] polysiloxane, more ideally 0.5 to 25 parts by mass, and even more ideally 1 to 20 parts by mass. From the viewpoint of more fully obtaining the effects of the present invention, the content of the [D] curing catalyst in the composition for forming the silicon-containing photoresist lower layer film of the second embodiment is ideally 0.1 to 30 parts by mass relative to 100 parts by mass of [A'] polysiloxane, more ideally 0.5 to 25 parts by mass, and even more ideally 1 to 20 parts by mass.

[0212] <[E]Ingredients: nitric acid> The underlying structure of the silicon-containing photoresist film contains [E] nitric acid. [E] Nitric acid can be added when preparing a composition for forming a silicon-containing photoresist underlayer film, or it can be used as a hydrolysis catalyst in the manufacture of the aforementioned polysiloxane or in the process of sealing silyl alcohols, and the portion of it remaining in the polysiloxane varnish is considered as [E] nitric acid.

[0213] [E] The amount of nitric acid (residual nitric acid) is based on the total mass of the components for forming the silicon-containing photoresist lower layer film, and may 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.

[0214] <Other Additives> In the composition for forming the silicon-containing photoresist underlayer film, various additives can be added according to the intended use of the composition. Additives, for example, include the following commonly known additives used in materials (compositions) that form various films used in the manufacture of semiconductor devices, such as photoresist underlayer films, antireflective films, and pattern reversal films: crosslinking agents, crosslinking catalysts, stabilizers (organic acids, water, alcohols, etc.), organic polymers, acid generators, surfactants (nonionic surfactants, anionic surfactants, cationic surfactants, silicon surfactants, fluorine surfactants, UV-curing surfactants, etc.), pH adjusters, metal oxides, rheology modifiers, adhesion aids, etc. Furthermore, although various additives are listed below, they are not limited to these.

[0215] Stabilizers Stabilizers are added to stabilize hydrolyzable silane hydrolysis condensates, and as specific examples, organic acids, water, alcohols, or combinations thereof may be added. Organic acids, for example, include oxalic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, lactic acid, and salicylic acid. Oxalic acid and maleic acid are ideal among these. When adding organic acids, the amount added is 0.1 to 5.0% by mass relative to the mass of the hydrolyzed condensate of the hydrolyzable silane. These organic acids can also be used as pH adjusters. Water, such as pure water, ultrapure water, or ion-exchanged water, can be used; when used, the amount added is 1 to 20 parts by mass relative to 100 parts by mass of the silicon-containing photoresist lower layer film forming component. Alcohols, ideally those that readily disperse upon heating after coating, include, for example, methanol, ethanol, propanol, isopropanol, and butanol. When alcohols are added, the amount added is 1 to 20 parts by mass relative to 100 parts by mass of the composition for forming the silicon-containing photoresist underlayer film.

[0216] <<Organic Polymers>> Organic polymers, by being added to compositions used in the formation of silicon-containing photoresist underlayers, can adjust the dry etching rate (the amount of film thickness reduction per unit time), as well as the attenuation coefficient or refractive index of the film (photoresist underlayer) formed by the composition. There are no particular limitations on the organic polymers used; appropriate selections can be made from various organic polymers (condensation polymers and addition polymers) depending on the purpose of their addition. Specific examples include: polyester, polystyrene, polyimide, acrylic polymers, methacrylic polymers, polyethylene ether, phenolic varnish, naphthol varnish, polyether, polyamide, polycarbonate, and other addition polymers and condensation polymers. In this invention, organic polymers containing aromatic or heteroaromatic rings such as benzene rings, naphthalene rings, anthracene rings, triazine rings, quinoline rings, and quinoline rings that function as light-absorbing sites can also be appropriately used when such function is required. Specific examples of such organic polymers include: addition polymers containing addition polymerizable monomers such as benzyl acrylate, benzyl methacrylate, phenyl acrylate, naphthyl acrylate, anthracene methacrylate, anthracene methyl methacrylate, styrene, hydroxystyrene, benzyl vinyl ether, and N-phenylmaleimide as their structural units; and condensation polymers such as phenolic varnish and naphtholic varnish, but are not limited to these.

[0217] When using addition polymers as organic polymers, the polymer can be either a homopolymer or a copolymer. Addition polymers are used in the manufacture of addition polymers. Specific examples of such addition polymers include, but are not limited to, acrylic acid, methacrylic acid, acrylate compounds, methacrylate compounds, acrylamide compounds, methacrylamide compounds, vinyl compounds, styrene compounds, maleimide compounds, maleic anhydride, acrylonitrile, etc.

[0218] Specific examples of acrylate compounds include: methyl acrylate, ethyl acrylate, n-hexyl acrylate, isopropyl acrylate, cyclohexyl acrylate, benzyl acrylate, phenyl acrylate, anthracene methyl acrylate, 2-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-adamantane acrylate, 5-acryloyloxy-6-hydroxynorcamphene-2-carboxylic acid-6-lactone, 3-acryloyloxypropyltriethoxysilane, glycidyl acrylate, etc., but are not limited to these.

[0219] Specific examples of methacrylate compounds include: methyl methacrylate, ethyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, anthracene 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-adamantane methacrylate, 5-methacryloxy-6-hydroxynorcamphen-2-carboxylic acid-6-lactone, 3-methacryloxypropyltriethoxysilane, glycidyl methacrylate, 2-phenylethyl methacrylate, hydroxyphenyl methacrylate, bromophenyl methacrylate, etc., but are not limited to these.

[0220] Specific examples of acrylamide compounds include, but are not limited to, acrylamide, N-methylacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, N,N-dimethylacrylamide, and N-anthraylacrylamide.

[0221] Specific examples of methacrylamide compounds include, but are not limited to, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamide, N-phenylmethacrylamide, N,N-dimethylmethacrylamide, N-anthraylmethacrylamide, etc.

[0222] 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, vinylacetic acid, vinyltrimethoxysilane, 2-chloroethyl vinyl ether, 2-methoxyethyl vinyl ether, vinylnaphthalene, vinylanthracene, etc.

[0223] Specific examples of styrene compounds include, but are not limited to, styrene, hydroxystyrene, chlorostyrene, bromostyrene, methoxystyrene, cyanostyrene, acetylstyrene, etc.

[0224] Specific examples of maleimide compounds include, but are not limited to, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and N-hydroxyethylmaleimide.

[0225] When condensation polymers are 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 butanediol. Examples of dicarboxylic acid compounds include succinic acid, adipic acid, terephthalic acid, and maleic anhydride. Furthermore, examples of polyesters, polyamides, and polyimides include, but are not limited to, poly(pyromellitic terephthalamide), poly(p-phenylene terephthalate), polybutylene terephthalate, and polyethylene terephthalate. When an organic polymer contains hydroxyl groups, these hydroxyl groups can undergo cross-linking reactions with hydrolysates and the like.

[0226] The weight-average molecular weight of organic polymers is typically 1,000 to 1,000,000. When organic polymers are combined, from the viewpoint of fully obtaining the functional effect of the polymer while suppressing precipitation in the composition, the weight-average molecular weight may be, for example, 3,000 to 300,000, or 5,000 to 300,000, or 10,000 to 200,000. Such organic polymers can be used alone or in combination of two or more.

[0227] When the composition for forming the lower layer of a silicon-containing photoresist film contains an organic polymer, its content is appropriately determined considering the function of the organic polymer, and therefore cannot be uniformly specified. However, relative to [A]polysiloxane or [A']polysiloxane, it can generally be in the range of 1 to 200% by mass. From the viewpoint of inhibiting precipitation in the composition, it can be, for example, 100% by mass or less, ideally 50% by mass or less, and even more ideally 30% by mass or less. From the viewpoint of fully obtaining its effect, it can be, for example, 5% by mass or more, ideally 10% by mass or more, and even more ideally 30% by mass or more.

[0228] <<Acid Generating Agents>> Acid generating agents include thermal acid generating agents and photoacid generating agents, with photoacid generating agents being the ideal choice. Photoacid generating agents include, but are not limited to, onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds. Furthermore, photoacid generating agents such as nitrates and maleates, as well as hydrochlorides, among the onium salt compounds described later, can also function as hardening catalysts, depending on their type. In addition, examples of hot acid generating agents include tetramethylammonium nitrate, but are not limited to these.

[0229] Specific examples of onium salt compounds include: diphenylmonium hexafluorophosphate, diphenylmonium trifluoromethanesulfonate, diphenylmonium nonafluorobutyrate, diphenylmonium perfluorooctyl sulfonate, diphenylmonium camphor sulfonate, bis(4-tri-butylphenyl)monium camphor sulfonate, bis(4-tri-butylphenyl)monium trifluoromethanesulfonate, etc.; triphenylspar hexafluoroantimonate, triphenylspar nonafluorobutyrate, triphenylspar camphor sulfonate, triphenylspar trifluoromethanesulfonate, triphenylspar nitrate, triphenylspar trifluoroacetate, triphenylspar maleate, triphenylspar chloride, etc., but are not limited to these.

[0230] Specific examples of sulfonamide compounds include, but are not limited to, N-(trifluoromethanesulfonoxy)succinimide, N-(nonafluorobutanoxy)succinimide, N-(camphorsulfonoxy)succinimide, and N-(trifluoromethanesulfonoxy)naphthalenedimethylimide.

[0231] Specific examples of disulfonyldiazomethane compounds include: bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylsulfonyl)diazomethane, methanesulfonyl-p-toluenesulfonyldiazomethane, etc., but are not limited to these.

[0232] When the composition for forming the lower layer of silicon-containing photoresist contains an acid-generating agent, its content should be determined appropriately considering the type of acid-generating agent, etc., and therefore cannot be specified in general. However, relative to [A]polysiloxane or [A']polysiloxane, it is usually in the range of 0.01 to 5% by mass. From the viewpoint of inhibiting the precipitation of acid-generating agents in the composition, it is ideal to be 3% by mass or less, and more ideal to be 1% by mass or less. From the viewpoint of fully obtaining its effect, it is ideal to be 0.1% by mass or more, and more ideal to be 0.5% by mass or more. Furthermore, acid generating agents can be used alone or in combination of two or more. In addition, photo-acid generating agents and thermal acid generating agents can be used together.

[0233] <<Surfactants>> Surfactants are used to effectively suppress pinholes and streaks when a silicon-containing photoresist underlayer film is coated onto a substrate or organic underlayer film. Examples of surfactants include: nonionic surfactants, anionic surfactants, cationic surfactants, silicon-based surfactants, fluorinated surfactants, and UV-curable surfactants. More specifically, examples include: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; and sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate. Sorbitan fatty acid esters, including polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, and other polyoxyethylene sorbitan fatty acid esters and other nonionic surfactants; trade names EFTOP (registered trademark) EF301, EF303, EF352 (Mitsubishi Materials Electronics & Chemicals Co., Ltd. (formerly Tohkem)). Fluorinated surfactants such as MEGAFACE (registered trademark) F171, F173, R-08, R-30, R-30N, R-40LM (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by 3M Corporation of Japan), AsahiGuard (registered trademark) AG710 (manufactured by AGC Corporation), SURFLON (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimei Chemical Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), but not limited to these. Surfactants can be used alone or in combination of two or more.

[0234] When the composition for forming the photoresist lower layer film containing silicon contains a surfactant, its content relative to [A]polysiloxane or [A']polysiloxane is typically 0.0001 to 5% by mass, ideally 0.001 to 4% by mass, and even more ideally 0.01 to 3% by mass.

[0235] <<Rheology Modifiers>> Rheology modifiers are mainly added for the purpose of enhancing the fluidity of the composition for forming a silicon-containing photoresist lower layer film, especially for the purpose of enhancing the film thickness uniformity of the formed film in the baking step and improving the filling property of the composition into the pores. Specific examples include: phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, octyl decyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, tetrahydrofurfuryl oleate; or stearic acid derivatives such as n-butyl stearate, glycerol stearate, etc. When using these rheology modifiers, the addition amount is usually less than 30% by mass relative to all the film-forming components of the composition for forming a silicon-containing photoresist lower layer film.

[0236] <<Adhesion aids>> Adhesion aids are mainly added for the purpose of enhancing the adhesion between the substrate, the organic lower layer film or the photoresist and the film (photoresist lower layer film) formed from the composition for forming a silicon-containing photoresist lower layer film, especially for the purpose of suppressing and preventing the peeling of the photoresist during development. Specific examples include: chlorosilanes such as trimethylchlorosilane, dimethylethenylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylethenylethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, trimethylsilylimidazole; other silanes such as γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine; and ureas such as 1,1-dimethylurea, 1,3-dimethylurea, or thiourea compounds. When using these adhesion aids, the addition amount is usually less than 5% by mass relative to the film-forming components of the composition for forming a silicon-containing photoresist lower layer film, and preferably less than 2% by mass.

[0237] <<pH adjuster>> In addition, pH adjusters may include acids other than those listed in the aforementioned stabilizers, such as organic acids having one or more carboxylic acid groups. When using a pH adjuster, the amount added may be 0.01 to 20 parts by mass, 0.01 to 10 parts by mass, or 0.01 to 5 parts by mass relative to 100 parts by mass of [A]polysiloxane or [A']polysiloxane.

[0238] <<Metal Oxides>> In addition, metal oxides that can be added to the composition for forming the silicon-containing photoresist underlayer film include, but are not limited to, oxides of one or more of the following metals: tin (Sn), titanium (Ti), aluminum (Al), zirconium (Zr), zinc (Zn), niobium (Nb), tantalum (Ta), and tungsten (W), as well as oxides of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0239] The concentration of the film-forming component in the composition for forming the silicon-containing photoresist lower layer film, relative to the total mass of the composition, may 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. The content of [A]polysiloxane or [A']polysiloxane in the film-forming component is typically 20% to 100% by mass. From the viewpoint of obtaining the effects of the present invention with good reproducibility, the lower limit is ideally 50% by mass, more ideally 60% by mass, even more ideally 70% by mass, and even more ideally 80% by mass; the upper limit is ideally 99% by mass; the remainder may be additives described later. Furthermore, the composition for forming the silicon-containing photoresist lower layer film ideally has a pH of 2 to 5, and more ideally has a pH of 3 to 4.

[0240] The first embodiment of the silicon-containing photoresist underlayer film composition can be manufactured by mixing [A] polysiloxane, [C] solvent, and other components as needed. In this case, a solution containing [A] polysiloxane can be prepared in advance, and this solution can be mixed with [C] solvent and other components. There is no particular restriction on the mixing order. For example, [C] solvent can be added to a solution containing [A] polysiloxane and mixed, and then other components can be added to the mixture; alternatively, a solution containing [A] polysiloxane, [C] solvent, and other components can be mixed simultaneously. If necessary, [C] solvent can be added at the end, or the mixture can be made so that it does not contain a component that is relatively soluble in [C] solvent initially, but is added at the end. However, from the viewpoint of suppressing the aggregation and separation of constituent components and preparing a homogeneous composition with good reproducibility, it is ideal to prepare a solution in which [A] polysiloxane is well dissolved beforehand and use this solution to prepare the composition. It should also be noted that [A] polysiloxane may aggregate or precipitate during mixing, depending on the type and amount of [C] solvent being mixed, the amount and properties of other components, etc. Furthermore, it should be noted that when using a solution containing dissolved [A] polysiloxane to prepare the composition, the concentration and amount of the [A] polysiloxane solution must be determined to ensure that the final composition contains the desired amount of [A] polysiloxane. When preparing the composition, heating can be applied appropriately within a range that will not decompose or deteriorate the components.

[0241] The second embodiment of the composition for forming a silicon-containing photoresist underlayer film can be manufactured by mixing [A'] polysiloxane, [B] a hydrolyzable silane (A) having carbon-carbon triple bonds, [C] a solvent, and other components as needed. In this case, a solution containing [A'] polysiloxane can be prepared in advance, and this solution can be mixed with [B] the hydrolyzable silane (A) having carbon-carbon triple bonds, [C] the solvent, and other components. There is no particular restriction on the mixing order. For example, [B] a hydrolyzable silane with carbon-carbon triple bonds (A) and [C] solvent can be added to a solution containing [A'] polysiloxane and mixed, and then other components can be added to the mixture; alternatively, a solution containing [A'] polysiloxane, [B] a hydrolyzable silane with carbon-carbon triple bonds (A), [C] solvent, and other components can be mixed simultaneously. If necessary, solvent [C] can be added at the end, or the mixture can be made to initially contain components that are relatively soluble in solvent [C], and these components can be added at the end. However, from the viewpoint of suppressing the aggregation and separation of constituent components and reproducibly preparing a homogeneous composition with excellent uniformity, it is ideal to prepare a solution in which [A'] polysiloxane is well dissolved beforehand and use this solution to prepare the composition. Furthermore, it should be noted that [A'] polysiloxane may aggregate or precipitate during mixing, depending on the type and amount of hydrolyzable silane (A) with carbon-carbon triple bonds ([B]) and solvent [C], as well as the amount and properties of other components. Additionally, it should be noted that when using a solution containing dissolved [A'] polysiloxane to prepare the composition, the concentration and amount of the [A'] polysiloxane solution must be determined to ensure that the final composition contains the desired amount of [A'] polysiloxane. When preparing the composition, heating can be applied appropriately within a range that will not decompose or deteriorate the components.

[0242] In this invention, filtration can be performed during the manufacturing process of the silicon-containing photoresist lower layer film formation composition, or after all components have been mixed, using a submicron-sized filter or the like. Furthermore, there are no restrictions on the type of filter material used; for example, nylon filters or fluoropolymer filters can be used.

[0243] The silicon-containing photoresist underlayer film formation composition of the present invention can be appropriately used as a photoresist underlayer film formation composition used in the lithography process.

[0244] (Photoresist underlayer, semiconductor processing substrate, patterning method and semiconductor device manufacturing method) The photoresist underlayer film of the present invention is a hardened form of the silicon-containing photoresist underlayer film formation composition of the present invention.

[0245] The semiconductor processing substrate of the present invention, for example, is equipped with the silicon-containing photoresist underlayer film of the present invention.

[0246] The method for manufacturing a semiconductor device according to the present invention includes, for example,: The step of forming an organic lower layer film on a substrate; The step of forming a photoresist underlayer film using the silicon-containing photoresist underlayer film formation composition of the present invention on an organic underlayer film; and The step of forming a photoresist film on top of the photoresist underlayer film.

[0247] The pattern forming method of the present invention, for example, includes: The step of forming an organic lower layer film on a semiconductor substrate; The step of coating the silicon-containing photoresist lower layer film of the present invention onto an organic lower layer film and then firing it to form a photoresist lower layer film; The step of forming a photoresist film by coating a composition for forming a photoresist film on a photoresist lower layer film; The steps of exposing and developing the photoresist film to obtain the photoresist pattern; The steps of using a photoresist pattern as a mask and etching the underlying photoresist film; and The steps involve using a patterned photoresist underlayer as a mask and etching the organic underlayer.

[0248] Hereinafter, as one aspect of the present invention, a semiconductor processing substrate, a patterning method, and a semiconductor device manufacturing method using the silicon-containing photoresist underlayer film of the present invention, or the composition for forming the silicon-containing photoresist underlayer film of the present invention will be described.

[0249] First, the silicon-containing photoresist underlayer film forming composition of the present invention is coated onto a substrate used for manufacturing precision integrated circuit elements [e.g., semiconductor substrates such as silicon wafers covered with silicon oxide films, silicon nitride films, or silicon oxynitride films; silicon nitride substrates; quartz substrates; glass substrates (including alkali-free glass, low-alkali glass, and crystallized glass); glass substrates with ITO (indium tin oxide) films or IZO (indium zinc oxide) films; plastic (polyimide, PET, etc.) substrates; substrates covered with low-k dielectric materials; flexible substrates, etc.] using a suitable coating method such as a heating plate. Then, the composition is hardened by firing using a heating means such as a heating plate, thereby forming the photoresist underlayer film. Hereinafter, in this specification, the photoresist underlayer film refers to the silicon-containing photoresist underlayer film of the present invention, or a film formed from the silicon-containing photoresist underlayer film forming composition of the present invention. The firing conditions can be selected from a firing temperature of 40℃~400℃ or 80℃~250℃ and a firing time of 0.3 minutes~60 minutes. The ideal firing temperature is 150℃~250℃ and the firing time is 0.5 minutes~2 minutes. The thickness of the photoresist underlayer film formed here is, for example, 10nm~1,000nm, or 20nm~500nm, or 50nm~300nm, or 100nm~200nm, or 10~150nm. Furthermore, the silicon-containing photoresist underlayer film used in forming the photoresist underlayer film may be a silicon-containing photoresist underlayer film forming composition filtered through a nylon filter. Here, "silicon-containing photoresist underlayer film forming composition filtered through a nylon filter" refers to the composition filtered through a nylon filter during the manufacturing process of the silicon-containing photoresist underlayer film forming composition, or after all components have been mixed.

[0250] One embodiment of the present invention is an embodiment in which an organic lower layer film is formed on a substrate, and then a photoresist lower layer film is formed on it. However, it is also possible to form an embodiment without an organic lower layer film, depending on the circumstances. There are no particular restrictions on the organic underlying film used here; any film commonly used in lithography processes to date can be selected. By employing a pattern of depositing an organic lower layer film on a substrate, then depositing a photoresist lower layer film on top of it, and then depositing the photoresist film described later on top of it, even in cases where a thin layer of photoresist film is applied to prevent the pattern width of the photoresist film from narrowing or the pattern from collapsing, the substrate can still be processed by selecting an appropriate etching gas described later. For example, a fluorine-based gas with a sufficiently fast etching rate for the photoresist film can be used as the etching gas to process the photoresist lower layer film; alternatively, an oxygen-based gas with a sufficiently fast etching rate for the photoresist lower layer film can be used as the etching gas to process the organic lower layer film; and a fluorine-based gas with a sufficiently fast etching rate for the organic lower layer film can be used as the etching gas to process the substrate. Furthermore, examples of substrates and coating methods that can be used at this time are the same as those described above.

[0251] Next, a layer of photoresist material (photoresist film) is formed on the photoresist underlayer film. The photoresist film can be formed using conventional methods, i.e., by coating a coating-type photoresist material (a component for photoresist film formation) onto the photoresist underlayer film and then firing it. The thickness of the photoresist film is, for example, 10nm~10,000nm, or 100nm~2,000nm, or 200nm~1,000nm, or 30nm~200nm.

[0252] The photoresist material used in the photoresist film formed on the lower photoresist layer is not particularly limited as long as it is photosensitive to the light used for exposure (such as KrF excimer laser, ArF excimer laser, etc.). Both negative and positive photoresist materials can be used. Examples include: positive photoresist materials made of phenolic varnish resin and 1,2-naphthoquinone diazidesulfonate; chemically amplified photoresist materials made of binders with groups that increase the alkali dissolution rate through acid decomposition and photoacid generating agents; chemically amplified photoresist materials made of low-molecular-weight compounds that increase the alkali dissolution rate of photoresist materials through acid decomposition, alkali-soluble binders, and photoacid generating agents; and chemically amplified photoresist materials made of binders with groups that increase the alkali dissolution rate through acid decomposition, low-molecular-weight compounds that increase the alkali dissolution rate of photoresist materials through acid decomposition, and photoacid generating agents, etc. Specific examples that can be obtained in the form of commercially available products include: APEX-E manufactured by Shipley Corporation, PAR710 manufactured by Sumitomo Chemical Co., Ltd., AR2772JN manufactured by JSR Corporation, and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd., but are not limited to these. In addition, examples include: fluorinated polymer photoresist materials described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0253] Furthermore, the photoresist film formed on the photoresist underlayer can be replaced with an electron beam lithography photoresist film (also known as an electron beam photoresist film) or an EUV lithography photoresist film (also known as an EUV photoresist film). That is, the silicon-containing photoresist underlayer film forming composition of the present invention can be used to form an electron beam lithography photoresist underlayer film or to form an EUV lithography photoresist underlayer film. It is particularly ideal as a composition for forming an EUV lithography photoresist underlayer film. Electron beam photoresist materials used to form electron beam photoresist films can be either negative or positive type materials. Specific examples include: chemically amplified photoresist materials composed of an acid-generating agent and a binder having groups that alter the alkali dissolution rate through acid decomposition; chemically amplified photoresist materials composed of an alkali-soluble binder, an acid-generating agent, and a low-molecular-weight compound that alters the alkali dissolution rate of the photoresist material through acid decomposition; chemically amplified photoresist materials composed of an acid-generating agent, a binder having groups that alter the alkali dissolution rate through acid decomposition, and a low-molecular-weight compound that alters the alkali dissolution rate of the photoresist material through acid decomposition; non-chemically amplified photoresist materials composed of a binder having groups that alter the alkali dissolution rate through electron beam decomposition; and non-chemically amplified photoresist materials composed of a binder having a portion that alters the alkali dissolution rate through electron beam cleavage, etc. When using such electron beam photoresist materials, the pattern of the photoresist film can be formed in the same way as when the irradiation source is an electron beam and a photoresist material is used. In addition, the EUV photoresist material used to form the EUV photoresist film can be a methacrylate resin-based photoresist material or a metal oxide photoresist material. Metal oxide photoresist materials, for example, include coating compositions containing metal oxo-hydroxo networks with organic ligands through metal carbon bonds and / or metal carboxylic acid ester bonds, as described in Japanese Patent Application Publication No. 2019-113855.

[0254] Next, the upper photoresist film formed on the lower photoresist film is exposed through a designated reticle. Exposure can be performed using KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), EUV (wavelength 13.5nm), electron beam, etc. After exposure, post-exposure baking can be performed as needed. Post-exposure baking is performed under suitable conditions, ranging from a heating temperature of 70°C to 150°C and a heating time of 0.3 minutes to 10 minutes.

[0255] Next, development is performed using a developer (e.g., an alkaline developer). In this way, for example, when using a positive photoresist film, the exposed portion of the photoresist film is removed, thereby forming a pattern of the photoresist film. Developers (alkaline developers) can be exemplified by aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; aqueous solutions of tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, and other quaternary ammonium hydroxides; and alkaline aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants can be added to these developers. Developing conditions are suitable when selected from a temperature range of 5–50°C and a development time range of 10–600 seconds.

[0256] Furthermore, in this invention, an organic solvent can be used as the developing solution, and development is performed using the developing solution (solvent) after exposure. This allows, for example, when using a negative photoresist film, the unexposed portions of the photoresist film to be removed, thereby forming a pattern on the photoresist film. Developers (organic solvents) can include, for example: methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy, ethyl ethoxy, 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 monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-methoxybutyl acetate -Ethoxybutyl ester, 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, lactate Butyl ester, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetate, ethyl acetate, 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 may be added to these developing solutions. For developing conditions, the temperature is suitable from 5°C to 50°C, and the time is suitable from 10 seconds to 600 seconds.

[0257] The patterned photoresist film (upper layer) is used as a protective film to remove the lower photoresist film (intermediate layer). Then, the film formed by the patterned photoresist film and the patterned lower photoresist film (intermediate layer) is used as a protective film to remove the lower organic film (lower layer). Finally, the patterned lower photoresist film (intermediate layer) and the patterned lower organic film (lower layer) are used as protective films for substrate processing.

[0258] The removal (patterning) of the lower (intermediate) photoresist film, which uses the pattern of the upper photoresist film as a protective film, is performed by dry etching. The following gases can be used: tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane. Furthermore, the dry etching of the photoresist underlayer is ideally performed using a halogen-based gas. In dry etching with a halogen-based gas, the photoresist film, which is essentially composed of organic matter, is difficult to remove. In contrast, the photoresist underlayer, containing a large number of silicon atoms, is rapidly removed by the halogen-based gas. Therefore, the reduction in the photoresist film thickness associated with the dry etching of the photoresist underlayer can be suppressed. Furthermore, as a result, the photoresist film can be used as a thin film. Therefore, the dry etching of the photoresist underlayer is ideally performed using a fluorine-based gas, such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, difluoromethane (CH2F2), etc., but not limited to these.

[0259] When an organic lower layer film exists between the substrate and the photoresist lower layer film, the removal (patterning) of the organic lower layer film (lower layer) is then performed using a protective film formed by the patterned photoresist film (upper layer) (if there are any remnants of the patterned photoresist film (upper layer) as well) and the patterned photoresist lower layer film (intermediate layer). Ideally, this is done by dry etching with an oxygen-based gas (a mixture of oxygen and oxygen / carbonyl sulfide (COS) gas). This is because the photoresist lower layer film of the present invention, which contains a large number of silicon atoms, is not easily removed by dry etching with an oxygen-based gas.

[0260] Then, the (semiconductor) substrate is processed (patterned) by using a patterned photoresist lower layer (intermediate layer) and a patterned organic lower layer (lower layer) as a protective film, ideally by dry etching with fluorine-based gas. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0261] The photoresist underlayer can be removed after the organic underlayer is removed (patterning) or after the substrate is processed (patterning). The removal of the photoresist underlayer can be carried out by dry etching or wet etching (wet method). Dry etching of the photoresist underlayer is ideally performed using fluorine-based gases, as listed in the patterning section. Examples of such gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2), but these are not limited to. The solutions used in the wet etching of the photoresist lower layer film can be listed as follows: dilute hydrofluoric acid (hydrofluoric acid), buffered hydrofluoric acid (a mixed solution of HF and NH4F), aqueous solution containing hydrochloric acid and hydrogen peroxide (SC-2 solution), aqueous solution containing sulfuric acid and hydrogen peroxide (SPM solution), aqueous solution containing hydrofluoric acid and hydrogen peroxide (FPM solution), and alkaline solutions containing ammonia and hydrogen peroxide (SC-1 solution). In addition to the aforementioned ammonia-hydrogen peroxide solution (SC-1 solution) obtained by mixing ammonia, hydrogen peroxide water, and water, alkaline solutions may also include aqueous solutions containing 1 to 99% by mass of the following substances: ammonia, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, DBU (diazabicycloundecene), DBN (diazabicyclononene), hydroxylamine, 1-butyl-1-methylpyrrolidone hydroxide, 1-propyl-1-methylpyrrolidone hydroxide, 1-butyl-1-methylpiperidinium hydroxide, 1-propyl-1-methylpiperidinium hydroxide, mepiquat hydroxide, trimethylammonium hydroxide, hydrazines, ethylenediamines, or guanidines. These solutions may also be used in combination.

[0262] Furthermore, an organic antireflective film can be formed on top of the photoresist film before the photoresist film is formed. There are no particular restrictions on the composition of the antireflective film used here. For example, it can be selected from any composition commonly used in lithography processes to date. In addition, the antireflective film can be formed by conventional methods such as coating and firing performed by a spinner or coating machine.

[0263] Furthermore, a substrate coated with a silicon-containing photoresist underlayer film formation composition may have an organic or inorganic antireflective film formed by CVD or similar methods on its surface, and a photoresist underlayer film may also be formed on it. When an organic underlayer film is formed on the substrate and then the photoresist underlayer film of the present invention is formed on it, the substrate used may also have an organic or inorganic antireflective film formed by CVD or similar methods on its surface.

[0264] The photoresist underlayer film formed from silicon-containing photoresist underlayer film can absorb light depending on the wavelength of the light used in the photolithography process. Furthermore, in this case, it can function as an anti-reflective film that prevents reflected light from the substrate. Furthermore, the photoresist lower layer film can also be used as a layer to prevent the interaction between the substrate and the photoresist film (photoresist film, etc.), a layer to prevent the materials used in the photoresist film or substances generated during exposure of the photoresist film from adversely affecting the substrate, a layer to prevent substances generated from the substrate during heating and firing from diffusing into the photoresist film, and a barrier layer to reduce the poisoning effect of the photoresist film caused by the dielectric layer of the semiconductor substrate, etc.

[0265] The photoresist lower layer film can be used in dual damascene processes on substrates with through-holes, and can also be used as a hole-filling material (embedding material) that can fill holes without gaps. In addition, it can also be used as a planarization material to planarize the surface of semiconductor substrates with uneven surfaces. Furthermore, the photoresist underlayer film of the present invention, as the underlayer film of EUV photoresist film, not only functions as a hard mask, but also prevents unwanted exposure light such as UV (ultraviolet) light and DUV (deep ultraviolet) light (ArF light, KrF light) from reflecting off the substrate or interface during EUV exposure (wavelength 13.5nm), without mixing with the EUV photoresist film. Therefore, the silicon-containing photoresist underlayer film forming composition of the present invention can be appropriately used to form the underlayer antireflection film of the EUV photoresist film. That is, it can effectively prevent reflection as the underlayer of the EUV photoresist film. When used as the underlayer film of EUV photoresist, its fabrication process can be carried out in the same way as that for the underlayer film of photoresist.

[0266] The semiconductor processing substrate described above, which incorporates the photoresist lower layer film and semiconductor substrate of the present invention, can be used to properly process the semiconductor substrate. Furthermore, the semiconductor device manufacturing method described above, which includes the steps of forming an organic underlayer film, forming a photoresist underlayer film using the silicon-containing photoresist underlayer film forming composition of the present invention on the organic underlayer film, and forming a photoresist film on the photoresist underlayer film, can achieve high-precision semiconductor substrate processing with good reproducibility, and therefore can be expected to ensure stable manufacturing of semiconductor devices. [Example]

[0267] The present invention will be described in more detail below with examples of synthesis and embodiments, but the present invention is not limited to the following embodiments.

[0268] Furthermore, in the embodiments, the apparatus and conditions for analyzing the physical properties of the samples are as follows. (1) Molecular weight determination The molecular weight of the polysiloxane used in this invention is obtained by converting it to polystyrene through GPC analysis. The determination conditions for GPC can be as follows: for example, using a GPC apparatus (trade name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (trade name Shodex (registered trademark) KF803L, KF802, KF801, manufactured by Showa Denko Corporation), a column temperature of 40°C, tetrahydrofuran as the dissolution solvent, a flow rate of 1.0 mL / min, and polystyrene (manufactured by Showa Denko Corporation) as the standard sample.

[0269] (2) 1H-NMR The evaluation was performed using a JEOL-made nuclear magnetic resonance apparatus (1H-NMR, 400MHz) and the solvent d6-Acetone.

[0270] (3) Nitric acid residue The amount of nitric acid remaining in the system was determined by ion chromatography.

[0271] [1] Synthesis of polymers (hydrolyzed condensates) (Synthesis example 1) 16.66 g of tetraethoxysilane, 12.87 g of methyltriethoxysilane, 2.43 g of O-(propynyl)-N-(triethoxysilylpropyl)carbamate, and 47.89 g of propylene glycol monoethyl ether were placed in a 300 mL flask. While stirring the resulting mixture with a magnetic stirrer, 20.18 g of 0.1 M nitric acid aqueous solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 60°C and allowed to react for 20 hours. Then, the ethanol and water byproducts were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution. Propylene glycol monoethyl ether was then added to the obtained solution to adjust the concentration to 20% by mass in the solid residue conversion at 140°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size). The obtained polymer contains a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight is 3,000 converted from polystyrene by GPC. Furthermore, according to 1H-NMR, the amount of propylene glycol monoethyl ether end-capped is 3 mol% relative to Si atoms. Additionally, the residual nitric acid content in the polymer solution is 0.07%. [Chemical 100]

[0272] (Synthesis example 2) 15.87 g of tetraethoxysilane, 9.51 g of methyltriethoxysilane, 6.93 g of O-(propynyl)-N-(triethoxysilylpropyl)carbamate, and 48.47 g of propylene glycol monoethyl ether were placed in a 300 mL flask. While stirring the resulting mixture with a magnetic stirrer, 19.22 g of 0.1 M nitric acid aqueous solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 60°C and allowed to react for 20 hours. Then, the ethanol and water byproducts were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution. Propylene glycol monoethyl ether was then added to the obtained solution to adjust the concentration to 20% by mass in the solid residue conversion at 140°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size). The obtained polymer contains a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight is 3,400 converted to polystyrene by GPC. Furthermore, according to 1H-NMR, the amount of propylene glycol monoethyl ether end-capped is 3 mol% relative to Si atoms. Additionally, the residual nitric acid content in the polymer solution is 0.08%. [Chemistry 101]

[0273] (Synthesis example 3) 15.9 g of tetraethoxysilane, 10.90 g of methyltriethoxysilane, 3.16 g of diallyl isocyanurate propyltriethoxysilane, 2.32 g of O-(propynyl)-N-(triethoxysilylpropyl)carbamate, and 48.4 g of propylene glycol monoethyl ether were placed in a 300 mL flask. While stirring the resulting mixture with a magnetic stirrer, 19.3 g of 0.1 mol / L nitric acid aqueous solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Then, the ethanol and water byproducts of the reaction were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution. Propylene glycol monoethyl ether was then added to the solution to adjust the concentration to 20% by mass in the solid residue conversion at 140°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size). The obtained polymer contains a polysiloxane with a structure represented by the following formula, and its weight average molecular weight is converted to polystyrene by GPC as Mw3,200. Furthermore, according to 1H-NMR, the amount of propylene glycol monoethyl ether end-capped is 2 mol% relative to Si atoms. Additionally, the residual nitric acid content in the polymer solution is 0.08%. [Chemistry 102]

[0274] (Synthesis Example 4) 16.39 g of tetraethoxysilane, 11.22 g of methyltriethoxysilane, 2.07 g of cyanothiopropyltriethoxysilane, 2.39 g of O-(propynyl)-N-(triethoxysilylpropyl)carbamate, and 48.1 g of propylene glycol monoethyl ether were placed in a 300 mL flask. While stirring the resulting mixture with a magnetic stirrer, 19.8 g of 0.1 mol / L nitric acid aqueous solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Then, the ethanol and water byproducts of the reaction were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution. Propylene glycol monoethyl ether was then added to the solution to adjust the concentration to 20% by mass in the solid residue conversion at 140°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size). The obtained polymer contains a polysiloxane with a structure represented by the following formula, and its weight-average molecular weight is converted to polystyrene by GPC, Mw 3,000. Furthermore, according to 1H-NMR, the amount of propylene glycol monoethyl ether end-capped is 3 mol% relative to Si atoms. Additionally, the residual nitric acid content in the polymer solution is 0.09%. [Chemical Engineering 103]

[0275] (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-(propynyl)-N-(triethoxysilylpropyl)carbamate, and 48.3 g of propylene glycol monoethyl ether were placed in a 300 mL flask. While stirring the resulting mixture with a magnetic stirrer, 19.5 g of 0.1 mol / L nitric acid aqueous solution was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Then, the ethanol and water byproducts of the reaction were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution. Propylene glycol monoethyl ether was then added to the solution to adjust the concentration to 20% by mass in the solid residue conversion at 140°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size). The obtained polymer contains a polysiloxane with a structure represented by the following formula, and its weight average molecular weight is converted to polystyrene by GPC as Mw3,500. Furthermore, according to 1H-NMR, the amount of propylene glycol monoethyl ether end-capped is 4 mol% relative to Si atoms. Additionally, the residual nitric acid content in the polymer solution is 0.08%. [Chemistry 104]

[0276] (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-(propynyl)-N-(triethoxysilylpropyl)carbamate, and 48.1 g of propylene glycol monoethyl ether were placed in a 300 mL flask. While stirring the resulting mixture with a magnetic stirrer, 19.9 g of nitric acid aqueous solution (0.1 mol / L) was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Then, the ethanol and water byproducts of the reaction were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution. Further add propylene glycol monoethyl ether, using a solvent ratio of 100% propylene glycol monoethyl ether, to adjust the concentration to 20% by mass in the solid residue conversion at 140°C, and then filter using a nylon filter (0.1μm pore size). The obtained polymer contains a polysiloxane with a structure represented by the following formula, and its weight average molecular weight is Mw2,800 converted from polystyrene by GPC. Furthermore, according to 1H-NMR, the amount of propylene glycol monoethyl ether end-capped is 3 mol% relative to Si atoms. Additionally, the residual nitric acid content in the polymer solution is 0.09%. [Chemistry 105]

[0277] (Synthesis Example 7) 16.6 g of tetraethoxysilane, 12.53 g of methyltriethoxysilane, 2.42 g of O-(propynyl)-N-(triethoxysilylpropyl)aminocarbamate, and 47.9 g of propylene glycol monoethyl ether were placed in a 300 mL flask. While stirring the resulting mixture with a magnetic stirrer, 0.36 g of dimethylaminopropyltrimethoxysilane and 20.1 g of nitric acid aqueous solution (0.2 mol / L) were added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Then, the reaction byproducts, ethanol, methanol, and water, were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution. Propylene glycol monoethyl ether was then added to the solution to adjust the concentration to 20% by mass in the solid residue conversion at 140°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size). The obtained polymer contains a polysiloxane with a structure represented by the following formula, and its weight average molecular weight is converted to polystyrene by GPC as Mw3,100. Furthermore, according to 1H-NMR, the amount of propylene glycol monoethyl ether end-capped is 3 mol% relative to Si atoms. Additionally, the residual nitric acid content in the polymer solution is 0.17%. [Chemistry 106]

[0278] (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. While stirring the resulting mixture with a magnetic stirrer, 20.2 g of nitric acid aqueous solution (0.1 mol / L) was added dropwise. After the addition, the flask was transferred to an oil bath adjusted to 60°C and refluxed for 20 hours. Then, the ethanol and water byproducts of the reaction were removed by vacuum distillation, and the mixture was concentrated to obtain a hydrolyzed condensate (polymer) solution. Propylene glycol monoethyl ether was then added to the solution to adjust the concentration to 20% by mass in the solid residue conversion at 140°C, with a solvent ratio of 100% propylene glycol monoethyl ether. The solution was then filtered using a nylon filter (0.1 μm pore size). The obtained polymer contains a polysiloxane with a structure represented by the following formula, and its weight average molecular weight is converted to polystyrene by GPC as Mw3,500. Furthermore, according to 1H-NMR, the amount of propylene glycol monoethyl ether end-capped is 4 mol% relative to Si atoms. Additionally, the residual nitric acid content in the polymer solution is 0.08%. [Chemistry 107]

[0279] [2] Modulation of the composition coated by the photoresist 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 filtered through a 0.1 μm fluoropolymer filter to separately prepare compositions coated with photoresist patterns. The amounts added in Table 1 are expressed in parts by mass. Furthermore, although the hydrolysis condensate (polymer) is formulated in the form of a solution containing the condensate obtained in the synthesis example, the polymer addition ratio in Table 1 does not represent the amount of polymer solution added, but rather the amount of polymer itself added.

[0280] The meanings of the codes 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: Triphenylspar Maleate ･TPSTfAc: Triphenylsilane trifluoroacetate • IMTEOS: Triethoxysilylpropyl-4,5-dihydroimidazole ･TPSAc: Triphenylsulphuracetate BTEAC: Benzyltriethylammonium chloride salt

[0281] [Table 1] ※ Examples 1-7 and Comparative Example 1 each further contain nitric acid contained in the polymer solutions prepared in Synthetic Examples 1-7 and Comparative Synthetic Example 1.

[0282] [3] Modulation of the composition for forming the lower layer of organic photoresist film Under nitrogen atmosphere, the following were added to a 100 mL four-necked flask: carbazole (6.69 g, 0.040 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 9-fenestrone (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.). Then, 1,4-dioxane (6.69 g, manufactured by Kanto Chemical Co., Ltd.) was added and stirred. The mixture was heated to 100 °C to dissolve the compounds and initiate polymerization. After 24 hours, the mixture was allowed to cool to 60 °C. Chloroform (34g, manufactured by Kanto Chemical Co., Ltd.) was added to the cooled reaction mixture for dilution, and then the diluted mixture was added to methanol (168g, manufactured by Kanto Chemical Co., Ltd.) to precipitate it. The obtained precipitate was filtered and recovered, and the recovered solid was dried at 80°C for 24 hours using a vacuum dryer to obtain 9.37 g of the target polymer represented by formula (X) (hereinafter referred to as PCzFL). Furthermore, the 1H-NMR determination results of PCzFL are 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 is 2,800 when converted to polystyrene using GPC, and the polydispersity Mw / Mn is 1.77. [Chemistry 108]

[0283] 20g of PCzFL, 3.0g of tetramethoxymethylethynylurea (manufactured by Cytec Industries Japan (formerly Mitsui Cytec Co., Ltd.), trade name Powderlink 1174) as a crosslinking agent, 0.30g of pyridinium p-toluenesulfonate as a catalyst, and 0.06g of MEGAFACE R-30 (manufactured by DIC Co., Ltd., trade name) as a surfactant were mixed and dissolved in 88g of propylene glycol monomethyl ether acetate to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.10μm, and further filtered using a polyethylene microfilter with a pore size of 0.05μm, thereby preparing a composition for forming the lower layer of an organic photoresist film used in the lithography process of multilayer films.

[0284] [4] Solvent resistance and developer resistance test The compositions prepared in Examples 1-7 and Comparative Example 1 were respectively coated onto silicon wafers using a spinner. The wafers were heated at 215°C for 1 minute on a hot plate to form Si-containing photoresist underlayers, and the thickness of the obtained underlayers was measured. Subsequently, a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (V / V)) was coated onto each Si-containing photoresist lower layer film, and then spin-dried. The film thickness of the lower layer film after coating was measured, and the film thickness before coating with the mixed solvent was used as a baseline (100%) to calculate the percentage change in film thickness after coating with the mixed solvent. Film thickness changes of less than 1% before and after coating with the mixed solvent were evaluated as "good", and film thickness changes of more than 1% were evaluated as "uncured". Furthermore, on each Si-containing photoresist lower layer film fabricated on a silicon wafer using the same method, an alkaline developer (2.38% aqueous solution of tetramethylammonium hydroxide (TMAH)) was coated and spin-dried. The film thickness of the lower layer film after coating was measured, and the film thickness before coating with the developer was used as a baseline (100%) to calculate the percentage change in film thickness after coating with the developer. Film thickness changes of less than 1% before and after coating with the developer were evaluated as "good", and film thickness changes of more than 1% were evaluated as "uncured". The results are shown in Table 2.

[0285] [Table 2]

[0286] [5] Formation of photoresist patterns by EUV exposure: positive solvent development The above-mentioned composition for forming the organic photoresist lower layer film was coated onto a silicon wafer using a spinner and baked on a hot plate at 215°C for 60 seconds to obtain an organic lower layer film (layer A) with a thickness of 90 nm. The composition obtained in Example 1 was spin-coated onto the substrate and heated at 215°C for 1 minute to form a photoresist lower layer (layer B) (film thickness 20 nm). The EUV photoresist solution (methacrylate resin-based photoresist) was further spin-coated onto the surface and heated at 110°C for 1 minute to form an EUV photoresist film (C layer). Subsequently, exposure was performed using an ASML EUV exposure apparatus (NXE3400) under the conditions of NA=0.33, σ=0.63 / 0.84, and Quadropole. After exposure, post-exposure heating (PEB, 105℃ for 1 minute) is performed, followed by cooling to room temperature on a cooling plate. Then, development is carried out using TMAH 2.38% developer for 30 seconds, and finally, rinsing is performed to form a photoresist pattern. Photoresist patterns were formed using the same procedures with each component obtained in Examples 2-7 and Comparative Example 1. Next, for each obtained pattern, the shape of the pattern obtained by observing the pattern cross section is confirmed to evaluate whether a line pattern with a 28nm pitch and 12nm can be formed. In the observation of pattern shape, a condition where the shape from the base to the undercut is good and there are no obvious residues in the gaps is evaluated as "good"; a poor condition where the photoresist pattern collapses is evaluated as "collapsed". The results obtained are shown in Table 3.

[0287] [Table 3]

Claims

1. A composition for forming a silicon-containing photoresist underlayer film, comprising: [A] component: a polysiloxane containing a carbon-carbon triple bond, and [C] component: a solvent; wherein the polysiloxane containing a carbon-carbon triple bond contains a structural unit derived from a hydrolyzable silane (A) having a carbon-carbon triple bond; the hydrolyzable silane (A) is a compound represented by the following formula (A-1): [Chemical 1] (In formula (A-1), a represents an integer from 1 to 3; b represents an integer from 0 to 2; a+b represents an integer from 1 to 3; R1 represents an organic group having a carbon-carbon triple bond, and an oxygen atom and / or a nitrogen atom and may have an ionic bond;) R2 represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted halogenated alkyl group, a substituted aralkyl halide, a substituted aralkyl halide, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or an organogroup having an epoxy group, an organogroup having an acrylonitrile group, an organogroup having a methacrylonitrile group, an organogroup having a mercapto group, an organogroup having an amino group, an organogroup having an alkoxy group, an organogroup having a sulfonylurea group, or an organogroup having a cyano group, or a combination of two or more of these; X represents an alkoxy group, an aralkyloxy group, an acrylonitrile group, or a halogen atom; when there are multiple R1, R2, and X, the multiple R1, R2, and X may be the same or different); R1 in formula (A-1) is represented by the following formula (A-2a): [Chemical 2] (In formula (A-2a), R11 represents a divalent organic group that may have ionic bonds; R12 represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms that may have substituents, or an aryl group that may have substituents; * represents a bond); The polysiloxane containing carbon-carbon triple bonds in component [A] is a polysiloxane modified by alcohol modification or acetal protection of a portion of the silanol group.

2. A composition for forming a silicon-containing photoresist underlayer film, comprising: [A'] component: polysiloxane, [B] component: hydrolyzable silane (A) having a carbon-carbon triple bond, and [C] component: solvent; wherein the hydrolyzable silane (A) is a compound represented by the following formula (A-1): [Chemical 3] (In formula (A-1), a represents an integer from 1 to 3; b represents an integer from 0 to 2; a+b represents an integer from 1 to 3; R1 represents an organic group having a carbon-carbon triple bond, and oxygen and / or nitrogen atoms and may have ionic bonds; R2 represents a substituted alkyl group, a substituted aryl group, a substituted aralkyl group, a substituted halogenated alkyl group, a substituted aralkyl halide, a substituted aralkyl halide, a substituted alkoxyalkyl group, a substituted alkoxyaryl group, a substituted alkoxyaralkyl group, or a substituted alkenyl group, or an organogroup having an epoxy group, an organogroup having an acrylonitrile group, an organogroup having a methacrylonitrile group, an organogroup having a mercapto group, an organogroup having an amino group, an organogroup having an alkoxy group, an organogroup having a sulfonylurea group, or an organogroup having a cyano group, or a combination of two or more of these; X represents an alkoxy group, an aralkyloxy group, an acrylonitrile group, or a halogen atom; when there are multiples of R1, R2, and X, the multiple R1, R2, and X may be the same or different); R1 in formula (A-1) is represented by the following formula (A-2a): [Chemistry 4] (In formula (A-2a), R11 represents a divalent organic group that may have ionic bonds; R12 represents a hydrogen atom, an alkyl group with 1 to 6 carbon atoms that may have substituents, or an aryl group that may have substituents; * represents a bond); The polysiloxane of the component [A'] is a polysiloxane modified by alcohol modification or acetal protection of a portion of the silanol group.

3. The composition for forming a silicon-containing photoresist underlayer film as described in claim 1 or 2, wherein, The component [C] contains an alcohol solvent.

4. The composition for forming a silicon-containing photoresist underlayer film as described in claim 3, wherein, The [C] component contains propylene glycol monoalkyl ether.

5. The composition for forming a silicon-containing photoresist underlayer film as described in claim 1 or 2, wherein, The silicon-containing photoresist underlayer film formation composition system further contains [D] component: hardening catalyst.

6. The composition for forming a silicon-containing photoresist underlayer film as described in claim 1 or 2, wherein, The composition system for forming the silicon-containing photoresist underlayer film further contains an [E] component: nitric acid.

7. The composition for forming a silicon-containing photoresist underlayer film as described in claim 1 or 2, wherein, The component [C] contains water.

8. The composition for forming a silicon-containing photoresist underlayer film as described in claim 1 or 2, wherein, This silicon-containing photoresist underlayer film formation composition is used to form a photoresist underlayer film for EUV lithography.

9. A silicon-containing photoresist underlayer film, which is a cured form of the composition for forming a silicon-containing photoresist underlayer film as described in claim 1 or 2.

10. A substrate for semiconductor processing, comprising: a semiconductor substrate and a silicon-containing photoresist underlayer as described in claim 9.

11. A method for manufacturing a semiconductor device, comprising: a step of forming an organic underlayer film on a substrate; a step of forming a photoresist underlayer film on the organic underlayer film using a silicon-containing photoresist underlayer film forming composition as described in claim 1 or 2; and a step of forming a photoresist film on the photoresist underlayer film.

12. A method for manufacturing a semiconductor device as described in claim 11, wherein, The photoresist film is formed from EUV lithography photoresist.

13. A method for manufacturing a semiconductor device as described in claim 11, wherein, In the step of forming the photoresist underlayer film, a silicon-containing composition for forming the photoresist underlayer film, filtered through a nylon filter, is used.

14. A pattern forming method comprising: forming an organic underlayer film on a semiconductor substrate; coating a silicon-containing photoresist underlayer film forming composition as described in claim 1 or 2 onto the organic underlayer film, and firing it to form a photoresist underlayer film; coating a photoresist film forming composition onto the photoresist underlayer film to form a photoresist film; exposing and developing the photoresist film to obtain a photoresist pattern; using the photoresist pattern as a mask and etching the photoresist underlayer film; and using the patterned photoresist underlayer film as a mask and etching the organic underlayer film.

15. The pattern forming method as described in claim 14, wherein, The pattern formation method further includes: after etching the organic underlayer film, removing the photoresist underlayer film by a wet method using a chemical solution.

16. The pattern forming method as described in claim 14, wherein, The photoresist film is formed from EUV lithography photoresist.